Two component polyurethane (PU) flame retardant coatings were prepared by blending trichloro modified polyesters (TCMPs) and isophorone diisocyanate isocyanurate. TCMPs were synthesized by polycondensation of trichlorobenzoic acid (TCBA), a flame retardant component, with adipic acid, 1,4 butanediol, and trimethylolpropane. The content of TCBA was varied in 10, 20, and 30 wt% for the reaction. Theses new flame retardant coatings showed various properties comparable to other non flame retardant coatings. Moreover, we carried out the combustion test and the flammability test for our flame retardant coatings. The results of vertical burning test for the coatings containing more than 20 wt% of TCBA were determined as no burn. The results of flammability test for the coatings with 20 wt% and 30 wt% of TCBA contents indicated the limiting oxygen index (LOI) values of 26% and 29% respectively, which implied relatively good flame retardancy.

The flame-retardant coatings were prepared by blending the synthesized triphosphorus modified polyester in the previous paper and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. It was confirmed that no deterioration of physical properties of PU coatings was observed with the increasing phenylphosphonic acid (PPA) contents. Flame retardancy was tested by a 45˚ Meckel burner method and LOI method. With the 45˚ Meckel burner method, CATBTP-20C and CATBTP-30C that contain 20 wt% and 30 wt% of PPA, flame retarding component, respectively, showed the first grade flame retardancy with 2.8~3.9 cm of char length ; and, with LOI method, they exhibited a good flame retardancy as a range of 30~32% of combustion values.

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.

Three phosphorus functional groups were introduced in one structural unit of polymer backbone to enhance the flame retardancy of PU coatings. In the first step, we synthesized tetramethylene bis(orthophosphate) (TBOP) that contained two phosphorus functional groups in one structural unit. In the next step, we synthesized modified polyesters (ATBTP-10C, -20C, -30C) that contained triphosphorus group using TBOP, 1,4-butanediol, trimethylolpropane, adipic acid, and another functional monomer, phenylphosphonic acid (PPA). The amount of PPA in ATBTPs was adjusted from 10 wt% to 30 wt%. The structure and characteristics of ATBTPs were examined using FT-IR, NMR, GPC, and TGA analysis. From the thermo-behavior test of diphosphorus modified polyester (ATBT) and ATBTPs, the afterglow of ATBT, ATBTP-10C, ATBTP-20C, and ATBTP-30C were 24.7, 27.1, 29.0, and 31.7%, respectively. It was found from this result that the afterglow increased with the amount of PPA component.

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 259~347 seconds, which means that the prepared coatings are good flame-retardant. With the 45˚ 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 30~35%, 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.

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, ˚45Meckel burner method and LOI method were performed. With the ˚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.

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 259~347 seconds, which means that the prepared coatings are good flame-retardant. With the 45˚ 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 30~35%, 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.

PU type flame-retardant coatings (TBAO/L-75, TBAOL ; TBAO/N-100, TBAON) were prepared by blending bromine-containing modified polyester (TBAO) which was synthesized in our earlier work. with two kinds of isocyanate curing agents, Desmodur L-75 and Desmodur N-100. Physical properties of the prepared flame-retardant coatings were tested. TBAOL shows better hardness than TBAON, while TBAON shows better viscosity, accelerated weathering resistance, yellowness index and lightness index difference than TBAOL. There were no remarkable differences in fineness of grind, 60˚ specular gloss, cross-hatch adhesion, and abrasion resistance of TBAOL and TBAON. There was no discernable difference in flame-retardancy between the two flame-retardant coatings, TBAOL and TBAON. When the content of tribromo acetic acid, which is flame-retarding component, was 30wt% the LOI value was in a range of 29~30%, which indicates that the two coatings are good flame-retardant coatings.

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 24~26% in LOI and 3.7~5.3 cm char length in 45˚ Meckel burner method.

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.

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˚ 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.

The aim of this study is to synthesis basic resins for the preparation of PU flame-retardant coatings that contain phosphorus and chlorine. After synthesizing intermediates of tetramethylene bis(orthophophate) (TMBO) and neohexanediol trichlorobenzoate (TBA-adduct), the condensation polymerization was performed with the intermediates, 1,4-butanediol, and adipic acid to obtain four-component copolymers. In the condensation polymerization, the content of phosphorus was fixed to be 2%, and the content of trichlorobenzoic acid (TBA) that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as TTBA-10C, TTBA-20C and TTBA-30C. Average molecular weight and polydispersity index of the prepared TTBAs decreased with increasing TBA content because of the increase in the number of hydroxyl groups that retards reaction. We found that the thermal stability of the prepared TTBAs increased with chlorine content at high temperatures.

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˚Meckel burner method and LOI method, were performed. With the 45˚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.

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.

Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate)(TBOP) were synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-S, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. Network structured PU flame-retardant coatings (APHD) were prepared by curing the synthesized benzoic acid modified polyesters containing phosphorus (APT B - 5 , -10, -15) with hexamethylene diisocyanate (HDI)-timer. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures. With the introduction of BZA, the film viscosity and film hardness of APHD decreased. With the introduction of caprolactone group, the flexibility, impact resistance, accelerated weathering resistance of APTBs increased. Flame retardancy of the coatings was tested. In a vertical burning method, APHD shows 210~313 seconds, which indicates that the coatings are good flame-retardant coatings. Moreover, the amount of afterglow and flame retardancy of the coatings are decreased with increasing BZA content.

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.

PU flame-retardant coatings (APHD) containing phosphorous were prepared by blending of hexamethylene diisocyanate-trimer, white pigment, dispersing agent, flowing agent, and previously prepared benzoic acid modified polyester (APTB) that contains phosphorous. Physical properties of the prepared APHD were examined. With the introduction of BZA (contained in APTB), the film viscosity and film hardness of APHD decreased. With the introduction of caprolactone group, the flexibility, impact resistance, accelerated weathering resistance of APTBs increased. Flame retardancy of the coatings was tested. In a vertical burning method, APHD shows 210~313 seconds, and in a 45˚ Meckel burner method, shows 1.3~4.0cm2 of char length, which indicates that the coatings are good flame-retardant coatings. Moreover, the amount of afterglow and flame retardancy of the coatings are decreased with increasing BZA content.

Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate) (TBOP) wer synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-5, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. The structure and characteristics of APTBs were examined using FT-IR, NMR, GPC, and TGA analysis. The increase of the amount of BZA in the synthesis of APTBs resulted in decrease in average molecular weight and kinematic viscosity. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures.

Pyrophosphoric modified polyesters (TATBs) were synthesized by polycondensation of adipic acid, trimethylolpropane, 1,4-butanediol, and tetramethylene bis(orthophosphate). Two-component PU flame-retardant coatings (TATBCs) were prepared by blending TATBs with HDI-Biuret. Most of the physical properties of the flame-retardant coatings were comparable to those of non-flame-retardant coatings. Coatings containing 10 and 15wt% 1,4-butanediol, TATBC-10C and TATBC-15C were not flammable in the vertical flame-retardancy test.

Two-component polyurethane flame retardant coatings (ATTBC) were prepared by blending polyisocyanate (TDI-adduct) with ATTBs mentioned at the previous paper. Most of the physical properties of the flame retardant coatings were comparable to those of non-flame retardant coatings. Especially, the hardness, impact resistance, and accelerated weathering resistance were remarkably improved with the increase of the content of 1,4-butanediol. Coatings containing 10 and 15 wt% 1,4-butanediol, ATTBC-10C and ATTBC-15C, were not flammable in vertical flame-retardancy test. Their char area recorded 1.1~11.6 cm2 in 45˚ eckel burner method.