• Journal of the Korean Applied Science and Technology
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• v.22 no.3
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• pp.270-280
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• 2005

To maximize a synergy effect in flame-retardancy of flame-retardant coatings, phosphorus and chlorine were introduced in polymer chains. Two-components PU flame-retardant modified polyesters (ABTTC-10C, -20C, -30C) were prepared by curing, at room temperature, of isocyanate (allophanate-trimer) and prepared modified polyesters which contain phosphorus and chlorine. To examine the film properties of the prepared flame-retardant coatings, film specimens were prepared with the prepared coatings. The film properties of ABTTC, ABTTC-10C and ABTTC-20C, which contain 0, 10 and 20wt%, 2,4-dichlorobenzoic acid (2,4-DCBA), respectively, were proved to be good, whereas the film properties of ABTTC-30C, which contains 30wt% 2,4-DCBA, were proved to be a little bit poor. Two kinds of flame retardancy tests, $45^{\circ}$Meckel burner method and LOI method, were performed. With the $45^{\circ}$Meckel burner method, three flame-retardant coatings except ABTTC showed less than 3.4 cm of char length, and showed less than 2 seconds of afterflaming and afterglow. From this result, the prepared flame-retardant coatings were proved to have the 1st grade flame retardancy. With the LOI method, the LOI values of the coatings containing more than 10wt% 2,4-DCBA were higher than 30wt%, which means that the coatings possess good flame-retardancy. From these results, it was found that synergistic effect in flame-retardancy was taken place by the introduced phosphorus and chlorine.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2643-2646
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• 2009

In this study, a novel phosphorus-containing flame retardant copolymer of spirocyclic pentaerythritol di(phosphate monochloride) and bisphenol S (SPD-BS) was successfully synthesized and used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) epoxy resins. The chemical structure of the SPD-BS was characterized using FT-IR and $^1H$ NMR spectra. The thermal properties were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The effects of SPD-BS and nano-$CaCO_3$ on the flame-retardant properties of DGEBA/SPD-BS systems were evaluated by measurement of the burning rate. As a result, the thermal stabilities of the DGEBA/SPD-BS systems were decreased with increasing SPD-BS content. The flame-retardant properties and char yields of the systems were significantly increased when SPD-BS content increased. The synergism of nano-$CaCO_3$ incorporation on flame retardancy was found for the DGEBA/SPD-BS systems.

• Macromolecular Research
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• v.13 no.2
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• pp.128-134
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• 2005

The phosphorus comonomer [(6-oxido-6H-dibenz<1,2>oxaphosphorin-6-yl)methyl]-methyl butane-dioate (DOP-MBDA) was synthesized through the addition reaction of dimethyl itaconate (DMI) with 9,10-dihydro­9-oxa-10-phosphaphenan threne-10-oxide (DOP). A series of novel flame retardant poly(butylene terephthalate)s (PBTs) containing different amounts of phosphorus were prepared using DOP-MBDA as a comonomer. These novel polymers were characterized by $^{1}H-NMR$, IR, and differential scanning calorimetry (DSC). The novel phosphorus­containing poly(butylene terephthalate)s, referred to as FR-PBTs, exhibited interesting thermal and mechanical behavior, as well as superior flame retardancy. These properties are attributed to the effect of incorporating the rigid structure of DOP-MBDA and the pendant phosphorus group into the poly(butylene terephthalate) (PBT) homopolymer. The UL 94-V2 rating could be achieved with this novel flame retardant PBT, which has a phosphorus content as low as $0.5 wt\%$, and the FR-PBTs emitted less fumes and toxic gases than the PBT homopolymer.

• Applied Chemistry for Engineering
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• v.27 no.6
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• pp.577-582
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• 2016

In this study, we compared and analyzed the flame retardancy and mechanical properties of three different rigid polyurethane foams (RPUF) containing noble non-halogen phosphorus flame retardant (BHP-RPUF) or halogen-phosphorus flame retardant (TCPP-RPUF) or no flame retardant material (Pure-RPUF). The noble phosphorus-based flame retardant, bis(3-(3-hydroxypropoxy)propyl) phenyl phosphate (BHP), was synthesized by the reaction between disodium phenyl phosphate and 3-chloro-1-propanol. Through universal testing machine (UTM) experiments, the compressive strength of BHP-RPUF was similar to that of TCPP-RPUF. From the result of foam morphology analysis, it was confirmed that BHP-RPUF has the lowest thermal conductivity of $0.023W/m{\cdot}K$. We also measured the size of air bubbles using reaction velocity and SEM, and analyzed how they affect the thermal conductivity. In addition, the heat-resisting property was investigated through TGA analysis. The limited oxygen index (LOI) test confirmed that BHP had the ability to increase the flame retardancy of RPUF.

• Elastomers and Composites
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• v.37 no.4
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• pp.224-233
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• 2002

This study has investigated the flame retardant properties of EPDM rubber with the addition of various flame retardants. Carbon black, stearic acid, zinc oxide cross-linking agent were mixed with EPDM rubber to produce the base rubber E0 without the addition of flame retardants. Phosphorus flame retardant Tricrecyl phosphate(TCP) was added to E0 in 0.5, 1, 1.5, 2 phr to make E1~E4 samples and red phosphorus was added in 3, 6, 9, 12 phr to make E5~E8 samples. A flame retardant of the bromine family Decabromodiphenyloxide(DBDPO), and a chlorinated paraffin retardant of the chlorine family was added to E0 in 3, 6, 9, 12 phr to make E9~E12 and E13~E16 samples, repectively. Basic physical properties such as tensile strength, tear strength and hardness were measured for all the rubber samples with various flame retardant additions. There was no substantial differences. On the other hand, Oxygen index and UL94 were measured to study flame retardant properties. From oxygen index measurements E0 sample showed a value of 23.5%, indicating the improvement of flame retardant properties. Also from UL94 measurements, it was found that addition of red phosphorus resulted in maximum flame retardant effect. It was found that increasing the amount of addition resulted in decreasing combustion rate and improving flame retardant effect regardless of the kind of flame retardant.

• Journal of the Korean Applied Science and Technology
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• v.23 no.4
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• pp.328-339
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• 2006

The PU flame-retardant coatings (TTBAH, ATBAH-10C, -20C, and -30C) were prepared using the synthesized ATBAs and HDI-trimer as curing agent at room temperature. The physical properties of PU flame-retardant coatings with chlorine and phosphorus were inferior to those with phosphorus only and the properties were getting worse with increasing chlorine content. Flame retardancy was tested with three methods. With the vertical method, complete combustion time of ATBAHs were $259^{\sim}347$ seconds, which means that the prepared coatings are good flame-retardant. With the $45^{\circ}$ Meckel burner method, char lengths of the three prepared coatings were less than 2.9 cm, which indicates that the prepared coatings are first grade. With the limiting oxygen index (LOI) method, the LOI values of the three prepared coatings were in the range of $30^{\sim}35%$, which proves good flame retardancy of the prepared coatings. from the result of flame retardancy tests of the specimens that contain the same amounts of flame retarding compounds. it was found that the coatings containing both phosphorus and chlorine show higher flame retardancy than the coatings containing only phosphorus. This indicates that there exists, some synergy effect between coexisting phosphorus and chlorine.

• Journal of the Korean Applied Science and Technology
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• v.23 no.1
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• pp.77-84
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• 2006

Modified polyesters (TTBA-10C, -20C, -30C) that contain phosphorus and chlorine were synthesized by the condensation polymerization of tetramethylene bis(orthophosphate), neohexanediol trichlorobenzoate, 1,4-butanediol and adipic acid, in which tetramethylene bis(orthophosphate) and neohexanediol trichlorobenzoate were prepared previously in our laboratory. In this study, two-component flame-retardant polyurethane coatings (TTBA-10C/HDI-trimer=TTHD-10C, TTBA-20C/ HDI-trimer= TTHD-20C, TTBA-30C/HDI-trimer= TTHD-30C) were obtained by curing at room temperature with the synthesized TTBAs and hexamethylene diisocyanate (HDI)-trimer as a curing agent. The obtained TTHDs were made into coating samples and used as test samples for various physical properties. The physical properties of the flame-retardant coatings containing chlorine and phosphorus groups were generally inferior to those containing only phosphorus group. Flame retardancy was tested by vertical and horizontal combustion method, and $45_{\circ}$ Meckel burner method. Since the retardancy of flame-retardant coatings containing chlorine and phosphorus groups was better than that containing only phosphorus group, it could be concluded that the retardancy by the synergism effect of chlorine and phosphorus groups exhibited.

• Journal of the Korean Applied Science and Technology
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• v.24 no.1
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• pp.31-46
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• 2007

This study was focused on the maximization of flame-retardancy of polyesters by a synergism of simultaneously introduced chlorine and phosphorus into polymer chains of modified polyesters. To prepare modified polyesters, reaction intermediates, TD-adduct (prepared from trimethylolpropane/2,4-dichlorobenzoic acid (2,4-DCBA)) and TMBO (prepared from tetramethylene bis(orthophosphate)), were prepared first, then condensation polymerization of the prepared intermediates, adipic acid, and 1,4-butanediol were carried out. In the condensation polymerization, the content of phosphorus was fixed to be 2%, and the content of 2,4-DCBA that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as ABTT-10C, -20C, -30C. Two-component PU flame-retardant coatings (ABTTC, ABTTC-10C, ABTTC-20C, ABTTC-30C) were prepared by the curing of synthesized ABTTs with a curing agent of allophanate/trimer at room temperature. To examine the film properties of the prepared PU flame-retardant coatings, film specimens were prepared with the prepared coatings. The film properties of ABTTC, ABTTC-10C and ABTTC-20C, which contain 0, 10 and 20wt% 2,4-DCBA, respectively, were proved to be good, whereas the film properties of ABTTC-30C, which contains 30wt% 2,4-DCBA, was proved to be a little bit poor. Two kinds of flame retardancy tests, $^{\circ}45Meckel$ burner method and LOI method were performed. With the $^{\circ}45Meckel$ burner method, three flame-retardant coatings except ABTTC showed less than 3.4cm of char length, and showed less than 2 seconds of afterflaming and afterglow. From this result, the prepared flame-retardant coatings were proved to have the 1st grade flame retardancy. With the LOI method, the LOI values of the coatings containing more than 10wt% 2,4-DCBA were higher than 30%, which means that the coatings possess good flame retardancy. From these results, it was found that synergistic effect in flame retardancy was taken place by the introduced phosphorus and chlorine.

• Polymer(Korea)
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• v.26 no.5
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• pp.623-633
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• 2002

The flame retardant and thermal properties of ortho-cresol novolac (OCN) and biphenyl epoxy blends containing red-phosphorus were investigated. For five types of compounds designed with the volume ratio of OCN and biphenyl epoxy, thermal properties were analysed by TGA or DTC, and flame retardancy effectiveness was estimated through UL-94V test. While the flame retardant and thermal properties were improved with the content of filler and red-phosphorus, the excessive amount of red-phosphorus caused to deteriorate those properties. Using the blends of OCN/biphenyl rather than pure OCN or biphenyl epoxy as a matrix the flame retardancy of composites could be improved by the synergic effects of high thermal resistance of OCN and intumescent property of biphenyl. The flame retardant me chanism of epoxy compound containing red-phosphorus could be thought of the heat-insulating effect of intumescent char-layer formed in the surface of composites.

• Polymer(Korea)
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• v.30 no.3
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• pp.238-246
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• 2006

The aim of this study is to enhance the flame retardancy by the synergism effect of chlorine and phosphorus groups. The flame-retardant polyurethane coatings containing chlorine and phosphorus compounds were synthesized. After synthesizing the intermediate products of tetramethylene bis (orthophosphate) (TMBO) and neohexanediol trichlorobenzoate (TBA-adduct), the condensation polymerization was performed with four different monomers of two intermediates, 1,4-butanediol, and adipic acid to obtain four-component copolymer(TTBA). The two-component flame-retardant polyurethane coatings (TTBA-10C/HDI-trimer=TTHD-10C, TTBA-20C/HDI-trimer=TTHD-20C, TTBA-30C/HDI trimer=TTHD-30C) were obtained by curing reaction at room temperature with the synthesized TTBAs and hexamethylene diisocyanate (HDI)-trimer as a curing agent. The obtained TTHDs were made into coating samples and used as test samples for various physical properties. The physical properties of the flame-retardant coatings containing chlorine and phosphorus groups were generally inferior to those containing only phosphorus group. Flame retardancy was tested by vortical and horizontal combustion method, and $45^{\circ}$ Meckel burner method. Since the retardancy of flame-retardant coatings containing chlorine and phosphorus groups was better than that containing only phosphorus group, it could be concluded that the retardancy by the synergism effect of chlorine and phosphorus groups exhibited.