• Polymer(Korea)
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• v.29 no.6
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• pp.575-580
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• 2005

The hydroxy terminated aliphatic hyperbranched polyesters having different generations were synthesized by using melt polycondensation procedure. Then, the terminal groups of hyperbranched polyesters were modified by using acryloyl chloride and characterized by $\^{1}H$-NMR and GPC techniques. As a result of the modification of terminal groups for hyperbranched polyesters, the phase of the polymers were changed from sticky solid to high viscous liquid indicating that the glass transition temperatures of modified hyperbranched polyesters were lower than the original one. The thermal stabilities of hydroxy terminated hyperbranched polyesters were higher than those of terminal group-modified polymers.

• Journal of the Korean Applied Science and Technology
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• v.22 no.3
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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.

• Journal of the Korean Applied Science and Technology
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• v.23 no.2
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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.

• Journal of the Korean Applied Science and Technology
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• v.24 no.1
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• pp.31-46
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• 2007

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, $^{\circ}45Meckel$ burner method and LOI method were performed. With the $^{\circ}45Meckel$ 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.

• Polymer(Korea)
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• v.25 no.3
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• pp.391-398
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• 2001

Two-component polyurethane (PU) flame-retardant coatings were prepared by blending tribromo modified polyesters ($TBAO_s$) and isocyanate.$TBAO_s$ were synthesized by condensation polymerization of tribromoacetic acid, a flame-retardant component, with 1,4-butanediol, adipic acid, and trimethylolpropane. The content of tribromoacetic acid was varied by 10, 20, and 30 wt% for the reaction. Various physical properties of these new flame-retardant coatings were comparable to nonflame-retardant coatings. Coatings with 20 wt% tribromoacetic acid did not burn during the vertical burning test.

• Journal of the Korean Applied Science and Technology
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• v.20 no.1
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• pp.57-63
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• 2003

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.

• Journal of the Korean Applied Science and Technology
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• v.24 no.3
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• pp.287-295
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• 2007

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.

• Journal of the Korean Applied Science and Technology
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• v.23 no.1
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• pp.77-84
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• 2006

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 $45_{\circ}$ 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.

• Journal of the Korean Applied Science and Technology
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• v.23 no.3
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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.

• Journal of the Korean Applied Science and Technology
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• v.17 no.4
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• pp.240-247
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• 2000

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.