에너지함유 열가소성탄성체 적용을 위한 아지드화 폴리부타디엔/에틸렌-비닐아세테이트 공중합체 블렌드 제조

윤상원; 최명찬; 장영욱; 노시태; 권순길; Sang Won Yoon; Myung Chan Choi; Young-Wook Chang; Si-Tae Noh; Soon Kil Kwon

Korean Chemical Engineering Research, Vol.53, No.3, 282-288, June, 2015

DOI10.9713/kcer.2015.53.3.282 Export Citation

에너지함유 열가소성탄성체 적용을 위한 아지드화 폴리부타디엔/에틸렌-비닐아세테이트 공중합체 블렌드 제조

Preparation of Azidated Polybutadiene(Az-PBD)/Ethylene-Vinyl Acetate Copolymer(EVA) Blends for the Application of Energetic Thermoplastic Elastomer

윤상원, 최명찬, 장영욱 ^†, 노시태 , 권순길¹

한양대학교 융합화학공학과, 426-791 경기 안산시 상록구 한양대학로 55
¹국방과학연구소, 305-600 대전 유성구 유성우체국 사서함 35호

Sang Won Yoon, Myung Chan Choi, Young-Wook Chang^†, Si-Tae Noh , and Soon Kil Kwon¹

Department of Fusion Chemical Engineering, Hanyang University, 55 Hanyangdaehak-ro, Sangnok-gu, Ansan, Gyeonggi 426-791, Korea
¹Agency for Defense Development, P.O. Box 35, Yuseong-gu, Daejeon 305-600, Korea

E-mail:

초록

에틸렌-비닐아세테이트(EVA)와 아지드화 폴리부타디엔(Az-PBD)를 블렌드 함으로써 새로운 에너지함유 열가소성탄성체를 제조하고, 이들의 미세구조 및 제반물성을 SEM, DSC, DMA, 인장실험 및 연소시험으로부터 조사하였다. Az-PBD는 1,2-비닐기를 갖는 폴리부타디엔(PBD)을 첨가반응에 의해 비닐기를 브롬화시킨 후, NaN3를 이용하여 브롬기를 아지드기(-N3)로 치환시킴으로써 제조하였다. EVA/Az-PBD 블렌드는 EVA/Az-PBD 비율이 무게비로 각각 90/10, 80/20, 70/30이 되도록 용액 블렌딩으로 제조하였다. SEM, DSC, DMA 분석 결과 이들 블렌드는 부분적으로 상용성이며, EVA가 연속상을 이루고 Az-PBD가 분산상을 이루는 미세구조를 갖는 것을 알 수 있었다. 인장실험으로부터 Az-PBD 함량이 증가될수록 인장모듈러스 및 영구신장변형율이 증가되고 파단신율이 감소되는 경향을 보였으나, 제조된 모든 블렌드들은 700% 이상의 파단신율과 5% 이하의 영구인장변형율을 나타내어, 일반적인 탄성고무소재와 같은 특 성을 나타내었다. 또한, 연소 시 Az-PBD 함량 증가함에 따라 더 큰 불꽂이 발생되어 연소 시 더 높은 에너지를 발생 시킬 수 있음을 확인할 수 있었다.

A new energetic thermoplastic elastomer based on the azidated polybutadiene(Az-PBD)/ethylene vinyl acetate copolymer (EVA) blends was prepared, and structure and properties of the blends were invetigated by SEM, DSC, DMA, tensile testing and combustion test. The Az-PBD was synthesized via a two-step process involving the addition reaction of commercially available 1,2-PBD with Br2 and subsequent nucleophilic substitution reaction of the brominated PBD with NaN3. EVA/Az-PBD with 90/10, 80/20, 70/30 (wt/wt) was prepared by a solution blending. SEM, DSC, and DMA results revealed that the blends are partially compatible and Az-PBD is dispersed in continuous EVA matrix. Tensile test showed that modulus and tension set increased while elongation-at-break of the blends decreased with increasing Az-PBD content in the blends, but all the blends showed a elongation at break as high as 700% and a tension set of less than 5%, indicating that the blends are typically elastomeric. Combustion test showed that, with increasing Az-PBD content in the blend, higher energy can be released.

Keywords:Energetic Thermoplastic Elastomer (ETPE);Azidated Polybutadiene (Az-PBD);Ethylene-vinyl Acetate (EVA);Blend

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[Related Articles]

[1] Hsieh WH, Peretz A, Huang IT, Kuo KK, J. Propul., 7(4), 497 (1991)

[2] Miyazaki T, Kubota N, Propel. Explos. Pyrotech, 17(1), 5 (1992)

[3] Talukder MAH, Lindsay GA, J. Polym. Sci. A: Polym. Chem., 28(9), 2393 (1990)

[4] Eroglu MS, Guven O, J. Appl. Polym. Sci., 60(9), 1361 (1996)

[5] Varma IK, Macromol. Symp., 210, 121 (2004)

[6] Eroglu MS, Guven O, Polymer, 39(5), 1173 (1998)

[7] Bui VT, Ahad E, Rheaume D, Raymond MP, J. Appl. Polym. Sci., 62(1), 27 (1996)

[8] Xue H, Gao HX, Shreeve JM, J. Polym. Sci. A: Polym. Chem., 46(7), 2414 (2008)

[9] Shin JA, Lim YG, Lee KH, Bull. Korean Chem. Soc., 32(2), 547 (2011)

[10] Manser GE, Fletcher RW, “Energetic Thermoplastic Elastomers,” Summary Report, Office of Naval Research Contract N00014-87-C-0098(1988). (1998)

[11] Diaz E, Brousseau P, Ampleman G, Prud'homme RE, PROPELLANT-EXPLOS-PYROTECH, 28(3), 101 (2003)

[12] Pisharath S, Ang HG, Polym. Degrad. Stabil., 92(7), 1365 (2007)

[13] Duo YQ, Tan HM, Chen FT, J. Appl. Polym. Sci., 83(14), 2961 (2002)

[14] Walker BM, Rader CP, “Handbook of Thermoplastic Elastomers,” 2ndEd. New York(1998). (1998)

[15] De SK, Bhowmick AK, “Thermoplastic Elastomers from Rubber-plastic Blends,” Ellis Horwood, New York(1990). (1990)

[16] Jin SH, Song GS, Lee DS, Korean Chem. Eng. Res., 50(1), 167 (2012)

[17] Choi MC, Chang YW, Noh ST, Kwon JO, Kim DK, Kwon SK, J. Korean Ind. Eng. Chem., 20(4), 375 (2009)

[18] http://www.jsr.co.jp/jsr_e/pd/tpe_rb.shtml.

[19] www.dupont.com/content/.../elvax_40l_03.pdf.

[20] Shi XM, Zhang J, Jin J, Chen SJ, eXPRESS Polym. Lett., 2(9), 623 (2008)