Co-reporter:Hong-Xia Ma;Chen Zhao;Jin-Jun Qiu;Yun Liu
Journal of Applied Polymer Science 2017 Volume 134(Issue 6) pp:
Publication Date(Web):2017/02/10
DOI:10.1002/app.44453
ABSTRACTFour cyclotriphosphazene-based benzoxazine monomers (I, II, III, and IV) with relatively high molecular weight were synthesized by a nucleophilic substitution reaction, and their chemical structures were confirmed by 1H-NMR and 31P-NMR. A new term, oxazine value (OV, similar to epoxy value), was first proposed to explain the structure–property relationship of the cured polymers. The polymerization behaviors of the four monomers were studied by differential scanning calorimetry and Fourier transform infrared spectroscopy. The maximum exothermic peaks of the four monomers are in the range 244–248 °C. All monomers possess a wide processing window despite their high molecular weight. The thermal stability, glass-transition temperature (Tg), and mechanical properties of each cured polymer were studied by thermogravimetric analysis and dynamic mechanical thermal analysis. The char yield at 850 °C, Tg, and storage moduli of PIV (polybenzoxazine obtained from monomer IV) are 60.0%, 218 °C, and 9.0 GPa, respectively. The surface property and humidity absorption character of the cured polybenzoxazines were also studied. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44453.
Co-reporter:Hong-Xia Ma, Zhi-Bo Xu, Jin-Jun Qiu, Cheng-Mei Liu
Polymer 2017 Volume 132(Volume 132) pp:
Publication Date(Web):6 December 2017
DOI:10.1016/j.polymer.2017.10.053
•A novel solvent-free ring-opening method was proposed to prepare artificial urushi.•Cardanol and 1,3-Benzoxazine reacted readily under mild conditions without any catalyst.•The artificial urishiol showed similar reactivity as natural urushiol.•Fire retardancy of cured films was dramatically improved by incorporating with phosphazene unit.A branched urushiol analogue (CBCP) was first prepared by a ring-opening reaction of a benzoxazine containing a phosphazene core with renewable cardanol under solvent-free and catalyst-free conditions. The structure of CBCP was identified using nuclear magnetic resonance (1H NMR, 13C NMR, 31P NMR) and Fourier transform infrared spectroscopy (FTIR) technique. The preparation process for the cured CBCP film was simple, and the curing reaction of CBCP was monitored using differential scanning calorimetry (DSC) and FTIR methods. CBCP undergoes cross-linking under ambient conditions, resulting in polymeric films (artificial urushi) that are optically transparent, scratch-free and wrinkle-free. The cured film, with a high hardness and glossy surface, showed excellent thermal, excellent adhesion to the metal substrates and good chemical resistances due to strong hydrogen-bonding interactions and a compact, highly cross-linking structure containing a hard phosphazene core. Interestingly, the limited oxygen index (LOI) of cured film is 30, suggesting that the artificial urushi has flame retardant performance.Download high-res image (309KB)Download full-size image
Co-reporter:Hong-Xia Ma, Jun- Jie Li, Jin-Jun Qiu, Yun Liu, and Cheng-Mei Liu
ACS Sustainable Chemistry & Engineering 2017 Volume 5(Issue 1) pp:
Publication Date(Web):November 22, 2016
DOI:10.1021/acssuschemeng.6b01714
A novel star-shaped cardanol oligomer (HCPP) derived from cardanol and hexachlorocyclotriphosphazene was prepared, and its structure was identified using proton nuclear magnetic resonance (1H NMR, 13C NMR, 31P NMR) and Fourier transform infrared spectroscopy (FTIR) techniques. The HCPP underwent a thermal-initiated curing reaction both with and without catalyst. Oxygen was essential to this curing reaction, and the film preparation process was very simple. The curing reaction of HCPP was monitored by differential scanning calorimeter (DSC) and Fourier transform infrared (FTIR) methods. The catalyst (cobalt naphthenate) could remarkably improve the curing reaction speed. The cardanol-based cured films show excellent thermal stabilities. Interestingly, the char yield of the film cured at 800 °C in nitrogen is above 29%, implying that the fire-retardancy of cardanol-based polymers can be notably increased by in traducing a hard phosphazene core into the structure. Meanwhile, all cured films are highly transparent and have Tg values above 50 °C.Keywords: Biobased coatings; Cardanol; Green fire-retardant; Phosphazene; Star-shaped precursor; Thermal curing reaction;
Co-reporter:Gang Guo, Jian Sun, Chen Zhao, Yun Liu and Cheng-Mei Liu
Green Chemistry 2016 vol. 18(Issue 5) pp:1278-1286
Publication Date(Web):25 Sep 2015
DOI:10.1039/C5GC01919B
A novel hydrolysis-resistant trialkyne, namely tris(prop-2-yn-1-yloxy methyl)phosphane oxide (TPOPO) was prepared from an environmentally friendly tetrakis(hydroxymethyl)phosphonium sulfate (THPS). The chemical structure of TPOPO was characterized by FT-IR, NMR (1H, 13C, 31P) and MS. The TPOPO underwent metal-free and solvent-free 1,3-dipolar cycloaddition reaction with azidated soybean oil (AzSBO) at different alkyne/azide molar ratios. The gel contents of the cured polymers were higher than 95% and the char yields of polymers at 850 °C were over 16.4%. DMA analysis showed that the glass transition temperatures were over 45.9 °C. The cured polymers showed high dielectric constant and dielectric loss due to their high polarity.
Co-reporter:Ying-Xuan Liu, He-Ming Ma, Yun Liu, Jin-Jun Qiu, Cheng-Mei Liu
Polymer 2016 Volume 82() pp:32-39
Publication Date(Web):15 January 2016
DOI:10.1016/j.polymer.2015.11.036
•Vinyl benzoxazine (VBOZN), a heterobifunctional monomer, was successfully prepared.•Functional P(VBOZN) was obtained by selectively polymerizing the double bond.•P(VBOZN) can be regarded as a novel green and intrinsic fire retarded polymers.•The molecular weight of P(VBOZN) can be improved by copolymerization with electron-deficient monomers.•P(VBOZN) has the potential to be a “real” thermoplastic thermoset.AbstractA heterobifunctional monomer, namely, 3-(4-ethenylphenyl)-3,4-dihydro-2H-1,3-benzoxazine (VBOZN), which contains both vinyl group and benzoxazine group, was successfully prepared by three-step method with high purity and satisfactory yield. The chemical structure of VBOZN was identified by NMR, FTIR and elemental analysis. VBOZN selectively underwent free radical polymerization initiated by azodiisobutyronitrile to obtain homopolymer P(VBOZN) with Mn 4960 and Mw 11700. The benzoxazine-containing linear P(VBOZN) has Tg about 112 °C and shows better thermal stability than that of polystyrene. The P(VBOZN) was cured by heating without any catalyst and the peak temperature assigned to cationic ring-opening polymerization of P(VBOZN) centered at 244 °C. The molecular weight of P(VBOZN)could be improved dramatically by copolymerization of VBOZO with N-phenylmaleimide. Both homopolymer and copolymers show high stability and theoretical limiting oxygen index are near 30. P(VBOZN) and copolymers are not only new kinds of well-defined multifunction polymers with the potential of postpolymerization and/or chemical modification, they are also novel intrinsic fire retarded polymers.
Co-reporter:He-Ming Ma, Yun Liu, Ying-Xuan Liu, Jin-Jun Qiu and Cheng-Mei Liu
RSC Advances 2015 vol. 5(Issue 124) pp:102441-102447
Publication Date(Web):17 Nov 2015
DOI:10.1039/C5RA18058A
A novel heterobifunctional monomer, namely (6-ethenyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazine (VBOZO)), which contains both a vinyl group and benzoxazine group, was successfully prepared using the normal Wittig method from an aldehyde-containing benzoxazine precursor of 3-phenyl-3,4-dihydro-2H-1,3-benzoxazine-6-carbaldehyde. VBOZO underwent free radical polymerization initiated by azodiisobutyronitrile (AIBN) to form a homopolymer P(VBOZO) with a number-average molecular weight of about 5050 g mol−1. Meanwhile the benzoxazine group remains unchanged in the copolymer and can undergo cationic polymerization at high temperature to form crosslinked polymers. Benzoxazine-containing linear P(VBOZO) has a Tg of about 125 °C and shows much better thermal stability than polystyrene. The peak temperature assigned to the cationic ring-opening polymerization of P(VBOZO) was centered at 263.0 °C. The VBOZO also copolymerized with styrene under free radical conditions to get the copolymer P(VBOZO-co-St). The polymerization character of VBOZO is very similar to styrene and the copolymer composition is very close to the feed ratio of monomers. All copolymers show high thermal stability and the char yields at 800 °C are over 20%.
Co-reporter:Zhi-Wei Tan;Xiong Wu;Min Zhang;Jin-Jun Qiu
Polymer Bulletin 2015 Volume 72( Issue 6) pp:1417-1431
Publication Date(Web):2015 June
DOI:10.1007/s00289-015-1345-0
To improve the performance of traditional polybenzoxazines, copolymerized 3-phenyl-3,4-dihydro-2H-1,3-benzoxazine (Pa) and bisphenol-A benzoxazine (Ba) with three kinds of cyclotriphosphazene (CP)-based benzoxazine monomers, respectively. The ring-opening copolymerization behaviors of the benzoxazines mixtures are investigated by differential scanning calorimetry (DSC), the results imply that the CP-based benzoxazines could decrease the polymerization temperature of common benzoxazines. Due to the different structures of the CP-based benzoxazines that possess different numbers of organic benzoxazine moieties tether onto the inorganic CP ring, they produce the different dimensional crosslinking structures of the CP-based benzoxazines under ring-opening polymerization, the TGA and DMA results display the CP-based benzoxazines exhibit different degrees of improvement on the thermal stability and mechanic properties to the co-polybenzoxazines.
Co-reporter:Min Zhang, Zhiwei Tan, Hongxia Ma, Jinjun Qiu and Chengmei Liu
RSC Advances 2014 vol. 4(Issue 96) pp:53505-53513
Publication Date(Web):29 Sep 2014
DOI:10.1039/C4RA07035F
A novel dendritic organic–inorganic hybrid polyphenol (T2) based on cyclotriphosphazene was synthesized by the condensation reaction of T1 and phenol catalysed by phosphotungstic acid. The dendritic polyphenol T2 comprising twelve phenolic hydroxyl groups exhibited excellent solubility in common organic solvents. Three branched benzoxazine monomers with different oxazine ring content were synthesized via Mannich condensation reaction. These branched benzoxazine monomers showed low initial curing temperature. The properties of corresponding polybenzoxazines, such as thermal stabilities, mechanical properties, dielectric properties and gel contents significantly depended on the oxazine ring content of T3. With the increase of the oxazine ring content for T3, these properties could be greatly improved due to their high crosslinking density.
Co-reporter:Min Zhang, Zhiwei Tan, Siqian Hu, Jinjun Qiu and Chengmei Liu
RSC Advances 2014 vol. 4(Issue 83) pp:44234-44243
Publication Date(Web):15 Aug 2014
DOI:10.1039/C4RA05136J
Phosphoester groups were conveniently introduced into benzoxazine monomers by chemical bonding through nucleophilic reaction of a benzoxazine ring with diethyl phosphite (DEP). The reaction process was monitored by phosphorus 31 nuclear magnetic resonance (31P-NMR). The characteristic peaks of 31P-NMR corresponding to DEP disappeared entirely when the reaction was run at 90 °C for 24 h, which implied the completion of the nucleophilic reaction. The products obtained then underwent direct ring-opening polymerization to produce DEP-modified polybenzoxazines. The introduction of DEP into polybenzoxazines led to a reduction of the onset of the polymerization temperature The adsorption ability for Cd(II) was improved because the phosphoester group provided an efficient chelating site for heavy metal ions.
Co-reporter:Zhiwei Tan, Chengyan Wu, Min Zhang, Wenzhong Lv, Jinjun Qiu and Chengmei Liu
RSC Advances 2014 vol. 4(Issue 79) pp:41705-41713
Publication Date(Web):13 Aug 2014
DOI:10.1039/C4RA06080F
Two kinds of new phosphorus-containing crosslinked polymer materials were prepared via thiol-ene photopolymerization and their properties were studied. In order to prepare these crosslinked polymer materials, multifunctional monomer tris(allyloxymethyl)phosphine oxide (TAOPO) was synthesized from an eco-friendly raw material, tetrakis(hydroxymethyl) phosphonium sulfate (THPS). Crosslinked poly(phosphine oxide) networks were then produced by a thiol-ene reaction in which TAOPO reacts with the two kinds of polythiol under ultraviolet (UV) irradiation. The new crosslinked polymers possess long-term hydrolysis-resistance property because the monomer TAOPO contains a phosphorus–carbon bond. The crosslinked polymers have a high gel content, high dielectric constant, low dielectric loss, and excellent transparency with a high refractive index and high Abbe number. DMA and TGA results indicated that all cured poly(phosphine oxide) were uniform networks and exhibited a high thermal stability.
Co-reporter:Shu-Zheng Liu, Jin-Jun Qiu, Ai-Qing Zhang and Cheng-Mei Liu
RSC Advances 2013 vol. 3(Issue 20) pp:7472-7478
Publication Date(Web):07 Mar 2013
DOI:10.1039/C3RA23358H
Recently, we have reported the self-assembly of nanobelts and microbelts originating from the organic–inorganic hybrid molecule hexakis-(4-(5-phenyl-1,3,4-oxazodiazol-2-yl)-phenoxy)-cyclotriphosphazene (HPCP) by a simple solution method. Inspired by [2 + 2] photodimerization, our group has further attempted to verify the proposed self-assembly mechanism of oxadiazole-containing cyclotriphosphazene by solid-state photochemical reaction. We modified the molecular structure of HPCP, introducing a vinyl group into it to obtain a new oxadiazole-containing cyclotriphosphazene, hexakis-(4-(5-styryl-1,3,4-oxazodiazol-2-yl)-phenoxy)-cyclotriphosphazene (HSCP). The microbelts and flower-like particles of HSCP were self-assembled through a simple solvent exchange process by exploiting the π–π interactions between neighboring HSCP molecules as the driving force. The as-prepared materials were capable of [2 + 2] photodimerization and shape maintenance, as well as forming insoluble fluorescent materials. The self-aggregating and photoreaction properties of HSCP were characterized by UV-vis, FESEM, TEM, 1H-NMR, etc.
Co-reporter:Ya-Ni Guo;Jin-Jun Qiu;He-Qing Tang
Journal of Applied Polymer Science 2011 Volume 121( Issue 2) pp:727-734
Publication Date(Web):
DOI:10.1002/app.33806
Abstract
Highly transparent optical resins based on poly(methyl methacrylate) (PMMA) and two cyclotriphosphazene derivatives which acting as halogen-free flame retardants were prepared. The refractive indices, visible light transmittance, water absorption, flame-resistant characteristic, and the mechanical properties of the resins were studied. Comparing with pure PMMA, the as-prepared resins with the two additives exhibited higher refractive index (nd), longer UV cutoff wavelength and better surface hardness. The water absorption of the resins was decrease with increasing of the additives. The visible light transmittance of all the samples adding Additive A was higher than 90%. When the weight ratio of additive/MMA was 20/100, the limiting oxygen index (LOI) of the samples were 26 (with Additive A) and 22 (with Additive B), respectively. The surface hardness was increased from HB to 2H with increasing the content of the additives, and the impact and the tensile strength changed little for the formulas of the additives lower than 30% by weight. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Co-reporter:Ya-Ni Guo;Jin-Yang Ming;Chao-Yu Li;Jin-Jun Qiu;He-Qing Tang
Journal of Applied Polymer Science 2011 Volume 121( Issue 6) pp:3137-3144
Publication Date(Web):
DOI:10.1002/app.33797
Abstract
Transparent copolymers composed of hexa(allyl 4-hydroxybenzoate) cyclotriphosphazene (compound 1) and styrene as potential halogen-free, flame-retardant optical resins were prepared by radical copolymerization. The thermal performances of the cured resins were studied with thermogravimetric analysis; the decomposition mechanism of the copolymers was investigated with integrated thermogravimetry–Fourier transform infrared analysis. Compared with conventional polystyrene, the synthesized copolymers exhibited a higher refractive index and a higher thermal stability both under nitrogen and air atmospheres at elevated temperature, and the visible-light transmittance of the copolymers decreased slightly. With increasing ratio of compound 1 to styrene in the copolymers, the onset decomposition temperature and the char yield both increased gradually. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Co-reporter:Shu-Zheng Liu, Xiong Wu, Ai-Qing Zhang, Jin-Jun Qiu, and Cheng-Mei Liu
Langmuir 2011 Volume 27(Issue 7) pp:3982-3990
Publication Date(Web):March 4, 2011
DOI:10.1021/la104547z
A new oxadiazole-containing cyclotriphosphazene, namely, hexakis-(4-(5-phenyl-1,3,4-oxazodiazol-2-yl)-phenoxy)-cyclotriphosphazene (HPCP) was synthesized. Single-crystal nano- and microbelts of HPCP were self-assembly via two simple solution methods. The shapes of the as-prepared nano- and microstructures can be readily controlled by varying the solvent and aging time in the self-assembly process. A growth mechanism was proposed for the formation of the 1D morphological structures. Crystal structure analysis demonstrated that the overlap between the aryl units attached to the cyclotriphosphazene backbone forms effective intermolecular π−π linking for crystal growth. Electronic and optical properties of the as-prepared nano- and microstructures are investigated.
Co-reporter:Xiong Wu, Shu-Zheng Liu, Da-Ting Tian, Jin-Jun Qiu, Cheng-Mei Liu
Polymer 2011 Volume 52(Issue 19) pp:4235-4245
Publication Date(Web):1 September 2011
DOI:10.1016/j.polymer.2011.07.037
Well-defined organic–inorganic hybrid benzoxazine monomers based on cyclotriphosphazene (CP) cores have been synthesized. Theses monomers possessed controllable number of organic benzoxazine moieties and biphenyl groups distributed on the inorganic ring of CP. Corresponding ring-opening polymerization under heat led to highly cross-linked polymers with different number of crosslinking sites. The ring-opening polymerization behaviors of the new benzoxazine monomers were investigated by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMA). The results indicated that the polymerization activity of the monomers depended on the number of benzoxazine moiety of corresponding monomers. Those monomers with more benzoxazine moieties resulted in higher polymerization rate. Due to the high crosslinking nature with rigid and stable inorganic CP ring and biphenyl groups in the networks, the resulted polybenzoxazines from the monomers showed excellent thermal stability, mechanic property and humidity resistance.
Co-reporter:Xiong Wu, Yun Zhou, Shu-Zheng Liu, Ya-Ni Guo, Jin-Jun Qiu, Cheng-Mei Liu
Polymer 2011 Volume 52(Issue 4) pp:1004-1012
Publication Date(Web):17 February 2011
DOI:10.1016/j.polymer.2011.01.003
A hyperbranched organic–inorganic hybrid benzoxazine monomer based on cyclotriphosphazene (CP) has been synthesized, which possesses six organic benzoxazine moieties distributed on the inorganic ring of CP. The high molecular weight (1491 g/mol) monomer showed excellent solubility in common organic solvents. Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) were used to study the thermal ring-opening polymerization reaction of the novel benzoxazine monomer. FT-IR spectrum implied that the characteristic absorption peaks of the benzoxazine ring disappeared completely after curing at 240 °C for 1 h, which illustrated that the completion of polymerization reaction. DSC plots indicated that the melting point of the new monomer was 77 °C and an exothermic peak was 225 °C owing to the ring-opening polymerization of the monomer. Due to its highly steric crosslinking structure with rigid and thermal stable inorganic CP as the core, the polybenzoxazine based on the new monomer showed excellent thermal stability and mechanic properties. The char yield of the polymer at 850 °C was 66.9% in nitrogen, and the Tg of the polybenzoxazine was 152 °C.
Co-reporter:Rui Bao, Min Pan, Jin Jun Qiu, Cheng Mei Liu
Chinese Chemical Letters 2010 Volume 21(Issue 6) pp:682-685
Publication Date(Web):June 2010
DOI:10.1016/j.cclet.2009.12.020
The synthesis and mesomorphic properties of a new class of liquid crystalline cyclotriphosphazenes with rigid cyanostilbene groups and flexible alkoxy groups are reported. The thermal behaviors of cyclotriphosphazene derivatives 5a–5d are studied by the means of differential scanning calorimetry, polarizing optical microscopy. Nematic phases were observed in compounds 5a–5d both on heating and cooling. The clear temperatures of compounds 5a–5d slightly increased with increasing length of terminal alkyl chain. Compounds 5a–5d showed different mesogenic region from minimum 5 °C to maximum 142 °C.
Co-reporter:Rui Bao, Min Pan, Jin Jun Qiu, He Qing Tang, Cheng Mei Liu
Chinese Chemical Letters 2010 Volume 21(Issue 11) pp:1330-1333
Publication Date(Web):November 2010
DOI:10.1016/j.cclet.2010.05.010
A new approach to synthesize liquid crystalline polymer with narrow polydispersity index (PDI) was developed. Photo-polymerization of 4-cyanophenyl-4′-(6-acryloyloxyhexyloxy)benzoate (RM23) in nematic liquid crystals with macroscopic orientation was studied. The effects of the monomer concentration on the molecular weight and PDI of the resulting polymers were studied through gel permeation chromatography (GPC) and polarized optical microscopy. The low PDI of 1.19 and 1.22 was obtained in the reverse and normal modes, respectively. The PDI and molecular weight increased with monomer concentration.
Co-reporter:Ya-Ni Guo;Chen Zhao;Shu-Zheng Liu;Dong Li;Shu-Jiang Wang
Polymer Bulletin 2009 Volume 62( Issue 4) pp:421-431
Publication Date(Web):2009 April
DOI:10.1007/s00289-008-0035-6
Cyclomatrix polyphosphazenes attract more and more interest because they possess thermal stability and halogen-free flame retardant property. The hexa(Allyl 4-hydroxybenzoate)cyclotriphosphazene is synthesized using hexachlorocyclotriphosphazene (HCTP), 4-hydroxybenzoic acid and allyl alcohol, its structure is confirmed by FTIR, 1H NMR, 13C NMR, 31P NMR and mass spectrometer. Through radical homopolymerization of itself and copolymerization with methyl methacrylate (MMA), a series of optical resins containing cyclotriphosphazene units are obtained. The refractive indices, the visible light transmittance, the density, the water absorption, the thermal and flame-retardant characteristic of the cured resins are studied. Among the tested cured resins, the cyclomatrix homopolymer has the highest refractive index (nd = 1.596), the highest thermal stability (starting decomposed at 337 °C) and the best halogen-free flame-retardant characteristic (limited oxygen index is 34.33% via the 40.03% char yield data at 850 °C by the semi-empirical formula).
Co-reporter:Jin-Jun Qiu;Qi-Xing Zheng;Xiao-Dong Guo;Fen Hu
Journal of Applied Polymer Science 2006 Volume 102(Issue 4) pp:3095-3101
Publication Date(Web):29 AUG 2006
DOI:10.1002/app.23720
Polyphosphoester is a kind of biodegradable polymer with excellent biocompatibility and have been used in drug delivery, tissue engineering, and other bioapplications. A novel unsaturated polyphosphoester (UPPE) based on bis(1,2-propylene glycol) fumarate (BPGF) and ethyl dichlorophosphate was synthesized by polycondensation reaction, and crosslinkable double bonds was introduced into the resulting polymer through the fumarate groups. NMR results indicate that there are three possible bonding models in polyphosphoester because of three isomers of BPGF. The GPC results express that increase in polymerization time leads to high molecular weight of polyphosphester and narrow distribution of molecular weight. After 18 h of polymerization reaction, the molecular weight reached to 5956 g mol−1 and the polydispersity index was 1.12. The UPPE was soluble in N-vinyl pyrrolidone and easily crosslinked by free-radical polymerization. At the constant temperature (37°C), the maximum temperature due to heat release during crosslinking reaction varied from 41.1°C to 82.30°C and the setting time was between 1.95 and 10.28 min, according to different formulas. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3095–3101, 2006
Co-reporter:Zhi-Wei Tan, Jian Sun, Cheng-Yan Wu, Jin-Jun Qiu, Cheng-Mei Liu
Journal of Hazardous Materials (15 January 2017) Volume 322(Part B) pp:540-550
Publication Date(Web):15 January 2017
DOI:10.1016/j.jhazmat.2016.10.021
•Novel way for deep utilization of PH3 toxic gas.•Converting PH3 to high value-added polymers.•Green THPS as key intermediate.•Phosphorus-containing polybenzoxazine with excellent properties.A convenient route to convert the highly toxic phosphine (PH3) tail gas into high-performance polybenzoxazines was first described in this paper. Two aliphatic polyamines, namely tris(aminomethyl)phosphine oxide and bis(aminomethyl)phenylphosphine oxide, were synthesized from tetrakis(hydroxymethyl)phosphonium sulfate (THPS), a green derivative of PH3 tail gas. And then two novel phosphorus-containing benzoxazine monomers, tris(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl)phosphine oxide (TBOz) and benzylbis(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl) phosphine oxide (BBOz) were prepared by three-steps procedure. FT-IR and DSC technologies were adopted to study the thermal-initiated polymerization behaviors of two benzoxazine monomers. Thermal properties of these crosslinked polymers were studied by TGA and DMA. The results display that the polybenzoxazines (PTBOz and PBBOz) exhibite good thermal stabilities and high glass transition temperatures. The char yield of polybanzoxazine is high as 47% and indiactes that phosphorus-containing polybenzoxazines show high fire-retardancy. The surface free energies of the PTBOz and PBBOz are 37.1 and 40.4 mJ m−2 by Owens two-liquid method. The dielectric properties of the PTBOz and PBBOz remaine near constant in the experimental frequency range.Download full-size image
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