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.

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.

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.

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.

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.

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.

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.

Methyl glycoside oleic acid polyester was successfully prepared from methyl glycosides and methyl oleate by emulsion interesterification in the presence of methyl fructoside oleic acid polyester as an emulsifier. Emulsion interesterification process was optimized to obtain 98% yield of methyl glycoside polyester within 3~5hr at temperatures as relatively low as 90~150℃ and 20~200mmHg pressure with a five-fold molar ratio of oleic acid methyl ester to methyl glycoside in the presence of 2(w/w)% potassium carbonate and 2O(v/v)% methyl fructoside polyester based on oleic acid methyl ester.

Two-component polyurethane flame-retardant coatings were prepared by blending trichloro aromatic modified polyesters(TCMPs) and polyisocyanate. 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. These 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 25% and 28% respectively, which implied relatively good flame retardancy.

Pyrophosphoric lactone modified polyester(PATT) that contains two phosphorous functional groups in one unit base resin structure was synthesized to prepare a non-toxic reactive flame retardant coatings. Then the PATT was cured at room temperature with isocyanate, Desmodur IL, to get a two-component polyurethane flame retardant coatings(PIPUC). Comparing the physical properties of the films of PIPUC with the film of non-flame retardant coatings, there was no degradation observed in physical properties by the introduction of a flame-retarding component into the resin. We found that the char lengths measured by 45˚Meckel burner method were 3.1~4.4cm and LOI values recorded 27~30%. These results indicate that the coatings prepared in this study is good flame retardant one. The surface structure of coatings investigated with SEM does not show any defects and phase separation.

Methyl fructoside oleic acid polyester(MFPE), fructose-based sugar polyester, was synthesized by solvent-free, soap-free transesterification of methyl oleate with methyl fructoside(MF) as a sugar starting material in the presence of conventional potassium carbonate basic catalyst. Methyl fructoside was found to be an effective sugar starting material, because of its low softning point, high heat stability, high miscibility, and high reactivity than other sugars. Yield 98% of purified MFPE based on initial weight of MF was obtained at 1:5 of the molar ratio of methyl fructoside to methyl oleate, 2%(w/w) of potassium carbonate catalyst content, 20~200mmHg of reduced pressure and 180℃ of reaction temperature. MFPE structure was confirmed by infrared and proton nuclear magnetic resonance spectroscopy. Physical properties of methyl of fructoside oleic acid polyester such as viscosity, HLB, solubility, color, refractive index, specific gravity, and density were similar to physical properties of sucrose polyesters(SPE) and vegetable oils. Then, it was elucidated that MFPE was sufficient to replace the SPE and conventional oils.

Two-component polyurethane flame retardant coatings were prepared by blending phosphate-containing modified polyesters(PMPEs) and TDI-adduct. PMPEs were synthesized by polycondensation of dimethyl phenylphosphonate, a flame retardant component, with 1,4-butanediol, adipic acid, and trimethylolpropane. The content of dimethyl phenylphosphonate was varied 10, 15, and 20wt% for the reaction. Various physical properties of these new flame retardant coatings were comparable to non-flame retardant coatings. Coatings with 20wt% dimethyl phenylphosphonate did not burn during the vertical burning test.

Two-packaged polyurethane coatings were prepared by blending benzoic acid lactone modified polyester polyol(BLMPs) and HDI-biuret. BLMPs were synthesized by polycondensation of benzoic acid, viscosity depression component, with 1,4-butanediol, adipic acid, and polycaprolactone polyol. Kinematic viscosity of BLMP was gradually decreased with increasing benzoic acid content in BLMP. The low viscosity of modified polyester has an advantage of making a high-solid content coatings. After the film was coated with the prepared polyurethane coatings and cured at room temperature, the various physical properties were measured. They showed good physical properties such as flexibility, impact resistance, cross hatch adhesion, yellowness index, and rust resistance. These advantages are the results of introducing polycaprolactone polyol.

SMC(Sheet molding compound)욕조 생산시 발생하는 폐 FRP를 보강재로서 재활용하기 위하여 불포화 폴리에스테르 매트릭스 수지에 보강하고 보강재와 매트릭스 수지의 계면 결합력을 증진시키기 위하여 보강재를 실란계 커플링제[3-methylacryloxyviny1 silane (MAOS)]로 전 처리하여 복합재를 제조하고 기계적 물성 및 계면현사에 대하여 관찰하였다. 보강률이 20wt%인 복합재의 굴곡강도 및 굴곡탄성률이 각 각 110MPa, 8.0GPa로 가장 우수하였으며 커플링제(MAOS)의 노동가 0.50wt%인 복합재의 굴곡강도 및 굴곡탄성률은 약 10%정도 향상되어 각 각 120MPa, 9.2GPa을 나타내었다. 또한 주사전자현미경 관찰 결과 보강재를 커플링제(MAOS)로 처리한 복합재의 보강재와 매트릭스 수지는 물리, 화학적을 잘 결합하여 보강재와 매트릭스 수지의 계면에서 pull out현상이 확인되지 않았으며 크랙도 발생하지 않았다.

The Wastewater from the weight reduction process of polyester is more difficult to be treated biologically than the general wastewater from dyeing and finishing processes in textile industries. Above wastewater shows high pH, high organic strength and wide variation of organic loading. These characteristics are due to TPA and EG resulting from alkaline weight-reduction process and make trouble in the operation of activated sludge process. Therefore, the objective of this study is to develop the pretreatment method for the successful operation of treatment process. For the successful pretreatment process, the wastewater from weight-reduction process should be segregated from other wastewater stream and then acidified with concentrated sulfuric acid to precipitate out TPA from DST solution. At the optimum pH of 2. 2, the initial $COD_{cr}$ 60,000mg/l is reduced to 11,500mg/l and the removal efficiency of $COD_{cr}$ is 81.1%. The required amount of sulfuric acid for pretreatment is not greater than the amount for the the existing neutralization process. Moreover, the supernatant of pretreatment process can be reused in acidification of wastewater.