Tris 2-hydroxyethyl Isocyanurate Research Articles

Synergistic flame retardancy of 4A-zeolite/MF-THEIC/ammonium polyphosphate in PP

In this paper, a melamine formaldehyde resin modified with tris(2-hydroxyethyl) isocyanurate (THEIC), named MF-THEIC, was synthesized via a solid-phase reaction between hexahydroxymethyl melamine (HMM) and THEIC. MF-THEIC was firstly used as a charring agent in an intumescent flame-retardant system together with APP as well as 4A-zeolite in flame-retarding PP. APP/MF-THEIC (3/1) can effectively reinforce the flame retardancy of PP at a total 24.0 % additive amount, moreover, 1.5 % 4A-zeolite is sufficient to achieve an optimum synergistic effect. The corresponding composites (Sample-17) had passed UL-94 V-0 classification well. The synergistic flame-retarding mechanism was systematically investigated by SEM, 31P NMR, TGA, FTIR spectra, and TG-MS. 4A-zeolite can react with APP to generate highly-active phosphates with good catalytic efficacy on polyphosphate esterification, and then to promote the formation of the char layer, simultaneously, 4A-zeolite is helpful to enhance the char graphitization degree and the strength of the intumescing char layer, thereby reinforcing its flame retardancy via a synergistic effect.

The flame retardant properties and mechanism of the composites based on DOPS and triazine-trione groups in epoxy resin

To reduce the risk of fire due to the flammability of epoxy resins (EP), the use of low-cost, non-toxic raw materials for the synthesis of efficient flame retardants is becoming an important research direction in the field of flame retardant technology. This research with tris (2-hydroxyethyl) isocyanurate (THEIC), maleic anhydride (MAH) and 9,10-dihydro-9-oxa-10- phospha-phenanthrene-10-sulfide (DOPS) as raw materials, through esterification reaction successfully synthesised a novel structure of DOPS-triazine-trione flame retardant tris (3-(9,10-dihydro-9-oxa-10-phospha-phenant hrene-10-sulfide)-butanedioic acid monoethyl ester-based) triazine-trione (DOPS-THEIC) and apply it to EP to prepare EP/DOPS-THEIC. The results demonstrate that the incorporation of 12.5 wt% DOPS-THEIC in EP leads to a significant increase in the Limiting Oxygen Index (LOI) value, reaching 32.8 %, which corresponds to achieving a UL-94 V-0 rating. Moreover, the CONE test revealed notable reductions in the peak heat release rate (PHRR), total heat release (THR), and mass loss rate (MLR) values by 74.1 %, 32.4 %, and 52.6 %, respectively, compared to pure EP. These findings indicate that the addition of DOPS-THEIC effectively suppresses the heat release during combustion, attributed to the formation of a char layer that minimizes mass loss and acts as an improved flame retardant in the condensed phase. Furthermore, as the DOPS-THEIC content increased, the EP composites exhibited remarkable retention of their excellent mechanical properties. This observation reinforces the promising potential of DOPS-THEIC as an effective flame retardant for enhancing the fire resistance of EP materials.

Synthesis of DOPO-Based Phosphorus-Nitrogen Containing Hyperbranched Flame Retardant and Its Effective Application for Poly(ethylene terephthalate) via Synergistic Effect.

To obtain industrialized poly(ethylene terephthalate) (PET) composites with highly efficient flame retardancy, a phosphorus-nitrogen (P-N) containing hyperbranched flame retardant additive was synthesized by 9,10-dihydro-9-oxa-10-phospho-phenanthrene-butyric acid (DDP) and tris(2-hydroxyethyl) isocyanurate (THEIC) through high temperature esterification known as hyperbranched DDP-THEIC (hbDT). The chemical structure of the synthesized hbDT was determined by FTIR, 1H NMR, 13C NMR, and GPC, etc. Subsequently, hbDT/PET composites were prepared by co-blending, and the effects of hbDT on the thermal stability, flame retardancy, combustion performance, and thermal degradation behavior of PET were explored to deeply analyze its flame retardant mechanism. The test results showed that hbDT was successfully synthesized, and that hbDT maintained thermal stability well with the required processing conditions of PET as retardant additives. The flame retardant efficiency of PET was clearly improved by the addition of hbDT via the synergistic flame-retardant effect of P and N elements. When the mass fraction of flame retardant was 5%, the LOI of the hbDT/PET composite increased to 30.2%, and the vertical combustion grade reached UL-94 V-0. Compared with pure PET, great decreased total heat release (decreased by 16.3%) and peak heat release rate (decreased by 54.9%) were exhibited. Finally, the flame retardant mechanism of hbDT/PET was supposed, and it was confirmed that retardant effect happened in both the gas phase and condensed phase. This study is expected to provide a new idea for the development of low toxic, environment-friendly and highly efficient flame retardant additive for polyesters in an industry scale.

Effects of intumescent flame retardant based on THEIC-based oligomeric ester as char forming agent on thermal，mechanical and flame retardant properties of HDPE composites

In this study, a new phosphor-ester (TPE) was prepared by one-spot polycondensation of tris (2-hydroxyethyl) isocyanurate (THEIC) and phenyl phosphonic dichloride (PPDC) and used as a charring agent in combination with ammonium polyphosphate (APP) to develop new intumescent flame retardant (IFR) for high-density polyethylene (HDPE). The thermal and flame retardant properties of composites were investigated by thermogravimetric analysis (TGA), limiting oxygen index measurement (LOI), and cone calorimetry (CCT). At the same time, the morphology and chemical structure of the char residue were analyzed by scanning electron microscopy, Fourier transfer infrared spectroscopy, and laser Raman spectroscopy. The results showed the LOI value of the composite HD/APP/TPE containing 25 wt. % of APP/THE reaches 28.2 %. The CCT test suggested that the peak heat released rate (PHRR) of the flame retardant composite is decreased by 37 % compared to that of pure HDPE. The use of IFR based on APP and TPE produces a compact char residue that acts as a barrier for heat, oxygen, and volatile combustibles and protects the underlying polymer. Besides TPE can produce the PO-type radicals that show some gas phase flame retardant action. However, the tensile strength of the composites is still lower than that of pure polymer.

Investigation on novel flame retardant low-density polyethylene composites based on THEIC and MCAPP

The low-density polyethylene (LDPE) composites with excellent fire resistance were fabricated based on the novel intumescent flame retardant (IFR) composed of tris(2-hydroxyethyl) isocyanurate (THEIC) and silica-gel microencapsulated ammonium polyphosphate (MCAPP). The influence of the IFR with varied mass ratio of THEIC and MCAPP on the flame retardancy and thermal properties of LDPE composites were investigated. Results show that the introduced IFR improves the flame retardancy significantly, and the highest limited oxygen index of 33.2% is obtained in the case with MCAPP/THEIC equaling 2:1 (LDPE3), achieving V-0 rating of UL-94. The peak heat release rate and total heat release of LDPE3 are decreased remarkably by 74.8% and 71.9%, respectively, in comparison with pure LDPE. Thermogravimetric analysis demonstrates LDPE composites with IFR having the dramatic enhanced thermal stabilities than that of pure LDPE at high temperature. This study provides an valuable approach to prepare the intumescent flame retardant LDPE composites.

Fire hazard suppression of intumescent flame retardant polypropylene based on a novel Ni‐containing char‐forming agent

Reducing the fire hazard of polypropylene (PP) is an important research direction in the fields of fire safety materials. In this article, a novel Ni‐containing char‐forming agent (TTPN) was successfully synthesized, using tris(2‐hydroxyethyl) isocyanurate (THEIC), terephthalic acid, and nickel dihydrogen phosphate. Then, TTPN was combined with the silica‐gel microencapsulated ammonium polyphosphate (OS‐MCAPP) to prepare intumescent flame retardant PP composites. From the results of the limiting oxygen index (LOI) test and cone calorimeter, the composite containing 30% IFR (OS‐MCAPP: TTPN = 3:2) shows the highest LOI value of 33.5%, and its peak heat release rate is 275.5 kWm−2, decreased by 79.0% and 37.4% than those of pure PP and the composite containing the char‐forming agent without Ni. Meanwhile, the composite containing TTPN present the best smoke and CO2/CO suppression. The results indicate that TTPN has an excellent ability to dramatically reduce the fire hazard of PP.

Effects of intumescent flame retardant system consisting of tris (2-hydroxyethyl) isocyanurate and ammonium polyphosphate on the flame retardant properties of high-density polyethylene composites

An intumescent flame retardant (IFR) system composed of tris (2-hydroxyethyl) isocyanurate (THEIC) and ammonium polyphosphate (APP) was used to prepare high density polyethylene (HDPE) composites, and their thermal and flammability properties were studied. The limiting oxygen index of the HDPE composite containing 30 wt% of IFR with an APP: THEIC weight ratio of 3:1 (HD31) reaches 31.5%. The cone calorimeter analysis shows that the peak and average heat release rate of HD31 are reduced by 69.5% and 58.1% respectively; while the average mass loss rate is reduced by 77.2%. The thermogravimetric analysis suggests that the IFR/HDPE composites have good char forming ability. The structural analysis of the char residue shows that the intumescent char is composed of a polyaromatic structure containing nitrogen in five or six-membered ring linked to phospho-carbonaceous structure via the POC linkage, and some phosphorous degradation products containing POP structure.

Synthesis of tris(2‐hydroxyethyl) isocyanurate homopolymer and its application in intumescent flame retarded polypropylene

ABSTRACTA macromolecular homopolymer (named as Homo‐THEIC) was synthesized through self‐etherification of tris(2‐hydroxyethyl) isocyanurate (THEIC) molecules and used as charring agent. Its chemical structure was characterized by FTIR and 13C‐NMR. The charring agent was mixed with ammonium polyphosphate (APP) and applied in flame retarded polypropylene (PP). Results of UL‐94, LOI, and cone calorimeter test showed that the LOI of flame retarded PP can reach 32.8% and UL‐94 V‐0 rating can be achieved at 30 wt % loading. The heat release rate and smoke production rate during the combustion of PP were substantially reduced. TGA results indicated that the synergistic effect between APP and Homo‐THEIC existed and the addition of intumescent flame retardant (IFR) dramatically enhanced the thermal stability of PP. According to the results of TGA, SEM, TG‐FTIR, FTIR, and Raman, the char forming process of IFR can be separated into three stages: the formation of viscous phosphate ester (Tonset−330 °C), the expanding process along with the decomposition of phosphate ester and the release of a large amount of gases (330–480 °C), and the final formation of graphitic‐like char without any expanding feature (480–670 °C). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44663.

Synthesis of an integrated intumescent flame retardant and its flame retardancy properties for polypropylene

An integrated intumescent flame retardant (TPM) was prepared by using tris(2-hydroxyethyl) isocyanurate (THEIC), polyphosphoric acid and melamine as raw materials. The structure of TPM was characterized by FTIR, 1H NMR and 31P NMR spectra. The flame retardancy of PP/TPM composites were evaluated by limited oxygen index (LOI), UL-94 and cone calorimeter test (CCT), and compared with that of PP/(APP/PER) composite. The thermal degradation and swollen process of PP/TPM composite were studied by TGA, TG-FTIR, SEM and FTIR. It was found that PP/TPM composite could reach UL-94 V-0 rating and had a better mechanical property than PP/(APP/PER) at 20 wt% IFR loading. The mean heat release rate (HRR) and total smoke production (TSP) of PP/TPM decreased 65.6% and 17.7% in comparison with pure PP. TGA results showed that 20.7 wt% and 6.8 wt% chars remained in TPM and PP/TPM at 800 °C, respectively, showing a good char forming ability. Finally, the swollen process and flame retardant mechanism were studied through analysis of gaseous products, morphology and structure of residual char of PP/TPM composites.

Synthesis and evaluation of a novel N--P-containing oil-based fire-retardant plasticizer for poly(vinyl chloride)

A novel N--P-containing soybean-oil-based fire-retardant plasticizer was synthesized using soybean oil methyl ester, 9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide (DOPO), and tris(2-hydroxyethyl) isocyanurate (THEIC). The structure was verified by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR) spectroscopy. The blends were characterized by thermogravimetric analysis (TGA), FTIR spectrometry, scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA). TGA showed that the thermal stability of the blends were acceptable. DMA indicated that the plasticizer had good plasticity for PVC. The limiting oxygen index (LOI) of the blends ranged from 21.3 to 29.6. The flammability and thermal stability of PVC/THEIC-DOPO-ESOME was better than that of PVC/TCPP.

Influence of a nitrogen-containing oil-based plasticizer on mechanical, thermal stability and fire performance of plasticized poly(vinyl chloride) and study of its mechanism of flame retardancy with Py–GC/MS

An epoxy oil-based plasticizer with a triazine ring structure (THEIC-ESBO) has been prepared using tris(2-hydroxyethyl) isocyanurate (THEIC) and soybean oil methyl ester as the main raw materials. The structure of THEIC-ESBO has been characterized by 1H NMR and 13C-NMR and elemental analysis. THEIC-ESBO substituting epoxy soybean oil (ESO) was used to plasticize PVC blends (PVC/THEIC-ESBO). when 60-70% ESO was substituted by THEIC-ESBO in PVC blends, the results of the mechanical properties and the dynamic thermomechanical analysis (DMA) indicate that plasticizing and compatibility of the plasticizer with PVC remained excellent, and the glass transition temperature (Tg) was 46.4°C. The thermal stability of PVC blends was investigated by thermogravimetric analysis (TGA). The Fire performance of the PVC/THEIC-ESBO was investigated by the limiting oxygen index (LOI) and cone calorimeter test. When THEIC-ESBO was used as plasticizers alone, the LOI of the PVC blend reached 26.1%. The cone calorimetric data show that with increasing THEIC-ESBO, the time to ignition prolong, the value of the heat release rate (HRR) and the total heat release (THR) were reduced, the total smoke of release (TSR) was increased, both of the release rate of CO and CO2 were increased, but the value of CO/CO2 was decreased, the value of the residual char yield (C-Y) was significantly enhanced. All the data indicated that flame retardant of PVC blends using THEIC-ESBO substitute ESO was significantly improved, and THEIC-ESBO exhibits flame inhibition in the gaseous phase. The mechanism of flame retardancy of PVC/THEIC-ESBO was investigated by pyrolysis gas chromatographymass spectrometry (Py–GC/MS). The results indicate that nitrogen-containing compounds from THEIC-ESBO pyrolysis dilute the concentration of combustible gases, the cross-linking reaction is also promoted the char yield. SO, during PVC blends combustion process, the flame retardant of PVC/THEIC-ESBO was enhanced.

Non-isocyanate polyurethane (NIPU) from tris-2-hydroxy ethyl isocyanurate modified fatty acid for coating applications

Abstract Conventional polyurethanes, in spite of their excellent properties and wide applications possess safety and handling issues related to isocyanate compounds while synthesis. The cyclic carbonate-amine reaction resulting into hydroxyurethane is said to be an isocyanate free polyurethane system and novel route of synthesis as well as good alternative to conventional polyurethanes. In the present work, non-isocyanate polyurethane was synthesized by modification of dehydrated castor oil fatty acid (DCOFA) with tris-2-hydroxy-ethyl isocyanurate (THEIC). The synthesis involved three steps viz esterification of DCOFA with THEIC, epoxidation of the ester formed (TEFA) and subsequent cyclocarbonation of THEIC–ester of fatty acid (CTEFA). The products obtained were confirmed by Fourier Transform Infrared Spectroscopy (FTIR) as well as 1H and 13C Nuclear Magnetic Spectroscopy (NMR). The CTEFA was cured with various amines such as dimethyl diphenyl sulphone (DDS), Isophorone Diamine (IPDA) and hexamethylene diamine (HMDA) to obtain NIPU coatings. The cured coatings were studied for chemical, mechanical, thermal and electrochemical properties. Also, the effect of amine curing agents on the performance of NIPU coatings was investigated. Experimental results showed that incorporation of THEIC into the system significantly improved coating properties.

Flame‐retardancy properties of tris(2‐hydroxyethyl) isocyanurate based charring agents on polypropylene

ABSTRACTTris(2‐hydroxyethyl) isocyanurate based charring agent (TBCA) was synthesized by melt polycondensation with tris(2‐hydroxyethyl) isocyanurate (THEIC) and terephthalic acid as raw materials. It was characterized by Fourier transform infrared spectroscopy, elemental analysis, 1H‐NMR, and thermogravimetric analysis (TGA). TBCA was blended with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The charring properties of TBCA was tested by flame retardancy in the PP/APP/TBCA (PP/IFR2) composite and compared with that of the PP/APP/THEIC (PP/IFR1) composite. The results show that PP/IFR2 had lower flame‐retardant properties but better water resistance than that of the PP/IFR1 composite because PP/IFR2 could still obtain a V‐0 rating after it had been soaked in water at 70°C for 96 h, whereas PP/IFR1 could not achieve any rating after 36 h. Their combustion performance was further evaluated by a cone calorimeter test, their thermal degradation processes were studied by TGA, and the morphology of the char residue was observed by scanning electron microscopy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41810.

Study on the condensation and crosslinking reactions of furfuryl alcohol and tris(2-hy-droxyethyl)isocyanurate by thermal methods

Condensation and crosslinking reactions of furfuryl alcohol (FA) and FA with tris (2-hydroxyethyl )isocyanurate (THEIC) are studied by means of DSC, TG, TBA, NMR and elemental analysis. Four exothermic peaks are observed on the DSC curves of thermal condensation of FA and FA with THEIC in the presence of sulfuric acid. The peaks I, II (50–80°C), III (110–130°C) and IV (150–190°C) correspond to linear polycondensation of FA through head-to-tail condensation, head-to-head etherification, crosslinking dehydration reaction between methylene group and terminal hydroxy group of FA polymeric chain and to further crosslinking reaction at higher temperature, respectively. The reactivity of FA and THEIC increases sharply at 130–150°C and THEIC is reacted completely at 150°C. Addition of THEIC raises the initial decomposition temperature of FA polymer by 60°C.

Detailed structural elucidation of polyesters and acrylates using Fourier transform mass spectrometry.

The detailed structural characterization of complex polymer architectures, like copolymers and polymer mixtures, by mass spectrometry presents a challenge. Even though soft ionization analyses revolutionized the characterization of large molecules and provided a means for determining the polymer’s molecular weight distribution, polydispersity, and end groups, full microstructure elucidation and monomer sequencing by soft ionization alone is not possible. The combination of high-resolution Fourier transform mass spectrometry (FTMS) and tandem mass spectrometry (MSn) provides a powerful analytical tool for addressing these challenges. This tool was used in our work to separate and identify the products of polymerization between 12-hydroxystearic acid (HSA) and stearic acid (SA), to provide precise information about the exact location of caprolactones on the Tris(2-hydroxyethyl)isocyanurate (THEIC) molecule, and to sequence a glycidyl methacrylate/methyl methacrylate (GMA/MMA) copolymer. The results highlight the value of ultrahigh resolution and tandem mass spectrometry for fine structural characterization and sequencing of polymers.

Novel use of glycols in polyester coating compositions

PurposeTo study the effect of addition of free diols and triols in the coating formulation on coating properties.Design/methodology/approachPolyester resins were synthesised from maleic anhydride, dimerised fatty acid, neopentyl glycol and tris (2‐hydroxyethyl) isocyanurate (THEIC). Then, ethylene glycol, propylene glycol, glycerol, trimethylol propane and THEIC were added as reactive components to the coating formulation. These coatings were then analysed for various coating properties and compared with those obtained with the base resins.FindingsThe coatings obtained with the addition of these reactive components were found to have improved properties compared with those of the base resins except in cases where the reactive component itself contributed to a reduction in performance, e.g. reduced alkali resistance with the addition of THEIC.Research limitations/implicationsThe addition of the free diols and triols required a corresponding increase in the amount of the curing agent to be added.Practical implicationsThis process would allow for the tailoring of coatings to suit requirements to a certain extent without modifying the base resin. The addition of low molecular weight components in the coating formulation, which is then incorporated in coatings, could reduce the solvent requirement.Originality/valueAlthough polyesters are an established polymeric system in coatings, the use of reactive diluents has not been investigated with the exception of unsaturated polyesters, whose curing chemistry is fundamentally different from that of polyesters focused on in this paper.

Identification and determination of the glyceride and tris-(2-hydroxyethyl)isocyanurate structures in the average macromolecule of a polyester with carbon-13-NMR spectroscopy: Analysis of the polyester average structure

The 13C-NMR approach to quantitative analysis of a polyester resin synthesized from dimethylterephthalate, ethylene glycol, tris-(2-hydroxyethyl)isocyanurate (THEIC), and glycerol is presented. Various glyceride and isocyanurate structures formed during the esterification have been identified and analyzed, at first in simple model systems and then in the structure of the resin. The contents of particular structural units were determined as well as a hypothetical average macromolecule of the resin defined. The assignments of 13C-NMR signals were made and correlated with the 1H shifts using a 2D-HETCOR experiment. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 675–687, 1998