scholarly journals Preparation of γ-Divinyl-3-Aminopropyltriethoxysilane Modified Lignin and Its Application in Flame Retardant Poly(lactic acid)

Materials ◽  
2018 ◽  
Vol 11 (9) ◽  
pp. 1505 ◽  
Author(s):  
Yan Song ◽  
Xu Zong ◽  
Nan Wang ◽  
Ning Yan ◽  
Xueying Shan ◽  
...  

Lignin can be a candidate as a charring agent applied in halogen-free flame retardant polymers, and incorporation of silicon and nitrogen elements in lignin can benefit to enhancing its thermal stability and charring ability. In the present work, wheat straw alkali lignin (Lig) was modified to incorporate silicon and nitrogen elements by γ-divinyl-3-aminopropyltriethoxysilane, and the modified lignin (CLig) was combined with ammonium polyphosphate (APP) as intumescent flame retardant to be applied in poly(Lactic acid) (PLA). The flame retardancy, combustion behavior and thermal stability of PLA composites were studied by the limited oxygen index (LOI), vertical burning testing (UL-94), cone calorimetry testing (CCT) and thermogravimetric analysis (TGA), respectively. The results showed a significant synergistic effect between CLig and APP in flame retarded PLA (PLA/APP/CLig) occured, and the PLA/APP/CLig had better flame retardancy. CCT data analysis revealed that CLig and APP largely reduced the peak heat release rate (PHRR) and total heat release rate (THR) of PLA, indicating their effectiveness in decreasing the combustion of PLA. TGA results exhibited that APP and CLig improved the thermal stability of PLA at high temperature. The analysis of morphology and structure of residual char indicated that a continuous, compact and intumescent char layer on the material surface formed during firing, and had higher graphitization degree. Mechanical properties data showed that PLA/APP/CLig had higher tensile strength as well as elongation at break.

2012 ◽  
Vol 24 (8) ◽  
pp. 738-746 ◽  
Author(s):  
Rui Zhang ◽  
Xifu Xiao ◽  
Qilong Tai ◽  
Hua Huang ◽  
Jian Yang ◽  
...  

Lignin–silica hybrids (LSHs) were prepared by sol–gel method and characterized by Fourier transform infrared (FT-IR) spectra, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). LSH and ammonium polyphosphate (APP) were added into poly(lactic acid) (PLA) as a novel intumescent flame-retardant (IFR) system to improve the flame retardancy of PLA. The flame-retardant effect of APP and LSH in PLA was studied using limiting oxygen index (LOI), vertical burning (UL-94) tests and cone calorimeter. The thermal stability of PLA/APP/LSH composites was evaluated by thermogravimetric analysis (TGA). Additionally, the morphology and components of char residues of the IFR-PLA composites were investigated by SEM and XPS. With the addition of APP/LSH to PLA system, the morphology of the char residue has obviously changed. Compared with PLA/APP and PLA/APP/lignin, a continuous and dense intumescent charring layer with more phosphor in PLA composites is formed, which exhibits better flame retardancy. All the results show that the combination of APP and LSH can improve the flame-retardant property and increase the thermal stability of PLA composites greatly.


2018 ◽  
Vol 89 (10) ◽  
pp. 2031-2040 ◽  
Author(s):  
Fanglong Zhu ◽  
QQ Feng ◽  
YF Xu ◽  
JF Hu

Flame retardant mixtures of multi-walled carbon nanotubes (MWCNTs) and intumescent flame retardant (IFR) coatings were applied to polyamide 6,6 (PA 6,6) fabrics to explore whether MWCNTs acted as a good synergist on the thermal stability and flame resistance of the IFR system. The influence of MWCNTs on the flame retardant properties and thermal degradation of the PA 6,6 fabrics were investigated by limiting oxygen index (LOI), vertical burning test (VBT), thermogravimetric analyzer (TGA), scanning electron microscopy (SEM) and cone calorimeter test (CCT). The peak heat release rate and total heat release of the IFR-PA 6,6 fabric with three kinds of wt% MWCNTs were lower than those of the only traditional IFR-PA 6,6 fabric (reduced by 74.2–76.4% and 74.3–76.5%, respectively). As compared to the traditional IFR coating, it was found that no enhancements for thermal stability and flame retardancy in terms of the ability to retard ignition were achieved for the MWCNT/IFR coating. These results demonstrated that the introduction of MWCNTs into an IFR coating can improve the flame retardancy of PA 6,6 fabric in terms of the heat release rate from CCT analysis, but it failed other burning measurements, such as LOI and VBT.


2018 ◽  
Vol 31 (2) ◽  
pp. 186-196 ◽  
Author(s):  
Shuang Yang ◽  
Yefa Hu ◽  
Qiaoxin Zhang

In this article, a phosphorus–nitrogen-containing flame retardant (DOPO-T) was successfully synthesized by nucleophilic substitution reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and cyanuric chloride. The chemical structure of DOPO-T was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (NMR) and phosphorous-31 NMR, and elemental analysis. DOPO-T was then blended with diglycidyl ether of bisphenol-A to prepare flame-retardant epoxy resins. Thermal properties, flame retardancy, and combustion behavior of the cured epoxy resins were evaluated by differential scanning calorimetry, thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the glass transition temperature ( Tg) and temperature at 5% weight loss of epoxy resin (EP)/DOPO-T thermosets were gradually decreased with the increasing content of DOPO-T. DOPO-T catalyzed the decomposition of EP matrix in advance. The flame-retardant performance of EP thermosets was significantly enhanced with the addition of DOPO-T. EP/DOPO-T-0.9 sample had an LOI value of 36.2% and achieved UL94 V-1 rating. In addition, the average of heat release rate, peak of heat release rate, average of effective heat of combustion, and total heat release (THR) of EP/DOPO-T-0.9 sample were decreased by 32%, 48%, 23%, and 31%, respectively, compared with the neat EP sample. Impressively, EP/DOPO-T thermosets acquired excellent flame retardancy under low loading of flame retardant.


Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 1062 ◽  
Author(s):  
Junlei Chen ◽  
Jihui Wang ◽  
Aiqing Ni ◽  
Hongda Chen ◽  
Penglong Shen

In this work, a novel phosphorous–nitrogen based charring agent named poly(1,3-diaminopropane-1,3,5-triazine-o-bicyclic pentaerythritol phosphate) (PDTBP) was synthesized and used to improve the flame retardancy of high-density polyethylene (HDPE) together with ammonium polyphosphate (APP). The results of Fourier transform infrared spectroscopy (FTIR) and 13C solid-state nuclear magnetic resonance (NMR) showed that PDTBP was successfully synthesized. Compared with the traditional intumescent flame retardant (IFR) system contained APP and pentaerythritol (PER), the novel IFR system (APP/PDTBP, weight ratio of 2:1) could significantly promote the flame retardancy, water resistance, and thermal stability of HDPE. The HDPE/APP/PDTBP composites (PE3) could achieve a UL-94 V-0 rating with LOI value of 30.8%, and had a lower migration percentage (2.2%). However, the HDPE/APP/PER composites (PE5) had the highest migration percentage (4.7%), lower LOI value of 23.9%, and could only achieve a UL-94 V-1 rating. Besides, the peak of heat release rate (PHRR), total heat release (THR), and fire hazard value of PE3 were markedly decreased compared to PE5. PE3 had higher tensile strength and flexural strength of 16.27 ± 0.42 MPa and 32.03 ± 0.59 MPa, respectively. Furthermore, the possible flame-retardant mechanism of the APP/PDTBP IFR system indicated that compact and continuous intumescent char layer would be formed during burning, thus inhibiting the degradation of substrate material and improving the thermal stability of HDPE.


2021 ◽  
Vol 2021 ◽  
pp. 1-11
Author(s):  
MinYi Luo ◽  
Jiayou Xu ◽  
Shu Lv ◽  
XueFeng Yuan ◽  
Xiaolan Liang

Polyvinyl alcohol- (PVA-) based aerogels have attracted widespread attention owing to their low cost, eco-friendliness, and low density. However, the applications of PVA-based aerogels are limited by their flammability. In this study, a flame retardant, ammonium polyphosphate (APP), and a biopolymer, chitosan (CS), were added to polyvinyl alcohol (PVA), and the polymer was further crosslinked using boric acid (H3BO3). In the PVA aerogels, the negatively charged APP and positively charged CS formed a polyelectrolyte complex (PEC) through ionic interaction. Cone calorimetry and vertical burning tests (UL-94) indicated that the PVA composite aerogels have excellent flame retardancy; they could decrease the heat release rate, total heat release rate, and carbon dioxide (CO2) generation. Both PVA/H3BO3 and APP-CS in the composite aerogel could be burned to carbon, and the foamed char layer could act together to impart the PVA composite aerogels with good flame retardancy. Further, the decrease in the temperature at the backside of the aerogels with increasing APP-CS content, as determined by the flame-spraying experiment, indicated that the PVA-based aerogels with APP-CS can also serve as thermal insulation materials. This work provides an effective and promising method for the preparation of PVA-based aerogels with good flame retardancy and thermal insulation property for construction materials.


2020 ◽  
pp. 002199832096353
Author(s):  
Seda Hazer ◽  
Ayse Aytac

Poly (Lactic Acid) (PLA)/Polycarbonate (PC) blend has gained much attention as a bio-based polymeric material in various industrial fields. This study aims to improve the properties of PLA/PC blend reinforced with glass fiber (GF) and carbon fiber (CF) mixture to be produced for industrial use. For this purpose, 50PLA/50PC blend was prepared and used as a control sample. Then, 30% by weight CF and 30% GF were added to the matrix separately. To examine the effect of the use of CF and GF together, the composites were prepared as a mixture form of fibers by adding 5-10-15% CF and 5-10-15% GF, respectively, to the control blend in pairs. All composites compounded with the laboratory-scale twin-screw mini extruder and molded by injection molding. The effects of using synthetic fiber mixture were evaluated in terms of the mechanical, thermal and flammability properties. Differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), tensile test, scanning electron microscopy (SEM), limiting oxygen index (LOI), heat release rate (HRR) test were carried for the characterization of composites. The highest tensile strength values ​​and maximum % crystallinity values were obtained for the 15CF/15GF fiber mixture containing PLA/PC composite as 113.7 MPa and 21.4, respectively. CO yield (COY), HRR, and total heat release rate were reduced significantly by using synthetic fibers and fiber mixture.


2014 ◽  
Vol 997 ◽  
pp. 89-92
Author(s):  
Jia Chen ◽  
Yuan Fang Zhang ◽  
Da Jiang Du ◽  
Ji Yan Liu

In this paper, zinc magnesium methyl cyclohexylphosphinate double salt (ZnMg (MHP)) was synthesized and used as flame retardant for PA6. The structure and the flammability of ZnMg (MHP) had been studied. The results presented that the LOI of PA6 with 20wt% filler loading improved from 21.2% to 31.4%, and the vertical burning test passed UL94 V-0 rating. TG analyses showed that ZnMg (MHP) had excellent thermal stability. DSC displayed that ZnMg (MHP) melted at 235°C. The tests of flammability revealed that ZnMg (MHP) had a strong inhibition effect on heat release rate (HRR) of the composites.


Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 180 ◽  
Author(s):  
Ru Zhou ◽  
Zhuang Ming ◽  
Jiapeng He ◽  
Yanming Ding ◽  
Juncheng Jiang

In this study, paraffin was selected as the phase change material (PCM) and high-density polyethylene (HDPE) as the supporting material to prepare a flame-retardant PCM system. The system consisted of paraffin, HDPE, expanded graphite (EG), magnesium hydroxide (MH) and aluminum hydroxide (ATH). The thermal stability and flame retardancy were studied by thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM) and cone calorimeter test (CONE). The SEM proved that the addition of MH and ATH can produce an oxide film on the surface of the composite material and form a “physical barrier” with the char layer, generated by the expansion of EG, preventing the transfer of heat and oxygen. The TGA test showed that, compared with other flame-retardant systems, the materials with added MH and ATH have a higher thermal stability and carbonization ability, and the amount of char residue has increased from 17.6% to 32.9%, which reduces the fire risk of the material. The flame retardant effect is obvious. In addition, the addition of MH and ATH has no significant effect on the phase transition temperature and latent heat value of PCMs. The CONE data further confirmed that MH and ATH can work with EG to prevent heat release, reduce the total heat release rate (THR) value and effectively suppress the generation of smoke, CO and CO2. The peak heat release rate (PHRR) value also decreased, from 1570.2 kW/m2 to 655.9 kW/m2.


Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1129 ◽  
Author(s):  
Ningjing Wu ◽  
Jihang Yu ◽  
Wenchao Lang ◽  
Xiaobing Ma ◽  
Yue Yang

A novel flame-retardant and toughened bio-based poly(lactic acid) (PLA)/glycidyl methacrylate-grafted natural rubber (GNR) composite was fabricated by sequentially dynamical vulcanizing and reactive melt-blending. The surface modification of aluminum hypophosphite (AHP) enhanced the interfacial compatibility between the modified aluminum hypophosphite by silane (SiAHP) and PLA/GNR matrix and the charring ability of the PLA/GNR/SiAHP composites to a certain extent, and the toughness and flame retardancy of the PLA/GNR/SiAHP composites were slightly higher than those of PLA/GNR/AHP composites, respectively. The notched impact strength and elongation of the PLA composite with 20 wt. %GNR and 18 wt.% SiAHP were 13.1 kJ/m2 and 72%, approximately 385% and 17 fold higher than those of PLA, respectively, and its limiting oxygen index increased to 26.5% and a UL-94 V-0 rating was achieved. Notedly, the very serious melt-dripping characteristics of PLA during combustion was completely suppressed. The peak heat release rate and total heat release values of the PLA/GNR/SiAHP composites dramatically reduced, and the char yield obviously increased with an increasing SiAHP content in the cone calorimeter test. The good flame retardancy of the PLA/GNR/SiAHP composites was suggested to be the result of a synergistic effect involving gaseous and condensed phase flame-retardant mechanisms. The high-performance flame-retardant PLA/GNR/SiAHP composites have great potential application as replacements for petroleum-based polymers in the automotive interior and building fields.


Polymers ◽  
2019 ◽  
Vol 11 (5) ◽  
pp. 770 ◽  
Author(s):  
Benben Liu ◽  
Huiling Wang ◽  
Xiaoyan Guo ◽  
Rongjie Yang ◽  
Xiangmei Li

A novel organic-inorganic hybrid containing allyl benzoxazine and polyhedral oligomeric silsesquioxane (POSS) was synthesized by the thiol-ene (click) reaction. The benzoxazine (BOZ)-containing POSS (SPOSS-BOZ) copolymerized with benzoxazine/epoxy resin was used to prepare composites of SPOSS-PBZ-E nanocomposites(NPs). The polymerization behavior was monitored by FTIR and non-isothermal differential scanning calorimetry (DSC), which showed that the composites had completely cured with multiple polymerization mechanisms according to the oxazine ring-opening and epoxy resin (EP) polymerization. The thermal properties of the organic–inorganic polybenzoxazine (PBZ) nanocomposites were analyzed by DSC and thermogravimetric analysis (TGA). Furthermore, the X-ray diffraction analysis and the scanning electron microscopy (SEM) micrographs of the SPOSS-PBZ-E nanocomposites indicated that SPOSS was chemically incorporated into the hybrid nanocomposites in the size range of 80–200 nm. The flame retardancy of the benzoxazine epoxy resin composites was investigated by limiting oxygen index (LOI), UL 94 vertical burn test, and cone calorimeter tests. When the amount of SPOSS reached 10% or more, the vertical burning rating of the curing system arrived at V-1, and when the SPOSS-BOZ content reached 20 wt %, the thermal stability and flame retardancy of the material were both improved. Moreover, in the cone calorimeter testing, the addition of SPOSS-BOZ hindered the decomposition of the composites and led to a reduction in the peak heat release rate (pHRR), the average heat release rate (aHRR), and the total heat release (THR) values by about 20%, 25%, and 25%, respectively. The morphologies of the chars were also studied by SEM and energy dispersive X-ray spectroscopy (EDX), and the flame-retardant mechanism of POSS was mainly a condensed-phase flame retardant. The ceramic layer was formed by the enrichment of silicon on the char surface. When there are enough POSS nanoparticles, it can effectively protect the combustion of internal polymers.


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