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.

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.