Used polyurethane was chemically degraded by treatments with flame retardants such as tris(3-chloropropyl) phosphate (TCPP), triethyl phosphate (TEP), and trimethyl phosphate (TMP). The structure of degraded products (DEP) was analyzed by FT-IR and P-NMR and it turned out to be phosphorus containing oligourethanes. Rigid polyurethane foam was produced by using the degraded products (DEP) as flame retardants. The flammability of recycled rigid polyurethane was investigated. The recycled polyurethane shows a reduced flammability over virgin polyurethane. In order to evaluate flame retardant properties of the recycled polyurethane foams with various amounts of DEP, the combustion parameters of the foam was measured by a cone calorimeter. Scanning electron micrograph of recycled PU shows the same uniform cell morphology as virgin PU.

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.

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.

창포를 이용하여 질소와 인의 농도별, 식물의 생장단계별, 오염수의 체류시간별로 질소와 인의 제거효과를 분석하였던 바, 그 결과를 요약하면 다음과 같다. 체류 1시간 후에 수중의 질소와 인의 함량을 현저히 감소시켰으나, 2~4시간 후에는 감소율이 극히 낮았다. 이러한 현상은 식물의 생장초기, 생장기, 생장최성기에서 동일하였다. 수중에 질소와 인의 함량이 많을수록 제거율이 높았고, 인보다는 질소의 제거효과가 크게 나타났다. 생장최성기에 가장 많은 질소와 인을 제거하였고 다음으로 생장기, 생장초기의 순이었으나, 생장단계간의 차이는 극히 작았다. 동일 포트에 4일 동안 체류시킨 것보다 2일 체류 후에 다른 포트로 시험수를 옮긴 것이 질소와 인의 제거율이 약간 높았다.

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.

Aqueous polyurethane dispersion was synthesized using phosphorus compound which received significant attention for the replacement of halogenated flame retardants. In this study, polyols which have phosphorus moity in their structural unit were synthesized by two-step polycondensation reaction using dimethyl phenylphosphonate, ethylene glycols. adipic acid, and 1,4-butanediol. In the next step, polyurethane dispersion was prepared using these polyols, isophorone diisocyanate with dimethyl propionic acid. The particle size of polyurethane latex was reduced from 347 nm to 240 nm with increasing DMPA content. It was observed that the LOI values of prepared coatings increased from 27% to 35% with increasing phosphorus content.

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.

An intermediate, tetramethylene bis (orthophosphate), was prepared by the esterification of pyrophosphoric acid and l,4-butanediol. Then pyrophosphoric-containing modified polyesters (ATTBs) were synthesized by polycondensation of tetramethylene bis(orthophosphate), trimethylolpropane, adipic acid, and l,4-butanediol. The content of l,4-butanediol was varied from 10 to 20wt% for the reaction. The increase of the amount of l,4-butanediol in the synthesis of ATTBs resulted in increase in average molecular weight and decrease in kinematic viscosity owing to the excellent flowability and reactivity of l,4-butanediol.