• 한국응용과학기술학회지
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• 제22권3호
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• pp.270-280
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• 2005

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

• Bulletin of the Korean Chemical Society
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• 제30권11호
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• pp.2643-2646
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• 2009

In this study, a novel phosphorus-containing flame retardant copolymer of spirocyclic pentaerythritol di(phosphate monochloride) and bisphenol S (SPD-BS) was successfully synthesized and used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) epoxy resins. The chemical structure of the SPD-BS was characterized using FT-IR and $^1H$ NMR spectra. The thermal properties were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The effects of SPD-BS and nano-$CaCO_3$ on the flame-retardant properties of DGEBA/SPD-BS systems were evaluated by measurement of the burning rate. As a result, the thermal stabilities of the DGEBA/SPD-BS systems were decreased with increasing SPD-BS content. The flame-retardant properties and char yields of the systems were significantly increased when SPD-BS content increased. The synergism of nano-$CaCO_3$ incorporation on flame retardancy was found for the DGEBA/SPD-BS systems.

• Macromolecular Research
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• 제13권2호
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• pp.128-134
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• 2005

The phosphorus comonomer [(6-oxido-6H-dibenz<1,2>oxaphosphorin-6-yl)methyl]-methyl butane-dioate (DOP-MBDA) was synthesized through the addition reaction of dimethyl itaconate (DMI) with 9,10-dihydro­9-oxa-10-phosphaphenan threne-10-oxide (DOP). A series of novel flame retardant poly(butylene terephthalate)s (PBTs) containing different amounts of phosphorus were prepared using DOP-MBDA as a comonomer. These novel polymers were characterized by $^{1}H-NMR$, IR, and differential scanning calorimetry (DSC). The novel phosphorus­containing poly(butylene terephthalate)s, referred to as FR-PBTs, exhibited interesting thermal and mechanical behavior, as well as superior flame retardancy. These properties are attributed to the effect of incorporating the rigid structure of DOP-MBDA and the pendant phosphorus group into the poly(butylene terephthalate) (PBT) homopolymer. The UL 94-V2 rating could be achieved with this novel flame retardant PBT, which has a phosphorus content as low as $0.5 wt\%$, and the FR-PBTs emitted less fumes and toxic gases than the PBT homopolymer.

• 공업화학
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• 제27권6호
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• pp.577-582
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• 2016

본 연구에서는 새로운 비할로겐-인계 난연제를 포함하는 경질 폴리우레탄 폼[BHP-RPUF]과 할로겐-인계 난연제를 포함하는 경질 폴리우레탄 폼[TCPP-RPUF] 그리고 난연제를 포함하고 있지 않은 폴리우레탄 폼[Pure-RPUF]의 기계적 물성 및 난연 특성에 대해 비교 분석하였다. 새로운 비할로겐-인계 난연제인 bis(3-(3-hydroxypropoxy)propyl) phenyl phosphate [BHP]는 disodium phenyl phosphate와 3-chloro-1-propanol의 반응을 통해 합성하였다. BHP-RPUF, TCPP-RPUF, 그리고 Pure-RPUF의 압축강도는 BHP-RPUF와 TCPP-RPUF가 비슷한 압축강도를 나타내었고, 열전도도에서는 BHP-RPUF가 TCPP-RPUF보다 낮은 값인 $0.023W/m{\cdot}K$를 갖는 것을 확인하였다. 반응속도와 SEM을 통해 기공의 크기를 측정하여 열전도도에 미치는 영향에 대하여 분석하였고, TGA 분석을 통해 내열성을 확인하였다. 난연성은 한계산소지수(Limited Oxygen Index) 측정 실험을 통하여, Pure-RPUF보다 BHP-RPUF에서 난연성이 향상됨을 확인하였다.

• Elastomers and Composites
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• 제37권4호
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• pp.224-233
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• 2002

본 연구에서는 EPDM 고무를 기지재로 사용하여 유기 난연제에 따른 난연 특성을 살펴보았다. EPDM 원료 고무에 카아본블랙, 스테아르산, 산화아연 가교제 등을 배합하여, 난연제가 첨가되지 않은 EPDM 고무 혼합물인 E0를 제조하였다. E0에 인계 난연제인 Tricresyl phosphate(TCP)를 인 함량이 0.5, 1, 1.5, 2 phr로 변량 첨가하여 E1~E4를 제조하였고, 적인을 인 함량이 3, 6, 9, 15 phr로 변량 첨가하여 E5~E8를 제조하였다. 또한 브롬계 난연제인 데카브로모디페닐옥사이드(DBDPO)와 염소계 난연제인 염화파라핀은 각각 브롬과 염소 함량을 3, 6, 9, 15 phr로 변량 첨가하여 E9~E12와 E13~E16을 각각 제조하였다. 난연제의 종류에 따라 제조된 고무시료의 인장 및 인열, 경도 등의 기본 물성을 시험하였으나, 난연제 함량에 의한 이들 변화는 커다란 차이를 보이지 않았다. 또한 난연 특성을 알아보기 위한 산소지수 시험에서는 E0의 산소지수가 23.5%를 나타내었으며, 난연제를 첨가한 고무의 산소지수는 23.7~28.5%를 나타내어서 난연 특성이 향상됨을 알 수 있었다. 또한 UL94의 수평법에 의한 시험에서 난연제로 적인을 사용한 EPDM 고무 혼합물의 난연 효과가 가장 우수함을 확인 할 수 있었고 반면 TCP를 첨가한 고무 혼합물의 경우, 블리딩(Bleeding)현상이 심하여 시험 결과의 재현성을 얻지 못하였다. 전반적으로 난연제의 종류에 관계없이 함량 증가에 따라 연소율이 감소하였고 난연 효과가 향상됨을 확인하였다.

• 한국응용과학기술학회지
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• 제23권4호
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• pp.328-339
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• 2006

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 $259^{\sim}347$ seconds, which means that the prepared coatings are good flame-retardant. With the $45^{\circ}$ 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 $30^{\sim}35%$, 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.

• 한국응용과학기술학회지
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• 제23권1호
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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.

• 한국응용과학기술학회지
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• 제24권1호
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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.

• 폴리머
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• 제26권5호
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• pp.623-633
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• 2002

적인을 이용한 ortho-cresol novolac (OCN)과 biphenyl계 혼합 에폭시 수지 조성물의 열적 특성과 난연 특성을 검토하였다. OCN과 biphenyl 에폭시의 부피비에 따라 5가지 조성물을 디자인하였으며, TGA 및 DTG, 그리고 UL-94V 테스트를 통해 난연 효과를 평가하였다. 충전제와 적인의 함량이 증가할수록 열적 성질 및 우수한 난연 효과를 보였으나, 과량의 적인을 적용하였을 경우에는 열안정성의 저하를 유발하였다. 복합재료의 기저 수지호서 OCN/biphenyl 혼합 에폭시를 사용하였을 경우 OCN의 내열특성과 biphenyl 에폭시의 높은 발포 특성에 기인하여 보다 향상된 난연 특성을 확보할 수 있었다. 적인을 적용한 에폭시 수지 조성물의 난연 기구는 표면에서 형성된 발포성 탄화층 (char-layer)의 열적 방어 효과로 판단할 수 있었다.

• 폴리머
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• 제30권3호
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• pp.238-246
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• 2006

본 연구에서는 인과 염소를 공유한 폴리우레탄(PU) 난연도료를 제조하여 인과 염소기의 시너지 효과에 의해 난연성을 더욱 향상시키는데 그 연구목적을 두었다. 합성은 tetramethylene bis (orthophosphate) 중간생성물(TMBO)과 neohexanediol trichlorobenfoate 중간생성물(TBA-adduct)인 이들 2종류 중간생성물과 1,4-butanediol 및 adipic acid의 4종류 단량체를 축합중합을 수행하여 4원공중합물(TTBA)을 얻은 다음, 합성된 TTBA류와 hexamethylene diisocyanate(HDI)-trimer인 경화제를 상온경화시켜 2성분계 PU 난연도료(TTBA-10C/ HDI-trimer=TTHD-10C, TTBA-20C/HDI-trimer=TTHD-20C, TTBA-30C/HDI-trimer=TTHD-30C)를 제조하였다. 제조된 TTHD류의 난연도료로서 도막시편을 제작하여 도막물성 측정용 시료로 사용하였다. 도막물성 측정 결과, 전반적으로 인 단독 함유보다 인과 염소를 공유한 쪽의 도막물성이 저하되는 경향을 나타내었다. 또한 난연성 시험으로서 수직법과 수평법의 연소성 시험법 및 $45^{\circ}$ Meckel burner법을 선정하여 난연성을 알아본 결과, 인 단독 함유보다 인과 염소를 공유한 TTHD류 쪽의 난연성이 더 좋게 나타난 것으로 보아 인과 염소에 의한 난연 시너지 효과가 일부 일어남을 인지할 수 있었다.