Phenolic materials via ring-opening polymerization: Synthesis and characterization of bisphenol-A based benzoxazines and their polymers

Compounds with bifunctional benzoxazine groups in their molecular structures form crosslinked structures characteristic of phenolic materials through a ring-opening reaction mechanism. This family of compounds offers greater flexibility than conventional novolac or resole resins in terms of molecular design. It is also superior to conventional phenolic resin in process control since it releases no by-product during curing reactions. The materials thus obtained exhibit excellent mechanical integrity with glass transition temperatures over 200°C. The synthesis, composition, and structural analysis of precursors based on bisphenol-A are discussed herein. © 1994 John Wiley & Sons, Inc.     

Synthesis of novel tri‐benzoxazine and effect of phenolic nucleophiles on its ring‐opening polymerization

A trifunctional benzoxazine, 1,3,5‐tris(3‐phenyl‐3,4‐dihydro‐2H‐benzo[1,3]oxazin‐6‐yl)benzene (T‐Bz) was synthesized and in an effort to reduce its curing temperature (curing maxima at 238 °C), it was mixed with various phenolic nucleophiles such as phenol (PH), p‐methoxy phenol (MPH), 2‐methyl resorcinol (MR), hydroquinone (HQ), pyrogallol (PG), 2‐naphthol (NPH), 2,7‐dihydroxy naphthalene (DHN), and 1,1'‐bi‐2‐naphthol (BINOL). The influence of these phenolic nucleophiles on ring‐opening polymerization temperature of T‐Bz was examined by DSC and FTIR analysis. T‐Bz undergoes a complete ring‐opening addition reaction in the presence of bi‐ and trifunctional phenolic nucleophiles (MR/HQ/PG/DHN) at 140 °C (heated for 3 h) and forms a networked polybenzoxazine (NPBz). The NPBzs showed a high thermal stability with T_d20 of 350–465 °C and char yield of 67–78% at 500 °C; however, a diminutive weight loss (6.9–9.8%) was observed at 150–250 °C (T_d5: 215–235 °C) due to degradation of phenolic end groups. This article also gives an insight on how the traces of phenolic impurities can alter the thermal properties of pure benzoxazine monomer as well as its corresponding polymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2811–2819     

对甲基苯磺酸甲酯催化苯并噁嗪固化反应

以对甲基苯磺酸甲酯作为阳离子催化剂,研究了双酚A苯胺型苯并噁嗪的热聚合反应.通过凝胶时间、FT-IR、DSC和TGA对阳离子引发聚合作了研究.苯并噁嗪中加入质量分数为5 %的对甲基苯磺酸甲酯,其DSC图有多重放热峰存在,说明有多种固化反应同时或有序地发生.固化峰顶温度从222.91℃下降到137.03℃.     

Bimetallic Al(III) Compounds as Catalysts for the Synthesis of Biodegradable Polyesters and Polycarbonates

Ethylenediamine bridged benzoxazine proligands were synthesized by a modified Mannich condensation reaction. The reaction of the proligands with two equivalents of AlMe₃ resulted in the formation of dinuclear Al(III) compounds in high yield and purity. When the ligand binds to the Al(III) center, it forms two separate six-membered N,O-chelates with the two Al atoms that resembles the N-alkylated salan moiety. Each aluminum atom adopts a distorted tetrahedral geometry as revealed from the single-crystal X-ray diffraction studies of 1 . The catalytic activity of these aluminum compounds was investigated towards the ROP of rac-LA and ROCOP of epoxides (PO, CHO, tBuGE) and phthalic anhydride and ROCOP of CHO with CO₂. These aluminum compounds showed notable catalytic activity towards the ROP and ROCOP reactions in the absence of cocatalyst.     

Resist performances and structure of phenolic resins using multi-substituted phenols

Positive photoresist systems comprising phenolic resin and quinonediazide are studied in detail. The structure of several novolak resins, which were synthesized from multi-substituted phenols, are analyzed with ¹³C-NMR. It is proved that these phenols are useful for the structural control of novolak resins. Phenols with two methyl substituents at meta-positions especially show a remarkable structural effect to control methylene bond types of novolak resins. The alkaline dissolution rate is also investigated on novolak resins synthesized from multi-substituted phenols to understand both the dissolution inhibition effect and the dissolution promotion effect. Key-structure of novolak resins for realizing high resolution is elucidated. In addition, the molecular design concept of novolak resin is clarified from several standpoints. Unsubstituted aromatic carbon of resin, hydrophobic effect of methyl substitutent and suitable structure of low M_w parts of novolak resin are also explored. Furthermore, it is proposed that a resist using a resin, which is based on the molecular design concept, has enough potential to produce critical dimensions of 0.2 μm or less taking advantage of phase-shifting technology.     

Development of novel flame‐retardant thermosets based on benzoxazine–phenolic resins and a glycidyl phosphinate

Modified novolac resins with benzoxazine rings were prepared and copolymerized with a glycidyl phosphinate. Their curing behavior and the thermal properties of the curing resins were studied. Copolymerization was studied with model compounds considering the functionality of the benzoxazine‐based phenolic resins and the easy isomerization of the glycidyl phosphinate. Phenolic novolac resin acts as an initiator but p‐toluensulfonic acid had to be used to decrease the curing temperature and to prevent glycidyl phosphinate from isomerizing. The materials obtained exhibited high glass‐transition temperatures and retardation on thermal degradation rates. V‐0 materials were obtained when the materials were tested for ignition resistance with the UL‐94 test. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 279–289, 2004     

Synthesis and characterization of carborane bisphenol resol phenolic resins with ultrahigh char yield

Two carborane-containing resol phenolic resins(P1 and P2) with high boron content were synthesized via the reaction of carborane bisphenols(1 and 2) with formaldehyde in the presence of alkaline. HRMS results indicate that P1 is mainly composed of hydroxymethylated o-carborane bisphenols, the Mw of which was restrained around 500 due to the strong steric hindrance of o-carborane bisphenol. In contrast, the molecular weight of P2 was well regulated under various reaction conditions. The obtained resins were characterized with spectroscopic techniques including FTIR, 1H-NMR, 13C-NMR, and 11B-NMR, which gave satisfactory results. TGA studies show that P2 shows char yield of 88.9% and 92.9% at 900 ?C under nitrogen and air respectively. The imported carborane cage endows phenolic resin with ultrahigh char yield. Particularly, the char yield of the obtained carborane-containing phenolic resin under air is higher than that under nitrogen. FTIR and XRD confirm that the carborane cage could react with oxygen to form B2O3 at elevated temperatures, which postpones the thermal decomposition of phenolic resin and accounts for the high char yield.     

Thermal latency of novel chelating borate catalysts as latent catalysts for epoxy–phenolic resins

Novel quaternary ammonium bis(2‐oxybenzoyloxy)borate salts ( 1a – 1c ) or quaternary ammonium bis(1,2‐benzenedioxy)borate salts ( 2a and 2b ) with tetra‐n‐butylammonium (TBA⁺), tetra‐n‐octylammonium (TOA⁺), or bis(triphenylphosphoranylidene)ammonium (PNP⁺) cations were synthesized as latent catalysts of epoxy/phenol–novolac resins by the complexation between boric acid and salicylic acid or catechol, followed by neutralization with quaternary ammonium hydroxide. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with 1a – 1c in diglyme at 150 °C for 6 h proceeded up to 85–96% conversions and gave polymers with number‐average molecular weights of 4180–10,500, whereas the polyaddition at 80 °C for 6 h gave less than 8% conversions. However, the polyaddition with 2a containing TBA⁺ cation proceeded to only a 32% conversion at 150 °C for 6 h in diglyme and to a 64% conversion even at 180 °C for 6 h in triglyme and only gave low molecular weight oligomers, and no reaction proceeded in the polyaddition at 80 °C. However, polyaddition with 2b containing PNP⁺ cation proceeded up to a 96% conversion at 150 °C for 6 h in diglyme and gave a higher molecular weight polymer with a number‐average molecular weight of 8050, whereas the polyaddition at 80 °C for 6 h gave only a 5% conversion. The catalytic activity of ammonium borates 1a – 1c and 2a and 2b depended on the borate anion structure: 1a and 1c with bis(2‐oxybenzoyloxy)borate anion revealed higher activity than 2a and 2b with bis(1,2‐benzenedioxy)borate anion, respectively. In comparison with tetra‐n‐butylammonium bromide (TBAB) as a conventional ammonium salt or tetra‐n‐butylammonium tetrakis(benzoyloxy)borate (TBA‐TBB), 1a – 1c and 2b revealed better thermal latency. The catalytic activity of ammonium borates also depended on the bulkiness of the ammonium cation, and the order of activity was 1c (PNP⁺) > 1b (TOA⁺) ≧ 1a (TBA⁺) and 2b (PNP⁺) > 2a (TBA⁺). The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts 1a – 1c and 2a and 2b in bulk at 40 °C was much better than that with TBAB and TBA‐TBB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2702–2716, 2002     

Novel quaternary ammonium borates as latent catalysts for epoxy–phenolic resins

Novel tetrabutylammonium tetrakis(substituted benzoyloxy)borate salts ( 1a – 1d ) were synthesized by the reaction of tetrabutylammonium tetraphenylborate and corresponding substituted benzoic acids. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with the ammonium borates in diglyme at 150 °C for 6 h proceeded up to 84–94% conversions and gave polymers with number‐average molecular weights of 3750–5750, whereas the polyaddition at 80 °C for 6 h gave less than 9% conversions. The catalytic activity of ammonium borates 1a – 1d depended on the substituent of the phenyl group of the borates, and the order of activity was 1b (p‐OMe) > 1a (? H) > 1c (p‐NO₂) > 1d [3,5‐(NO₂)₂]. The ammonium borate catalyst with the substituent that yielded lower acidity of the corresponding substituted benzoic acid tended to reveal higher activity. In comparison with tetrabutylammonium bromide (TBAB) as a conventional ammonium salt, 1a – 1d revealed better thermal latency. The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts in bulk at 40 °C was better than that with TBAB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2689–2701, 2002     

Microdetermination of phenols, carboxylic acids and phenolic acids by potentiometric and visual titrations in dimethylformamide

Potentiometric titration of phenols with sodium methoxide in dimethylformamide, with a glass-calomel electrode system, is limited to monohydric phenols substituted with electron-attracting groups and dihydric phenols in which the two -OH groups are substituted in isolated benzene rings. Brilliant Orange has proved to be a suitable indicator in the titration of all types of mono- and dihydric phenols. Titan Yellow is recommended as indicator for the titration of carboxylic acids. Simultaneous visual titration of -OH and -COOH groups is also described. A detailed study with 62 structurally different compounds covering the various groups is reported, and a suitable procedure for the microdetermination of each class of these compounds with an error of +/- 0.2% absolute or less is presented.     

Reaction of trichlorides of phosphono carboxylic acids with acetylacetone,acetoacetic ester,and phenols

Reactions of trichloride of phosphono carboxylic acid with β-dicarbonyl compounds proceed at the active methylene group with the formation of the С-acylation product with a small admixture of the product of O-acylation. The C-acylation products undergo intramolecular condensation to form 1,2-oxophosphorines and compounds of the phosphate structure. The condensation of trichlorides with phenols proceeds selectively at the carbonyl carbon atom leading to C-phenyl esters. With more acidic phenols the splitting of the Р–С bond in the substitution product occurs.     

环单体的合成,聚合及与环氧树脂的固化反应

合成了新螺环原碳酸酯单体：３，９－二（对甲氧基苄基）－１，５，７，１１－四氧杂螺环［５，５］十一烷。以ＢＦ３·ＯＥｔ２为催化剂，实现了其阳离子聚合。聚合产物的＾１Ｈ ＮＭＲ、＾１３Ｃ ＮＭＲ、ＩＲ及元素分析均表明发生了双开环聚合反应。探讨了其聚合历程。用ＤＳＣ和ＩＲ跟踪环氧树脂及其与螺环单体混合后的固化反应过程，研究了固化剂、反应条件对固化反应的影响。     

Phenolic materials via ring-opening polymerization of benzoxazines: Effect of molecular structure on mechanical and dynamic mechanical properties

A series of benzoxazine compounds have been prepared from different bifunctional phenols and primary amines and the molecular compositions of the precursors are characterized by nuclear magnetic resonance, Fourier transform infrared, and size exclusion chromatography. It has been demonstrated that by design of the molecular structures of the benzoxazine precursors, therefore by tailoring of the network molecular architectures, new phenolic materials with superior mechanical and thermal properties, and ease-of-processing characteristics can be obtained. The characteristics of dynamic mechanical spectra of the phenolic materials are studied and related to their structural features. © 1994 John Wiley & Sons, Inc.     

Synthesis of the sulfonated condensed polynuclear aromatic (S-COPNA) resins as strong protonic acids

The mixture (PXG/PR=1.00) of pyrene (PR) and p-xylylene glycol (1,4-benzenedimethanol) (PXG) in the presence of 5 wt % of p-toluenesulfonic acid (TsOH) was heated at 140 °C for 45 min under nitrogen to give the highly viscous condensed polynuclear aromatic (COPNA) resin. It was converted into an infusible and insoluble solid by further heating at 300 °C for 1 h. The obtained material was treated with fuming sulfuric acid at 80 °C for 15 h under nitrogen to give the sulfonated COPNA resin. The similar acidic resin was prepared by the reaction of phenanthrene or naphthalene with PXG in the presence of TsOH followed by sulfonation. The performance of the sulfonated polymers as the strong protonic acids was evaluated.     

Synergism and multiple mechanical relaxations observed in ternary systems based on benzoxazine,epoxy, and phenolic resins

The synergism in the glass‐transition temperature (T_g) of ternary systems based on benzoxazine (B), epoxy (E), and phenolic (P) resins is reported. The systems show the maximum T_g up to about 180 °C in BEP541 (B/E/P = 5/4/1). Adding a small fraction of phenolic resin enhances the crosslink density and, therefore, the T_g in the copolymers of benzoxazine and epoxy resins. To obtain the ultimate T_g in the ternary systems, 6–10 wt % phenolic resin is needed. The molecular rigidity from benzoxazine and the improved crosslink density from epoxy contribute to the synergistic behavior. The mechanical relaxation spectra of the fully cured ternary systems in a temperature range of −140 to 350 °C show four types of relaxation transitions: γ transition at −80 to −60 °C, β transition at 60–80 °C, α₁ transition at 135–190 °C, and α₂ transition at 290–300 °C. The partially cured specimens show an additional loss peak that is frequency‐independent as a result of the further curing process of the materials. The ternary systems have a potential use as electronic packaging molding compounds as well as other highly filled systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1687–1698, 2000     

用三乙胺盐酸盐对酚醛环氧树脂开环合成水溶性感光高分子的研究

用三乙胺盐酸盐与酚醛环氧树脂开环反应合成了一种水溶性聚合物，研究了相转移催化剂、反应时间、反应温度、开环顺序等条件对反应程度的影响。研究了开环反应中丙烯酸及三乙胺盐酸盐与酚醛环氧树脂的比例对产物的水溶性及感兴性能的影响。     

Molecularly imprinted polymer based on magnetic ionic liquid for solid-phase extraction of phenolic acids

In this study, 1-allyl-3-octylimidazolium tetrachloroferrate ionic liquid was first synthesized. Molecularly imprinted polymer was prepared by suspension polymerization using 1-allyl-3-octylimidazolium tetrachloroferrate as functional monomer and chlorogenic acid as template molecule. The polymer was characterized by Fourier transformed infrared spectroscopy and scanning electron microscopy. Thermal stability of the polymer was investigated. The solid-phase extraction method based on magnetic molecularly imprinted polymer was developed for gallic acid, protocatechuic acid, caffeic acid, chlorogenic acid, p-coumaric acid, and ferulic acid. The sample pH, the type and volume of stripping solution, sorbent amount, and extraction time were optimized for phenolic acids. The analysis of phenolic acids after extraction was carried out using high-performance liquid chromatography with UV detection. Limit of detection, limit of quantification, linear range, correlation coefficient, and reproducibilities of within-day and between-day for phenolic acids were determined. The residues of phenolic acids in apple samples were successfully detected by the developed method. Recovery of standard spiked apple samples was ≥81 for all the phenolic acids.     

Synthesis and characterization of novel phenolic resins containing aryl‐boron backbone and their utilization in polymeric composites with improved thermal and mechanical properties

In the present study, a novel aryl‐boron‐containing phenolic resin named as PBPR has been synthesized from phenol and formaldehyde in the presence of phenylboronic acid. The chemical structure of the PBPR was confirmed by Fourier transform infrared, nuclear magnetic resonance and X‐ray photoelectron spectroscopy. The molecular weight, viscosity and curing behavior were examined to demonstrate that PBPRs have better processability than common boric acid‐modified phenolic resin. The thermal stability and fracture toughness of the cured PBPRs were greatly enhanced, where the char yield at 1000°C (nitrogen atmosphere) and the glass transition temperature reached 70.0% and 218°C, respectively. The excellent mechanical and ablative properties of the PBPR composites may have benefited from the good interfacial adhesion between the resin matrix and the reinforced fiber. The flexural strength and the linear ablative rate are 436.8 ± 5.2 MPa and 0.010 mm/sec, respectively. This study opens a new window for the preparation of high‐performance ablative composites by designing a resin matrix containing an aryl‐boron backbone. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural and transport characteristics of polyethylene oxide/phenolic resin blend solid polymer electrolytes

Details on the structure and transport characteristics of the solid polymer electrolyte polyethylene oxide (PEO)/lithium salt (LiClO₄) modified by novolac phenolic resin are presented here. From IR spectra it could be concluded that complex formation occurred through multiple interactions between the ether oxygen of PEO–lithium, phenolic lithium, and the phenolic ether oxygen of PEO. The free hydroxyl band in phenolic reflected that phenolic closely interacted with both the PEO polymer and ionic salt. With increasing salt content in PEO, the vibration band corresponding to the ClO anion (～623 cm^?1) displayed growth of a shoulder at ～635 cm^?1, suggesting the formation of Li⁺…ClO₄^? ion pairing. However, in the presence of phenolic, ion‐pairing formation was effectively suppressed, which suggested that the phenolic moiety facilitated a greater degree of LiClO₄ salt dissociation. Activation energy analysis revealed two conducting pathways: one through the amorphous PEO and the other through the PEO/phenolic amorphous matrix. The high ion conductivity originated from effective salt dissociation and the establishment of a new conduction network formed by PEO and phenolic. Furthermore, the structural modification also extended the thermal stability and mechanical strength of the solid polymer electrolyte composite. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3866–3875, 2004