• 한국응용과학기술학회지
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• 제22권1호
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• pp.1-8
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• 2005

Chlorine-containing modified polyester polyols were synthesized by two-step condensation reactions. Intermediate was synthesized by the esterification of monochloroacetic acid with trimethylolpropane in the first step. Polycondensation of the intermediate (MCAOs), 1,4-butanediol, and trimethylolpropane with adipic acid was carried out. Two-component polyurethane (PU) coatings were prepared by blending MCAOs and IPDI-isocyanurate. There new flame-retardant coatings showed various properties comparable to other non-flame-retardant coatings. They were superior to flammable coatings from the experimental results showing rapid and 10 to 13 hours of pot-life. Coatings with 30wt% monochloroacetic acid was not flammable by the vertical flame retardancy test.

• 한국응용과학기술학회지
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• 제22권3호
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• pp.257-269
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• 2005

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 tetramethlene 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 2wt%, 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 ABTTs. The prepared intermediates and modified polyesters were characterized with FT-IR, NMR, GPC, and TGA analysis. Average molecular weight and polydipersity index of the preparation of ABTTs were decreased with increasing 2,4-DCBA content because of the incease in hydroxyl group that retards reaction. We found that the thermal stability of the prepared ABTTs increased with chlorine content at high temperatures.

• 한국응용과학기술학회지
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• 제23권2호
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• pp.99-109
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• 2006

In order to obtain the maximum flame retardancy as well as the minimum deterioration of physical properties of PU flame-retardant coatings, chlorine and phosphorus functional groups were introduced into the pre-polymer of modified polyesters. In the first step, the tetramethylene bis(orthophosphate) (TBOP) and neohexanediol dichloroacetate (DCA-adduct) intermediates were synthesized. In the second step, 1,4-butanediol and adipic acid monomers were polymerized with the two kinds of intermediates to obtain copolymers. The modified polyesters containing chlorine and phosphorus (ATBA-10C, -20C, and -30C) were synthesized by adjusting that the content of phosphorus compound was fixed as 2wt% and the contents of chlorine compound (dichloroacetic acid) were varied as 10, 20, and 30wt%. Average molecular weight and polydispersity index of the preparation of ATBAs were decreased with increasing DCA content because of the increase in hydroxyl group that retards reaction.

• 한국응용과학기술학회지
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• 제23권4호
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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.

• 한국응용과학기술학회지
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• 제23권3호
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• pp.252-263
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• 2006

It is attempted to develop flame retardant polyurethane coatings, which have received significant attention in recent years. It is the purpose of this study to synthesize new reactive polyurethane coatings containing halogen. Lactone based modified polyester polyols, using trichlorobenzoic acid as chlorine moiety (TBAOs) were synthesized. These polyesters were cured with isophorone diisocyanate (IPDI)-isocyanurate at room temperature (TBAPUs). Physical properties of these flame retardant coatings were similar with those of non-flame retardant coatings. The flammability of coatings was strongly dependent on the chlorine contents. We found that the increasing chlorine contents showed better flame retarding properties and that, however, they also resulted in more smog generation during combustion. The detailed results of flammability test using various methods indicated $24{\sim}26%$ in LOI and $3.7{\sim}5.3\;cm$ char length in $45^{\circ}$ Meckel burner method.

• 한국응용과학기술학회지
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• 제22권3호
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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.

• 한국응용과학기술학회지
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• 제24권2호
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• pp.124-139
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• 2007

In order to obtain the maximum flame retardancy with the minimal deterioration of physical properties of PU flame-retardant coatings, chlorine and phosphorous functional groups were introduced into the pre-polymer of modified polyesters. In the first step, the tetramethylene bis(orthophosphate) (TBOP) and neohexanediol dichloroacetate (DCA-adduct) intermediates were synthesized. In the second step, 1,4-butanediol and adipic acid monomers were polymerized with the two kind of intermediates to obtain copolymer. The modified polyesters containing chlorine and phosphorous (ATBA-10C, -20C, and -30C) were synthesized by adjusting the contents of chlorine compound (dichloroacetic acid, 10, 20, 30 wt%) with fixed the content of phosphorous compound (2 wt%). The PU flame-retardant coatings (TTBAH -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 phosphorous were inferior to those with phosphorous 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 1st grade flame retardancy. 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 results of flame retardancy tests of the specimens that contain the same amounts of flame retarding compounds, it was found that the coatings containing both phosphorous and chlorine show higher flame retardancy than the coatings containing phosphorous alone. This indicates that some synergy effect of flame retardancy exists between phosphorous and chlorine.

• 한국응용과학기술학회지
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• 제24권4호
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• pp.319-331
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• 2007

The aim of this study is to enhance the flame retardancy by the synergism effect of phosphorus and bromine groups. The flame-retardant polyurethane coatings containing phosphorus and bromine compounds were synthesized. After synthesizing the intermediate products of tetramethylene bis(orthophosphate) (TBOP) and trimethylolpropane/2,3-dibromopropionic acid (2,3-DBP) [2,3-DBP-adduct], the condensation polymerization was performed with four different monomers of two intermediate products, 1,4-butanediol, and adipic acid to obtain four-components copolymer. In the condensation polymerization, the content of phosphorus was fixed to be 2wt%, and the content of 2,3-DBP that provides bromine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing phosphorus and bromine as DTBA-10C, -20C, -30C. Average molecular weight and polydispersity index of the preparation of DTBAs were decreased with increasing 2,3-DBP content because of increase of hydroxyl group that retards reaction. We found that the thermal stability of the prepared DTBAs increased with bromine content at high temperature.