- Bio-Based Alternative to the Diglycidyl Ether of Bisphenol A with Controlled Materials Properties
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A series of biobased epoxy monomers were prepared from diphenolic acid (DPA) by transforming the free acid into n-alkyl esters and the phenolic hydroxyl groups into diglycidyl ethers. NMR experiments confirmed that the diglycidyl ethers of diphenolates (DGEDP) with methyl and ethyl esters have 6 and 3 mol % of glycidyl ester. Increasing the chain length of DGEDP n-alkyl esters from methyl to n-pentyl resulted in large decreases in epoxy resin viscosity (700-to-11 Pa·s). Storage modulus of DPA epoxy resins, cured with isophorone diamine, also varied with n-alkyl ester chain length (e.g., 3300 and 2100 MPa for the methyl and n-pentyl esters). The alpha transition temperature of the cured materials showed a linear decrease from 158 to 86°C as the ester length increases. The Young's modulus and tensile strengths were about 1150 and 40 MPa, respectively, for all the cured resins tested (including DGEBA) and varied little as a function of ester length. Degree of cure for the different epoxy resins, determined by FTIR and DSC, closely approached the theoretical maximum. The result of this work demonstrates that diglycidyl ethers of n-alkyl diphenolates represent a new family of biobased liquid epoxy resins that, when cured, have similar properties to those from DGEBA. (Graph Presented).
- Maiorana, Anthony,Spinella, Stephen,Gross, Richard A.
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Read Online
- Green Esterification of Carboxylic Acids Promoted by tert-Butyl Nitrite
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In this work, the green esterification of carboxylic acids promoted by tert-butyl nitrite has been well developed. This transformation is compatible with a broad range of substrates and exhibits excellent functional group tolerance. Various drugs and substituted amino acids are applicable to this reaction under near neutral conditions, with good to excellent yields.
- Cheng, Xionglve,Jiang, Gangzhong,Li, Xingxing,Tao, Suyan,Wan, Xiaobing,Zhao, Yanwei,Zheng, Yonggao
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supporting information
p. 2713 - 2718
(2021/06/25)
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- Method for synthesizing hapten of TBBPA-DHEE (tetrabromobisphenol A 2-hydroxyethyl ether) derived from tetrabromobisphenol A and application of such hapten
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The invention provides a method for synthesizing a hapten of TBBPA-DHEE (tetrabromobisphenol A 2-hydroxyethyl ether) derived from tetrabromobisphenol A and application of such hapten. The method includes the synthesis steps of 1, enabling a raw material 4
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Paragraph 0032; 0033
(2017/08/29)
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- Synthesis of an intrinsically flame retardant bio-based benzoxazine resin
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An intrinsically flame retardant bio-based benzoxazine (diphenolic acid pentaerythritol caged phosphate benzoxazine, DPA-PEPA-Boz) monomer was synthesized from bio-based diphenolic acid (DPA) using a four-step process. The monomer of DPA-PEPA-Boz was characterized by FT-IR, 1H NMR and 13C NMR. The curing behavior of DPA-PEPA-boz was studied and compared with those of DPA based benzoxazine (DPA-Boz) and DPA ester derivative (MDP) based benzoxazine (MDP-Boz) without PEPA by means of non-isothermal differential scanning calorimetry. The results indicated that DPA-PEPA-Boz system showed a two-stage curing, assigned to the exothermic opening reactions of oxazine rings and P-O-C ring in PEPA respectively, while the DPA-Boz and MDP-Boz showed a one-stage curing. In addition, the effect of the introduction of PEPA on thermal and inflammable properties of the resin was evaluated. The residual char of the cured DPA-PEPA-Boz (P-DPA-PEPA-Boz) after 400 °C was much higher than those of cured DPA-Boz (P-DPA-Boz) and cured MDP-Boz (P-MDP-Boz) under nitrogen and air atmospheres. Meanwhile, total heat release (THR), peak heat release rate (PHRR) and heat release capacity (HRC) of P-DPA-PEPA-Boz were about half of those of P-DPA-Boz and P-MDP-Boz. P-DPA-PEPA-Boz had a limiting oxygen index (LOI) of 33.5% and achieved V0 rating in UL94 test. P-DPA-PEPA-Boz behaved as a very good intrinsic thermal and flame retardant bio-based benoxazine resin.
- Yan, Hongqiang,Sun, Chuang,Fang, Zhengping,Liu, Xiaoqing,Zhu, Jin,Wang, Hao
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p. 418 - 427
(2016/06/09)
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- 2, 2'-BIS (4-HYDROXYPHENYL) ALKYL AZIDES AND PROCESS FOR THE PREPARATION THEREOF
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The application discloses monomers based on bis phenols with pendent reactive azido groups. The application further provides a process for preparation of bisphenol monomers with pendent reactive azido groups which are used further for preparing polymers w
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Page/Page column 10
(2014/05/24)
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- Convenient and solventless preparation of pure carbon nanotube/ polybenzoxazine nanocomposites with low percolation threshold and improved thermal and fire properties
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This work contemplates the use of pristine multiwalled carbon nanotubes (MWNTs) as nanofillers in the preparation of bisphenol A-based polybenzoxazine and diphenolic acid derived polybenzoxazine. These materials were prepared by using a solventless method varying the MWNT amount from 0.1 to 1.0 wt%. MWNTs were found to disperse well within both benzoxazine monomers and the dispersion also appears to be good in the cured system. Rheological and electrical percolation thresholds were obtained for MWNT concentrations lower than 0.1 wt% indicating the existence of good affinity between MWNTs and polybenzoxazine matrices. The characterization of the resulting nanocomposites revealed that MWNTs affected polybenzoxazines differently. The limiting oxygen index of the nanocomposites increased as a function of the nanotube content, from 35.2 to 38.7 for a bisphenol A-benzoxazine based system (BPA-PBz) and from 31.2 to 37.4 for a methyl-4,4′-bis-[6-(3-phenyl-3,4-dihydro-2H-1,3-benzoxazine)] pentanoate based system (MDP-PBz), respectively. Moreover, MWNTs positively influenced the thermo-mechanical, thermal and mechanical properties of the nanocomposites. The resulting attractive properties have been attributed to good interaction between the polybenzoxazines and the finely dispersed nanofillers.
- Zuniga, Camilo,Bonnaud, Leila,Lligadas, Gerard,Ronda, Juan Carlos,Galia, Marina,Cadiz, Virginia,Dubois, Philippe
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p. 6814 - 6822
(2014/05/06)
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- Bronsted acidic ionic liquids catalyze the high-yield production of diphenolic acid/esters from renewable levulinic acid
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The high-yielding synthesis of diphenolic acid (DPA) using Bronsted acidic ionic liquids (BAILs) has been demonstrated in this study. Importantly, p,p′-DPA was obtained as the preferential product over o,p′-DPA with an isomer ratio over 100. Moreover, diphenolic esters were also prepared in high yield through a one-pot method.
- Liu, Hai-Feng,Zeng, Fan-Xin,Deng, Li,Liao, Bing,Pang, Hao,Guo, Qing-Xiang
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- A facile strategy for synthesis of α,α'-heterobifunctionalized poly (ε-caprolactones) and poly (methyl methacrylate)s containing "clickable" aldehyde and allyloxy functional groups using initiator approach
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Two new initiators, namely, 4-(4-(2-(4-(allyloxy) phenyl)-5-hydroxypentane 2-yl) phenoxy)benzaldehyde and 4-(4-(allyloxy) phenyl)-4-(4-(4-formylphenoxy) phenyl) pentyl 2-bromo-2-methyl propanoate containing "clickable" hetero-functionalities namely aldehy
- Sane, Prakash S.,Tawade, Bhausaheb V.,Parmar, Indravadan,Kumari, Savita,Nagane, Samadhan,Wadgaonkar, Prakash P.
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p. 2091 - 2103
(2013/05/21)
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- Aromatic aldehyde functionalized polycaprolactone and polystyrene macromonomers: Synthesis, characterization and aldehyde-aminooxy click reaction
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New bis-aldehyde functionalized initiators, viz, 4,4′-(4,4′-(5- hydroxypentane-2,2-diyl)bis(4,1-phenylene))bis(oxy)dibenzaldehyde (1) and 4,4′-bis(4-(4-(formylphenoxy) phenyl) pentyl 2-bromopropanoate (2) were synthesized starting from commercially available 4,4′-bis(4-hydroxyphenyl) pentanoic acid. These initiators were utilized, respectively, for ring opening polymerization of -caprolactone and atom transfer radical polymerization of styrene. Well-defined polycaprolactone macromonomers (MnGPC: 2600-19400, PDI: 1.37-1.47) and polystyrene macromonomers (MnGPC: 2800-28200, PDI: 1.11-1.16) with bis-aldehyde functionality were synthesized. The kinetic study of styrene polymerization showed controlled polymerization behaviour. The presence of aldehyde functionality in macromonomers was confirmed by 1H NMR spectroscopy. The reactivity of aldehyde functionality was demonstrated by carrying out aldehyde-aminooxy click reaction of polycaprolactone macromonomer with O-(2-azidoethyl) hydroxylamine which proceeded in a quantitative manner without backbone degradation.
- Sane, Prakash S.,Tawade, Bhausaheb V.,Palaskar, Dnyaneshwar V.,Menon, Shamal K.,Wadgaonkar, Prakash P.
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p. 713 - 721,9
(2012/12/11)
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- Renewable polybenzoxazines based in diphenolic acid
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The reaction of mixtures of renewable diphenolic acid (DPA) and its methylesterbenzoxazine derivative (MDP-Bz) has been studied. The DPA was introduced to lower the high temperature needed to complete the curing of the pure benzoxazine. In this way, sampl
- Zú?iga, Camilo,Lligadas, Gerard,Ronda, Juan C.,Galià, Marina,Cádiz, Virginia
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scheme or table
p. 1617 - 1623
(2012/06/29)
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- Polybenzoxazines from renewable diphenolic acid
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The novel benzoxazine monomers, DPA-Bz and MDP-Bz from renewable diphenolic acid (DPA), which mimics the structure of bisphenol A (BPA), were synthesized by traditional approaches. The structure and purity of the monomers was confirmed by FTIR, 1/su
- Zuniga,Larrechi,Lligadas,Ronda,Galia,Cadiz
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experimental part
p. 1219 - 1227
(2012/02/04)
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- Symmetrical bis(heteroarylmethoxyphenyl)alkylcarboxylic acids as inhibitors of leukotriene biosynthesis
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Symmetrical bis(quinolylmethoxyphenyl)alkylcarboxylic acids were investigated as inhibitors of leukotriene biosynthesis and 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt (47·Na) met our design parameters for a drug candidate (ABT-080). This compound was readily synthesized in three steps from commercially available diphenolic acid. Against intact human neutrophils, 47·Na inhibited ionophore-stimulated LTB4 formation with an IC50 = 20 nM. In zymosan-stimulated mouse peritoneal macrophages producing both LTC4 and PGE2, 47·Na showed 9000-fold selectivity for inhibition of LTC4 (IC50 = 0.16 nM) over PGE2 (IC50 = 1500 nM). Preliminary pharmacokinetic evaluation in rat and cynomolgus monkey demonstrated good oral bioavailability and elimination half-lives of 9 and 5 h, respectively. Pharmacological evaluation of leukotriene inhibition with oral dosing was demonstrated in a rat pleural inflammation model (ED50 = 3 mg/kg) and a rat peritoneal passive anaphylaxis model (LTB4, ED50 = 2.5 mg/kg; LTE4, ED50 = 1.0 mg/kg). In a model of airway constriction induced by antigen challenge in actively sensitized guinea pigs, 47·Na dosed orally blocked bronchoconstriction with an ED50 = 0.4 mg/kg, the most potent activity we have observed for any leukotriene inhibitor in this model. The mode of inhibitory action of 47·Na occurs at the stage of 5-lipoxygenase biosynthesis as it blocks both leukotriene pathways leading to LTB4 and LTC4 but not PGH2 biosynthesis. However, 47·Na does not inhibit 5-lipoxygenase catalysis in a broken cell enzyme assay; therefore it is likely that 47·Na acts as a FLAP inhibitor.
- Kolasa,Gunn,Bhatia,Basha,Craig,Stewart,Bouska,Harris,Hulkower,Malo,Bell,Carter,Brooks
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p. 3322 - 3334
(2007/10/03)
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- Synthesis and biological activity of substituted bis-(4-hydroxyphenyl)- methanes as N-type calcium channel blockers
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Voltage activated calcium channel (VACC blockers have been demonstrated to have utility in the treatment of stroke and pain. A series of aminomethyl substituted phenol derivatives has been identified with good functional activity and selectivity for N-typ
- Schelkun, Robert M.,Yuen, Po-wai,Malone, Thomas C.,Rock, David M.,Stoehr, Sally,Szoke, Balazs,Tarczy-Hornoch, Katalin
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p. 2447 - 2452
(2007/10/03)
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- Symmetrical bis-heteroaryl-methoxy-phenylalkyl carboxylates as inhibitors of leukotriene biosynthesis
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Compounds having the formula: STR1 wherein W is the same at each occurrence and is selected from optionally substituted quinolyl, optionally substituted benzothiazolyl, optionally substituted benzoxazolyl, optionally substituted benzimidazolyl, optionally
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- Synthesis of a series of focally-substituted organothiol dendrons
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The synthesis of new organothiol-functionalized dendrons of generation 1-4 is described. Several modifications to the original method for preparation of dendrons are detailed that were found to improve the yield and aid in scale-up. A particularly advanta
- Chen, Kang-Yi,Gorman, Christopher B.
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p. 9229 - 9235
(2007/10/03)
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