Conventional Bisphenol Research Articles

Polyurethane-modified room-temperature curing epoxy super adhesive for artifact restoration and light emitting diode encapsulation

Epoxy adhesives are widely used for their strong adhesion but face challenges due to high curing temperatures and brittleness, limiting their application in precision manufacturing and fine industries. In an innovative endeavor to address these limitations, we have synthesized a novel adhesive system by incorporating epoxy-functionalized polyurethane into the conventional bisphenol A-based epoxy resin. Upon subjecting the adhesive to a 24h curing period at ambient temperature, the resulting material exhibited remarkable mechanical properties. Specifically, the shear strength, tensile strength, and fracture toughness of the cured adhesive were 20.6 MPa, 36.7 MPa, and 2.87 MPa·m1/2, respectively, while the unmodified epoxy resin had values of only 1.9 MPa, 15.5 MPa, and 1.0 MPa·m1/2. Adhesive system unique crosslinked structure has been discovered to confer blue aggregation-induced emission fluorescent properties. We have successfully applied this interesting characteristic in the restoration of cultural relics and the encapsulation of light emitting diode. The research has yielded a groundbreaking adhesive formulation that not only overcomes the traditional limitations associated with epoxy materials but also introduces novel functionalities that extend its utility into diverse and sophisticated applications.

Protocatechualdehyde-based epoxy vitrimer with low dielectric, excellent flame retardancy, and recyclability

Conventional bisphenol A epoxy resins cannot meet the requirements of the new generation of electronic/electrical industries in terms of dielectric properties and flame retardancy and are challenging to reprocess after molding, resulting in waste of resources and environmental hazards. Therefore, a tetrafunctional active ester curing agent (TIE) was successfully synthesized by a one-pot method using biomass protocatechualdehyde as raw materials, followed by curing DGEBA to prepare an epoxy vitrimer (TIE/DGEBA). MHHPA/DGEBA was chosen for comparison since the –OH was also absent after curing. The results showed that TIE/DGEBA had good combinatorial performance, thanks to the unique structure of TIE, including active ester units, siloxane chains, and aromatic Schiff base groups. TIE/DGEBA possessed a lower dielectric constant (2.9 vs. 4.0) compared to MHHPA/DGEBA, which was attributed to the synergistic effect of the less-polar siloxane chain segments, bulky benzene structure, and lower cross-linking density (1971 vs. 733 mol/cm3) of TIE/DGEBA. The aromatic Schiff base not only imparted good thermal stability (T30% = 418.0 vs. 422.2 °C) to TIE/DGEBA but ensured that it allowed for recycling and reprocessing. After solvent recycling, the resin can be remolded without significant change in tensile strength (53.0 vs. 46.3 MPa). TIE/DGEBA displayed better flame retardancy with higher residual weight (28.2 % vs. 5.5 %), lower total heat release (29.6 vs. 43.5 kJ/g), and good resistance to thermal oxidization. The structural and performance characteristics of TIE/DGEBA offer a strategy for designing multifunctional epoxy-based materials in electrical/electronic applications.

Multifunctional deoxybenzoins: Preparation of low heat release polymer networks by orthogonal crosslinking

Multifunctional epoxide monomers present opportunities to design cross-linked networks with conveniently tunable thermal and mechanical properties. This paper describes the synthesis of a novel, multifunctional deoxybenzoin monomer containing both epoxide and allyl groups, and its use in the preparation of epoxide networks. The orthogonal reactivity of these functional groups, operating via epoxide-amine and thiol-ene chemistry, facilitated the formation of networks with tunable glass transition temperatures and crosslink densities. Thermogravimetric analysis (TGA) and microscale combustion calorimetry (MCC) characterization revealed these networks to possess impressively low heat release properties (∼50% lower than conventional bisphenol A (BPA)-based networks) and very high char residues that reached ∼60%. Overall, introducing functional deoxybenzoin epoxide monomers into these types of network architectures imparts a method for combining low heat release structures with the advantageously tunable physical and mechanical properties of polymer networks.

Synthesis and Characterization of Benzoxazine Resin Based on Furfurylamine

This paper presents an investigation of the modification of natural oxazines to traditional bisphenol A benzoxazines. Eugenol was reacted with furfurylamine to synthesize a new type of benzoxazine (eugenol-furfurylamine benzoxazine), with a yield of 77.65%; and another new type of benzoxazine (bisphenol A-furfurylamine benzoxazine) was generated from bisphenol A and furfurylamine, with the highest yield of 93.78%. In order to analyze and study the target molecules, IR (infrared radiation) spectroscopy, GPC (gel-permeation chromatograph), mass spectrometry, 1H-NMR (nuclear magnetic resonance), DSC (differential scanning calorimetry), and DMA (dynamic mechanical analysis) tests were conducted. Eugenol-furfurylamine benzoxazine and conventional bisphenol A-aniline benzoxazine (BZ) composite was also analyzed and cured at different mass ratios of 2:98, 5:95, 10:90, 20:80, and 40:60. When the content of eugenol furfurylamine in the blend reached 5%, the strength of the composite was greatly enhanced, while the strength decreased with the increase in eugenol furfurylamine oxazine content. Moreover, octamaleimide phenyl POSS (OMPS, polyhedral oligomeric silsesquioxane) and bisphenol A furamine benzoxazine were mixed at different molar ratios of 1:16, 1:8, 1:4, 1:2, and 1:1. The curing temperature sharply decreased with the increase in OMPS content. When the molar ratio reached 1:1, the curing temperature decreased from 248 to 175℃. A further advantage of using eugenol and furfurylamine is that they are renewable resources, which is important in terms of utilizing resources effectively and developing environmentally friendly products.

Biomass-derived dynamic covalent epoxy thermoset with robust mechanical properties and facile malleability

Biomass-derived dynamic covalent thermoset has been considered as a promising solution to the high dependence on fossil resources and the difficulty in recyclability after curing of conventional bisphenol A epoxy resins. However, the design and preparation of a dynamic covalent biobased epoxy thermoset with both comparable thermal and mechanical performances to bisphenol A epoxy resins and reprocessibility remains a significant challenge. Herein, based on imine chemistry, a novel Schiff base-containing dynamic covalent epoxy thermoset was facilely fabricated from biobased protocatechualdehyde and synthetic siloxane diamine. Due to the more reactive epoxides in the epoxy monomer than in bisphenol A epoxy oligomer, the thermoset exhibited a high cross-linking density, resulting in high thermal stability and glass transition temperature. The rigid aromatic Schiff base moieties endowed the thermoset with excellent mechanical properties: Thanks to the plasticization of the flexible siloxane, the thermoset displayed high impact strength. Meanwhile, owing to the high segmental mobility, the fast exchange of imine bonds was guaranteed; and the thermoset was able to be recycled through reprocessing. Taking these features, this work provided great potential for designing and preparing sustainable substitutes for bisphenol A epoxy resins in the high-performance applications.

Curing behavior and properties of high biosourced epoxy resin blends based on a triepoxy monomer and a tricarboxylic acid hardener from 10-undecenoic acid

Renewable propane-1,2,3-triyl tris(9-(oxiran-2-yl) nonanoate) (EGU, 100 wt% biogenic) and a tricarboxylic acid triglyceride (CGTU) hardener (85.7 wt% biogenic) were synthesized from 10-undecenoic acid (10-UDA) and used to produce epoxy resins with 52–92 wt% biobased carbon. CGTU was prepared by thermally activated thiol-ene coupling of thioglycolic acid onto propane-1,2,3-triyl tris(undec-10-enoate), (GUD) in the absence of solvent. The characterized CGTU was used as a green hardener of blends based on EGU and a conventional bisphenol A-based epoxy pre-polymer (DGEBA) at various mass percentages (0–100 wt%) with an stoichiometric epoxy/acid equivalent ratio. Calorimetric studies revealed higher peak temperature, lower reaction heats, and longer gelation times in resins with high EGU proportion, evidencing the lower reactivity of aliphatic EGU compared with aromatic DGEBA. Cured resins were yellowish transparent rubber-like materials with glass transition temperatures (Tg) varying from −14 °C to −42 °C and tensile strength in the range of 1750 kPa–790 kPa, for 0 and 100 wt % EGU, respectively. The soluble fraction of all resins was less than 4.3%, reflecting a high level of crosslinking. Thermosets with high biobased content showed both UV-light protection and visible light transparency.

Synthesis and thermal properties of silicon-containing benzoxazine

A novel benzoxazine, containing silicon (Si) in the main chain and bonded to two benzene ring, was synthesized from aniline, bis( p-hydroxyphenyl)dimethylsilane, and paraformaldehyde. The structure was characterized by proton nuclear magnetic resonance and Fourier transform infrared (FTIR) spectra. The curing behavior of the benzoxazine was evaluated by differential scanning calorimeter and in situ FTIR. The thermal stability of the resulting polybenzoxazine was studied by thermogravimetric analysis under nitrogen and air atmospheres. The results indicated that the Si-containing polybenzoxazine possessed significantly higher initial degradation temperature and char yield than conventional bisphenol A/aniline-based polybenzoxazine.

Synthesis of fully bio-based diepoxy monomer with dicyclo diacetal for high-performance, readily degradable thermosets

Thermosets are very versatile owing to their high dimensional stability, chemical resistance and thermal and mechanical properties; however, they are difficult to be recycled or reworked because of their permanent cross-linked structure. In this paper, we synthesized a novel fully bio-based diepoxy monomer via acetalization of lignin derivative vanillin with bio-based polyol erythritol followed by reacting with bio-derived epichlorohydrin. Due to the degradability of dicyclo diacetal structure in the diepoxy monomer, the cross-linked epoxy network could be readily decomposed (completely dissolved in 1 M HCl solution at 50 °C within 40 min). While it was stable under neutral and basic conditions even during hot-humid aging test. Meanwhile, due to the rigidity of the dicyclo diacetal structure, it showed high glass transition temperature of 184 °C, and its modulus (4.7 GPa) and hardness (0.30 GPa) are even higher than those of conventional bisphenol A epoxy resin.

Antibacterial surface based on new epoxy-amine networks from ionic liquid monomers

The design of new highly effective polymer materials as active surfaces or coatings against microorganisms such as Escherichia coli (E. coli) is a major challenge for public health. In the present work, novel imidazolium ionic liquid monomers (ILMs) having a similar structure of conventional Bisphenol A diglycidyl ether epoxy prepolymer (DGEBA) have been designed without requiring to the use of toxic and carcinogenic compounds i.e. Bisphenol A and epichlorohydrin. Then, a facile and efficient polyaddition reaction-based polymerization via a one step process was used in order to prepare unprecedented antibacterial epoxy-amine networks. The ultimate role of the monomers architecture on the epoxy conversion as well as on the reactivity of the epoxy-functionalized imidazolium ionic liquid monomers with an aliphatic amine (D-230) was investigated while the average molecular weight between crosslinks (Mc) and the relaxation temperature of the resulting networks were determined. Thus, new epoxy thermosets with an excellent thermal stability, high hydrophobic behavior and good storage modulus at room temperature were produced. Finally, antimicrobial tests against E. coli were performed for the first time on these new cross-linked epoxy networks leading to a very strong inhibition of E. coli biofilm formation (−95%).

Low Birefringent Properties of Poly(phosphonate) Derivatives

The birefringent properties of bisphenol A-based poly(phosphonate) and poly(thiophosphonate) were investigated. The orientational birefringences (CR values) of the poly(phosphonate) derivatives are in the range from +1.2 × 10–9 to +1.5 × 10–9 Pa–1, which are less than half of those of the conventional bisphenol A-based polymers. In addition, their photoelastic birefringences (CD values) are in the range from +5.7 × 10–11 to +6.1 × 10–11 Pa–1, which are also lower than those of the conventional bisphenol A-based polymers. From the DFT calculations of the polarizability anisotropies of the model compounds, the low birefringent properties of the poly(phosphonate) derivatives are most probably due to the presence of the P═O and P═S groups and the phenyl substituents perpendicularly oriented to the main chain direction.

Barrier properties and structure of liquid crystalline epoxy and its nanocomposites

There is ever increasing demand for a suitable sealant material to protect electronic devices, in particular, different displays. We present a new approach to generate a liquid processible material that possesses excellent barrier properties and flexibility that can be used for electronic encapsulation. The liquid processable material is based on liquid crystalline (LC) epoxy diglycidyl ether of 4, 4′-dihydroxy-α-methylstilbene (DGE-DHAMS or EDHAMS) and its nanocomposite comprising organo-modified montmorillonite clay. The best-achieved water vapor transmission rate is 4.5 g-mil/m2-day at ambient pressure, which is more than 20 times better than that of a conventional bisphenol A epoxy. The improved barrier performance comes from the reduction in the water diffusivity. The diffusivity in the liquid crystalline epoxy is 1.25 × 10−9 cm2/s, one order of magnitude lower than that of bisphenol A epoxy. The addition of 1 vol% of organoclay further reduces the diffusivity by 2 times. The cavity size of the free volume of the liquid crystalline epoxy is much smaller than that of conventional bisphenol A epoxy as measured by positron annihilation lifetime spectroscopy, suggesting that the improved barrier property originates from this reduced free volume cavity size. The free volume cavity size of the film with an addition of 1 vol% of an organically modified montmorillonite clay is similar to that of the liquid crystalline epoxy. We hypothesize that the additional barrier performance improvement by the nanoclay is due to its effect on the liquid crystalline phase morphology (reduced LC phase domain sizes) or the tortuosity effect of the high aspect ratio particles. The material also has excellent adhesion, optical transparency, and thermal stability.

Cytotoxicity and genotoxicity of a low-shrinkage monomer and monoacylphosphine oxide photoinitiator: Comparative analyses of individual toxicity and combination effects in mixtures

ObjectiveTo compare cytotoxicity and genotoxicity of novel urethane-based monomer FIT-852 and monoacylphosphine oxide photoinitiator (Lucirin TPO) with conventional Bisphenol A-glycidyl-methacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) monomers and camphorquinone (CQ)/amine photoinitiator system, respectively. Moreover, we quantified and analyzed the combinatorial effects of individual substances in resin-based mixtures concerning the nature of the combinatorial effects. MethodsCytotoxic and genotoxic effects of BisGMA, FIT, TEGDMA, CQ, DMAEMA and TPO and their combined toxicity in four clinically relevant mixtures (FIT/TPO, FIT/CQ, BisGMA/TPO, BisGMA/CQ) were tested on human fetal lung fibroblasts MRC-5 using MTT and Comet assays. We assessed combination effects of monomers and photoinitiators on overall toxicity from the measured concentration-effect relationships. Combination index (CI) was calculated on the basis of the median-effect equation derived from the mass-action law principle. ResultsIndividual substances showed decreasing cytotoxic effects in the following order: BisGMA>TPO>FIT>CQ>DMAEMA>TEGDMA. Experimental mixtures showed decreasing cytotoxic effects in the order BisGMA/TPO>BisGMA/CQ>FIT/CQ>FIT/TPO. FIT-based mixtures exhibited antagonistic cytotoxic effects between components while BisGMA-based mixtures demonstrated synergistic effects at ED50. TPO amplified both antagonistic and synergistic cytotoxic effects in mixtures. Pure substances showed genotoxicity in the following order: TPO>BisGMA>FIT>CQ>TEGDMA. We did not detect the genotoxic potential of DMAEMA. The rank of genotoxic concentrations of the mixtures was: BisGMA/TPO>BisGMA/CQ>FIT/CQ>FIT/TPO. SignificanceLower cytotoxicity and genotoxicity of FIT than BisGMA suggests its greater biocompatibility. Conversely, photoinitiator TPO was significantly more cytotoxic and genotoxic than both CQ and DMAEMA. CI values showed that components of FIT-based mixtures exhibit an antagonistic cytotoxic effect, while compontents of BisGMA-based mixtures show synergism.

Structural Foams of Biobased Isosorbide-Containing Copolycarbonate

Isosorbide-containing copolycarbonate (Bio-PC) is a partly biobased alternative to conventional bisphenol A (BPA) based polycarbonate (PC). Conventional PC is widely used in polymer processing technologies including thermoplastic foaming such as foam injection molding. At present, no detailed data is available concerning the foam injection molding behavior and foam properties of Bio-PC. This contribution provides first results on injection-molded foams based on isosorbide-containing PC. The structural foams were produced by using an endothermic chemical blowing agent (CBA) masterbatch and the low pressure foam injection molding method. The influence of weight reduction and blowing agent concentration on general foam properties such as density, morphology, and mechanical properties was studied. The test specimens consist of a foam core in the center and compact symmetrical shell layers on the sides. The thickness of the foam core increases with increasing weight reduction irrespective of the CBA concentration. The specific (mechanical) bending properties are significantly improved and the specific tensile properties can almost be maintained while reducing the density of the injection-molded parts.

Curing kinetics and mechanical properties of bio-based epoxy composites comprising lignin-based epoxy resins

Lignin-based epoxy resins derived from de-polymerized Kraft/organosolv lignins were blended with a conventional bisphenol A (BPA)-based epoxy resin at various percentages to prepare bio-based epoxy systems as polymer matrices for manufacturing of fiber-reinforced plastics (FRPs) and coatings. The curing process of epoxy composites was studied using DSC and the activation energy was calculated by isoconversional methods. Epoxy composites comprising a low percentage (25wt%) of lignin-based epoxy resin can be cured faster than the pure BPA-based epoxy resin used in particular at the early stage of curing. However, blending a large amount (>50wt%) of lignin-based epoxy resin with the BPA-based epoxy resin retarded the curing process particularly at the late stage of curing. Tensile and flexural strengths of the prepared FRPs using bio-based epoxy composites were found to be superior or comparable to those of the FRP with the pure BPA-based epoxy resin when the lignin-based epoxy resin blending ratio is less than 50–75wt%. Furthermore, the bio-based epoxy films comprising up to 50wt% of DOL-based epoxy resin were exhibited high adhesion strength on a metal substrate.

THERMAL DEGRADATION AND XRD STUDIES OF VEGETABLE OIL BASED NOVOLAC SCAFFOLDS FOR THE FORMULATION OF RESINS

Biomaterials, chemicals and energy from renewable resources have been the object of considerable interest in recent years. Vegetable oils are one of the cheapest and most abundant biological sources available in large quantities and their use as starting materials has numerous advantages such as low toxicity, inherent biodegradability and high purity. They are considered to be one of the most important classes of renewable resources for the production of bio-based thermosets. As a substitute to the use of conventional reinforcing synthetic resins, biobased resins were synthesized from cardanol, renewable and low cost industrial grade oil obtained by vacuum distillation of Cashew Nut Shell Liquid (CNSL), an abundant agricultural byproduct of cashew industry. On the other hand to further expand the field of application, cardanol-based novolac scaffolds, used in the formulation of thermosetting resins by blending with a conventional epoxy resin, especially designed to be compatible with conventional bisphenol- A epoxy resins. In the present study resins have been synthesized by condensing diazotized p-anisidine cardanol dye with urea, resorcinol and furfural as condensing agent.. The resins have been characterised by FT-IR, 1H-NMR and XRD studies. Thermal behavior of the resins has been studied by Thermogravimetric Analysis (TGA) and Differential thermal analysis (DTA). The DTA, SEM and XRD data indicated the percentage of crystallinity associated with the thermal stability of the resins.

Investigation of novel tri-functional epoxy resin derived from cardanol as partial replacement of BPA based epoxy in zinc rich primer

Purpose The purpose of this paper is to explore the application of triglycidyl resin (TGC) prepared from cardanol as partial replacement of conventional bis-phenol A (BPA) based epoxy resin for zinc rich primers (ZRPs). Design/methodology/approach The synthesis of new platform chemicals that are based on renewable resources has been accepted as a strategy to contribute to sustainable development due to the anticipated depletion of fossil oil reserves and rising oil prices. We prepared a tri-functional epoxy resin from cardanol which can be used as partial replacement of BPA based epoxy. The ZRPs were prepared using 50:50 ratio of TGC:BPA epoxy, and the coatings were evaluated for mechanical, chemical and anticorrosive properties. Findings The 50 per cent replacement of BPA based epoxy by TGC resulted in at par mechanical, chemical and anticorrosive properties as evaluated by various methods. The successful implementation can thus contribute to sustainable development by “green chemistry” route. Research limitations/implications The prepared TGC resin in the current work was studied for application in ZRPs. This can also be explored for high performance coatings, adhesives and other engineering applications. Practical implications The TGC binder was prepared by simple two-step reaction. This can successfully be used as binder for coating application without any modifications. Originality/value A novel approach of using green and ecofriendly TGC resin as replacement of high cost BPA based epoxy was explored and can be implemented for numerous applications.

Renewable resource-based epoxy resins derived from multifunctional poly(4-hydroxybenzoates)

Herein we report on the preparation and cure of epoxy resins derived from renewable resources such as 4-hydroxybenzoic acid, glycerol, pentaerythritol, dipentaerythritol, trimethylolpropane, and sorbitol, aiming at substituting bisphenol A-based epoxy resins. Subsequent to the catalytic transesterification of polyols with ethyl-4-hydroxybenzoate, derived from bioethanol and 4-hydroxybenzoic acid, the resulting poly(4-hydroxybenzoate) phenolic resins (PHB-phenol) are glycidized with epichlorohydrin, obtained from glycerol. The epoxy functionality of these liquid ester-functional epoxy resins (PHB-epoxy) varies between 2 and 5. The PHB epoxy viscosities decrease with increasing epoxy functionality. In dicyandiamide-mediated thermal cure, property profiles similar to that of bisphenol A-based epoxy resins are obtained. The monofunctional glycidyl ether of ethyl-4-hydroxybenzoate (EHB-epoxy), formed as a by-product when PHB-phenol is not purified, can remain in the PHB-epoxy resins, serving as a reactive diluent. The incorporation of ester-functional epoxy resins does not impair the water-resistance of epoxy resins. Contrary to the flexible epoxy resins based upon epoxidized plant oils and glycidyl derivatives of glycerol, sugars, and polyfunctional fatty acids, the glycidyl ethers of the corresponding poly(4-hydroxybenzoates) and most especially their blends with conventional bisphenol A-based epoxy resins afford much higher stiffness, strength and glass temperatures, thus meeting the demands for applications as components of structural adhesives.

Synthesis of new bio-based polycarbonates derived from terpene

In this work, a bio-based polycarbonate has been synthesized successfully from terpene diphenol and diphenyl carbonate by melt polymerization without using any catalysts. The polymerization process involves no usage of toxic phosgene. The reaction parameters such as monomer feed ratio, polymerization temperature and time have been systematically examined. A little excess of diphenyl carbonate for terpene diphenol affords the highest molecular weight. The chemical structure of the product is identified by 1H NMR and FT-IR. The DSC analysis shows that the glass transition temperature of the present bio-based polycarbonate is much higher than that of a conventional bisphenol A-based polycarbonate due to the rigid molecular structure of terpene diphenol. In addition, a series of copolycarbonates with adjustable glass transition temperature are prepared from terpene diphenol and bisphenol A. The present polycarbonate and copolycarbonates with high thermal stability synthesized via an environmental benign process have large potential for bio-based engineering plastics in various industrial fields.

Electrical properties of a novel fluorinated polycarbonate

The relative permittivity, loss and dielectric strength have been measured for a polycarbonate-based material, tetraaryl bisphenol A polycarbonate, that has been fluorine substituted (DiF p-TABPA-PC). The new material has a glass transition temperature, Tg=489K, that is higher than that for either conventional bisphenol A polycarbonate (BPA-PC) for which Tg=421K or for a copolymer of tetraaryl bisphenol A (TABPA) and bisphenol A (BPA) (TABPA-BPA-PC) for which Tg=464K. In addition, the dielectric strength of DiF p-TABPA-PC is almost identical to that for purified BPA-PC and slightly larger than the value for TABPA-BPA-PC. The relative permittivity and loss measurements were carried out from 10 to 105Hz over a wide temperature range and at pressures up to 0.25GPa. Variable temperature results for the α relaxation and both temperature and pressure results for the γ relaxation regions are reported. The α relaxation exhibits standard behavior. The γ relaxation exhibits unusual characteristics such as a strong increase in peak height as temperature increases and a strong decrease in peak height with increasing pressure. The data for the γ relaxation have been analyzed using several formulations. Expressions for the peak height and peak position based on a two state (inequivalent well) model and the resulting parameters are discussed in terms of the insight they provide into the molecular mechanisms responsible for the sub-Tg relaxation. Ab initio SCF results for a related model compound are presented. Finally, the real part of the relative permittivity for the new polymer is about 10% higher than for BPA-PC.

Synthesis and characterization of a novel siloxane‐imide‐containing polybenzoxazine

AbstractA novel siloxane‐imide‐containing polybenzoxazine based on N,N′‐bis(N‐phenyl‐3,4‐dihydro‐2H‐benzo[1,3]oxazine)‐5, 5′‐bis(1,1′,3,3′‐tetramethyldisiloxane‐1,3‐diyl)‐bis(norborane‐2,3‐dicarboximide) (BZ‐A1) was successfully synthesized. The thermal properties of BZ‐A1 are superior to those of conventional polybenzoxazines lacking siloxane groups. Polymerized BZ‐A1 possesses extremely low surface free energy (γs = 15.1 mJ m−2) after curing at 230 °C for 1 h. Moreover, the surface free energy of polymerized BZ‐A1 is more stable than conventional bisphenol A‐type polybenzoxazine during thermal curing and annealing processes, indicating that polymerized BZ‐A1 is more suitable for applications requiring low surface free energy materials for high temperatures over long periods of time. Copyright © 2010 Society of Chemical Industry