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Appl. Chem. Eng., Vol. 22, No. 6, December 2011, 679-684

분지형 폴리프로필렌/실리케이트 복합체의 유변학적 특성 연구
프러산터⋅윤경화⋅김연철†
공주대학교 신소재공학부 고분자공학 전공
(2011년 9월 2일 접수, 2011년 9월 22일 심사, 2011년 10월 12일 채택)

-

A Study on the Rheological Properties of Branched Polypropylene/silicate Composites
Prashanta Dahal, Kyung Hwa Yoon, and Youn Cheol Kim†
Department of Environment Engineering, Kongju National University, Cheonan 330-717, Korea
(Received September 2, 2011; Revised September 22, 2011; Accepted October 12, 2011)

고상(solid state) 반응과 용융(melt state) 반응을 이용하여 장쇄분지(long chain branch, LCB)를 가지는 분지화된 폴리프
로필렌(branched polypropylene, LCB-PP)을 제조하였다. 분지제(branching agent)로는 divinylbenzene (DVB), 1,4-benzenediol (RES), furfuryl sulphide (FS)가, LCB-PP/실리케이트 복합체를 제조하기 위해서는 층상 실리케이트가 사용되었다.
LCB-PP의 화학구조, 열적특성, 유변학적 특성을 적외선 분광기(FT-IR), 시차주사열용량분석기(DSC, TGA), 그리고 동
-1
적유변측정기(ARES)를 이용하여 분석하였다. LCB-PP의 화학구조는 3100 cm 에서 나타나는 분지제의 =C-H 신축진동
을 이용하여 확인하였다. DSC와 TGA의 결과로부터 고상반응보다 용융반응이 LCB-PP 제조에 보다 효과적이었고, 유
변학적 특성을 통하여 추가 확인되었다. 분지제 중에서는 FS가 가장 효과적이었다. LCB-PP의 경우 낮은 전단속도
영역에서 점도와 shear thinning tendency가 증가하였고, G'-G'' plot으로부터 탄성특성의 증가와 LCB의 도입에 의한 용
융상태의 불균일성(heterogeneousness)을 확인할 수 있었다. LCB-PP/실리케이트 복합체의 실리케이트 함량에 따른 유
변학적 특성을 관찰하였다. 실리케이트의 함량이 5 wt%인 경우 면찰 담화(shear thinning)와 G'-G'' plot에서의 기울기
변화가 가장 크게 나타났다.
Branched polypropylenes (LCB-PP) with a long chain branch were prepared by the solid-state and molt-state reaction.
Divinylbenzene (DVB), 1,4-benzenediol (RES), and furfuryl sulphide (FS) were used as branching agents of fabricate
LCB-PP/silicate composites. Chemical structures, thermal properties, and rheological properties of the LCB-PP were determined by FT-IR, DSC, TGA, and dynamic rheometer (ARES). The chemical structure of the LCB-PP was confirmed by
the existence of =C-H stretching peak of the branching agent at 3100 cm-1. From DSC and TGA results, the melting reaction
was more effective than the solid state reaction in the manufacture of LCB-PP, which was additionally certified by rheological
properties. Based on rheological properties, FS was the best for branching efficiency of PP. Compared to PP, LCB-PPs indicated an increase of complex viscosity in the low frequency and shear thinning tendency, and G'-G'' plot represented an
increase in elasticity and the heterogeneousness in a melt state. Rheological properties of LCB-PP/silicate composites were
observed with the silicate content. When 5 wt% silicate was added in LCB-PP, distinct changes in the shear thinning and
the slope of G'-G'' plots were observed.

Keywords: polypropylene, long chain branch, silicate, rheological property

1. 서

되는데, 일반적으로 PP는 선형 가지 구조와 좁은 분자량분포도로 인
하여 용융장력(melt strength)과 strain hardening 특성이 불량하여 블로
우 공정이나 발포 공정 등에 적용하기가 어렵다.
이러한 용융 특성을 개선하기 위한 방법으로 분자량 또는 분자량
분포도를 변경하거나[1,2], 실리케이트 또는 탄소나노튜브 등과의 나노
복합체를 형성하거나[3-8], 장쇄분지(long chain branch, LCB)를 도입
하기 위해 블렌드, 고상반응, 반응(용융) 압출, 그리고 전자빔 조사 등
의 방법들이[9-16] 연구되어 왔다. Bimodal의 분자량 분포도를 가지게
되면 고분자량 부분은 용융장력을 증가시켜주고 저분자량 부분이 가
공성을 향상시켜 주는 역할을 하게 되고, 장쇄분지가 도입되게 되면
용융상태에서 사슬간의 엉킴 현상이 일어나게 되고 유변학적으로 탄

론

1)

폴리프로필렌(polypropylene, PP)은 분자구조가 탄소와 수소만으로
이루어져 있기 때문에 리사이클링시 폴리머의 성능 저하가 없다는 점,
소각시에도 유해 독성 가스를 발행시키지 않는다는 점, 그리고 고분
자 소재 가운데 가장 가볍기 때문에 경량 소재로 주목을 받고 있어
범용 및 산업용 소재로서의 시장 규모를 확대해 나가고 있고, 상대적
으로 고 기술화 산업인 자동차 및 전자 산업으로의 확대가 요구되고
있다. 이들 산업으로의 적용을 위해서는 PP 발포에 대한 기술이 요구

† 교신저자 (e-mail: younkim@kongju.ac.kr)

<=?

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A Study on the Rheological Properties of Branched Polypropylene/silicate Composites

  • 1. Appl. Chem. Eng., Vol. 22, No. 6, December 2011, 679-684 분지형 폴리프로필렌/실리케이트 복합체의 유변학적 특성 연구 프러산터⋅윤경화⋅김연철† 공주대학교 신소재공학부 고분자공학 전공 (2011년 9월 2일 접수, 2011년 9월 22일 심사, 2011년 10월 12일 채택) - A Study on the Rheological Properties of Branched Polypropylene/silicate Composites Prashanta Dahal, Kyung Hwa Yoon, and Youn Cheol Kim† Department of Environment Engineering, Kongju National University, Cheonan 330-717, Korea (Received September 2, 2011; Revised September 22, 2011; Accepted October 12, 2011) 고상(solid state) 반응과 용융(melt state) 반응을 이용하여 장쇄분지(long chain branch, LCB)를 가지는 분지화된 폴리프 로필렌(branched polypropylene, LCB-PP)을 제조하였다. 분지제(branching agent)로는 divinylbenzene (DVB), 1,4-benzenediol (RES), furfuryl sulphide (FS)가, LCB-PP/실리케이트 복합체를 제조하기 위해서는 층상 실리케이트가 사용되었다. LCB-PP의 화학구조, 열적특성, 유변학적 특성을 적외선 분광기(FT-IR), 시차주사열용량분석기(DSC, TGA), 그리고 동 -1 적유변측정기(ARES)를 이용하여 분석하였다. LCB-PP의 화학구조는 3100 cm 에서 나타나는 분지제의 =C-H 신축진동 을 이용하여 확인하였다. DSC와 TGA의 결과로부터 고상반응보다 용융반응이 LCB-PP 제조에 보다 효과적이었고, 유 변학적 특성을 통하여 추가 확인되었다. 분지제 중에서는 FS가 가장 효과적이었다. LCB-PP의 경우 낮은 전단속도 영역에서 점도와 shear thinning tendency가 증가하였고, G'-G'' plot으로부터 탄성특성의 증가와 LCB의 도입에 의한 용 융상태의 불균일성(heterogeneousness)을 확인할 수 있었다. LCB-PP/실리케이트 복합체의 실리케이트 함량에 따른 유 변학적 특성을 관찰하였다. 실리케이트의 함량이 5 wt%인 경우 면찰 담화(shear thinning)와 G'-G'' plot에서의 기울기 변화가 가장 크게 나타났다. Branched polypropylenes (LCB-PP) with a long chain branch were prepared by the solid-state and molt-state reaction. Divinylbenzene (DVB), 1,4-benzenediol (RES), and furfuryl sulphide (FS) were used as branching agents of fabricate LCB-PP/silicate composites. Chemical structures, thermal properties, and rheological properties of the LCB-PP were determined by FT-IR, DSC, TGA, and dynamic rheometer (ARES). The chemical structure of the LCB-PP was confirmed by the existence of =C-H stretching peak of the branching agent at 3100 cm-1. From DSC and TGA results, the melting reaction was more effective than the solid state reaction in the manufacture of LCB-PP, which was additionally certified by rheological properties. Based on rheological properties, FS was the best for branching efficiency of PP. Compared to PP, LCB-PPs indicated an increase of complex viscosity in the low frequency and shear thinning tendency, and G'-G'' plot represented an increase in elasticity and the heterogeneousness in a melt state. Rheological properties of LCB-PP/silicate composites were observed with the silicate content. When 5 wt% silicate was added in LCB-PP, distinct changes in the shear thinning and the slope of G'-G'' plots were observed. Keywords: polypropylene, long chain branch, silicate, rheological property 1. 서 되는데, 일반적으로 PP는 선형 가지 구조와 좁은 분자량분포도로 인 하여 용융장력(melt strength)과 strain hardening 특성이 불량하여 블로 우 공정이나 발포 공정 등에 적용하기가 어렵다. 이러한 용융 특성을 개선하기 위한 방법으로 분자량 또는 분자량 분포도를 변경하거나[1,2], 실리케이트 또는 탄소나노튜브 등과의 나노 복합체를 형성하거나[3-8], 장쇄분지(long chain branch, LCB)를 도입 하기 위해 블렌드, 고상반응, 반응(용융) 압출, 그리고 전자빔 조사 등 의 방법들이[9-16] 연구되어 왔다. Bimodal의 분자량 분포도를 가지게 되면 고분자량 부분은 용융장력을 증가시켜주고 저분자량 부분이 가 공성을 향상시켜 주는 역할을 하게 되고, 장쇄분지가 도입되게 되면 용융상태에서 사슬간의 엉킴 현상이 일어나게 되고 유변학적으로 탄 론 1) 폴리프로필렌(polypropylene, PP)은 분자구조가 탄소와 수소만으로 이루어져 있기 때문에 리사이클링시 폴리머의 성능 저하가 없다는 점, 소각시에도 유해 독성 가스를 발행시키지 않는다는 점, 그리고 고분 자 소재 가운데 가장 가볍기 때문에 경량 소재로 주목을 받고 있어 범용 및 산업용 소재로서의 시장 규모를 확대해 나가고 있고, 상대적 으로 고 기술화 산업인 자동차 및 전자 산업으로의 확대가 요구되고 있다. 이들 산업으로의 적용을 위해서는 PP 발포에 대한 기술이 요구 † 교신저자 (e-mail: younkim@kongju.ac.kr) <=?