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1 서울대학교 공학기술과경영 9 강

2 목차 1. 석유화학과폴리올레핀 2. 폴리올레핀 ( 종류, 용도, 가공 ) 3. 폴리올레핀제조공정 4. 올레핀중합촉매 Ziegler-Natta 촉매 Metallocene 촉매 5. 한화토탈의촉매개발및상업적용사례

3 석유화학과폴리올레핀

4 석유화학산업? 석유 / 납사및천연가스로부터화학기초유분을생산하고, 이를원료로각종중간유도품과합성수지 ( 플라스틱 ), 합성섬유 ( 폴리에스터, 나일론등 ), 합성고무등의기초화학소재를생산하는산업

5 우리나라의석유화학산업 Ethylene Capacity (2014) 세계 4 위생산규모 ( 14 년 ) - 국내에틸렌생산규모 : 8.5 백만톤 / 년 - 세계점유율 : 1.9%( 90) 5.3%( 14) 국내제조업중 4 위규모 - 생산액 : 110 조원 - 제조업비중 : 2.8% ( 90) 7.4%( 13) 국내 5 위수출품목 - 수출 : 482 억불 ( 총수출의 8.4%) - 무역수지 : 21 억불 ( 90) 318 억불 ( 14) *Source : 한국석유화학협회

6 폴리올레핀산업 세계 Polyolefin 산업 Major polymer 총수요 ( 14): 2.24억톤 Polyolefins 수요 : 1.43억톤 (62%) - PP 5,800 만톤, PE 8,500 만톤 국내 Polyolefin 산업 총생산능력 : 930 만톤 / 년 - PP : 8개사 424 만톤 - PE : 7개사 500만톤 한화토탈 : 140 만톤 / 년 - PP 3개라인 70만톤 - PE 4개라인, 70만톤

7 폴리올레핀 1. 폴리올레핀종류 2. 용도 3. 가공방법

8 Polyolefin 의종류 PE (polyethylene) PP (polypropylene) Rubber/Elastomer Specialty Polymer LDPE (low density PE) EVA (ethylene-vinylacetate copolymer) HDPE (high density PE) LLDPE (linear low density PE) UHMWPE (ultra-high molecular weight PE) Homo-PP Random PP (propylene/ethylene) Ter-PP (propylene/ethylene/butene-1) Block PP (homo-pp+epr) EPR (ethylene-propylene rubber) EPDM (ethylene-propylene-diene monomer) POE (polyolefin elastomer, ethylene/octene-1) PB-1 (polybutene-1) PMP (poly(4-methylepentene-1)) COC (cyclic olefin copolymer, norbornene/ethylene)

9 Polyethylene (PE) HDPE density 0.945~0.965 g/cc LLDPE density 0.920~0.945 g/cc LDPE density 0.915~0.925 g/cc EVA VAM content : max 30wt%

10 Polypropylene (PP) Isotactic PP Syndiotactic PP Atactic PP

11 PE, PP 소재의특징 포화탄화수소구조의결정성고분자 뛰어난화학적안정성 친환경적 ( 무독, 무취 ) Recyclable 가격대비우수한물성 물성조절용이 ( 분자량, 분자량분포, 공중합 ) Melting temperature HDPE: 130~135 High performance polymer Technical polymer Basic polymer PC PPO SMA ABS PI PEI PES COC/COP PSU PEK FP LCP PPS PA4,6 PBT/PET UHMWPE POM PA6/66 EVA PMMA PP LDPE LLDPE PS SAN HDPE PVC PP : 160~165 Amorphous Crystalline

LDPE LLDPE/HDPE Iso-PP Syndio-PP Density(g/cc) 0.915-0.

91 Tm 95-120 115-135 160-165 140-150 Tg -100-100 -20-6

12 LDPE LLDPE/HDPE Iso-PP Syndio-PP Density(g/cc) Tm Tg Young Modulus (GPa) Solvent resistance < 0.3 < medium high high medium PP 의결정모양

13 PE, PP 수지의용도 생활용품 식품용기 / 포장 의료용품 전기전자 건축 / 농업

14 자동차소재 (PP, PP compound) 자동차경량화 ( 연비향상 ) - PP 비중 0.92 g/cc 차체중량의 10~15% 는 plastics 소재, 그중절반이폴리올레핀소재

15 PE Pipe (portable water and gas supply) LTHS(Long Term Hydrostatic Strength) 50 년수명보장

16 Encapsulation Layer of Solar Cell (EVA) Ethylene-Vinylacetate copolymer EVA Sheet

17 UHMWPE (Ultra High Molecular Weight PE) 인장강도, 내마모성, 내충격성탁월 방탄복

18 Battery Separator Film (LIBS) UHMWPE Porous film for LIBS

19 PE, PP 수지의가공방법 Extrusion ( 압출성형 ) Injection Molding ( 사출성형 ) Blow Molding ( 중공성형 ) Extrusion Rotomolding ( 회전성형 ) Compression Molding ( 압축성형 ) Calendering ( 캘린더링 ) Casting ( 캐스팅 ) Injection Molding Vacuum Foaming ( 진공성형 ) Foaming ( 발포성형 ) Film

20 폴리올레핀제조공정

better polymer morphology Polymerization Monomers Solvent Additives

21 올레핀중합공정 CH 2 =CH-R AlEt 3 Monomers + Co-catalyst + Catalyst Pre-polymerization Mild polymerization at low temp (10~30 ) for better polymer morphology Polymerization Monomers Solvent Additives Separation/Drying Removal of solvent & residual monomers Extrusion PE/PP Pellet

22 중합공정의종류 중합조건에따른분류 Solution process (high temp) Slurry process - Diluent slurry (iso-butane, n-hexane) - Bulk slurry (liquid C3 ) Gas-phase process 반응기형태에따른분류 Autoclave Reactor for LDPE Tubular Reactor for LDPE (PFR) CSTR (Continuous Stirred Tank Reactor) Loop reactor FBR (Fluidized Bed Reactor) MZCR (Multi-Zone Circulating Reactor)

23 Autoclave LDPE Process (radical polymerization) 200~300, 1300~2000 bar ICI (1938)

24 Tubular LDPE Process (radical polymerization) BASF(1953) Lyondell Basell 200~ ~3200 bar

25 CSTR (Continuous Stirred Tank Reactor) Mitsui s CX HDPE Process (Hx slurry, 80 ) Mitsui s Hypol PP Process (C3 bulk, 70 ) Hoechst HDPE Process (Hx slurry) Solution PE Process (150~350 ) Multi-reactors for broad MWD #1 #2 Mw(1) Mw(2)

26 Loop Reactor Phillips PE process (iso-butane slurry) LyondellBasell s Spheripol PP Process (C3 bulk slurry)

27 FBR (Fluidized Bed Reactor, Gas-phase) Unipol PE, PP Process BP LLDPE Process

28 MZCR (Multi-Zone Circulating Reactor, Gas-phase) Spherizone PP Process (LyondellBasell)

29 Residence Time Distribution

30 폴리올레핀종류별중합공정

31 올레핀중합촉매 1. Ziegler-Natta 촉매 2. Metallocene 촉매

32 Catalyst in olefin polymerization

Classification of Catalyst Types Peroxides LDPE, EVA 250~350, 2000~3000 atm O O R O C OO C O R R O C O OO C R (Peroxides) Phillips catalyst PE (HDPE, MDPE) Cr-type supported in SiO

33 Classification of Catalyst Types Peroxides LDPE, EVA 250~350, 2000~3000 atm O O R O C OO C O R R O C O OO C R (Peroxides) Phillips catalyst PE (HDPE, MDPE) Cr-type supported in SiO 2 Ziegler-Natta catalysts PE, PP TiCl 4 /MgCl 2, TiCl 4 /MgCl 2 /SiO 2 : PE TiCl 4 /ID/MgCl 2 : PP Single-site catalysts PE, PP, POE Metallocenes Non-metallocene (Post-metallocenes)

34 Catalyst Technology Evolution Timeline

35 Phillips Catalyst Catalytic sites for ethylene polymerization

Ziegler-Natta Catalyst Historical development of Z-N

Giulio Natta (1903~1979, Italy) Discovered TiCl4/AlEt2Cl

Mülheim (1953) Discovered isotactic polypropylene at the

36 Ziegler-Natta Catalyst Historical development of Z-N catalyst Prof. Karl Ziegler (1898~1973, Germany) Prof. Giulio Natta (1903~1979, Italy) Discovered TiCl4/AlEt2Cl catalyst for polyethylene at the Max-Planck Institute in Mülheim (1953) Discovered isotactic polypropylene at the Polytechnical Institute of Milan (1954). Nobel Prize in Chemistry (1963)

38 Mechanism for Ziegler-Natta Catalysis

39 Molecular Structure of Polypropylenes Isotactic PP High Tm (161~164 ) High modulus Most of commercial PP Syndiotactic PP 3 1 -helical structure of iso-pp crystal Low Tm (Tm 130~140 ) Low modulus Meta-stable crystalline structure Not successful in commercialization Atactic PP Amorphous and sticky Used for limited application (hot melt)

40 Generations of polypropylene catalysts (generations)

41 Commercial Z-N Catalysts for PP Main catalyst Cl Ti Mg Catalyst support : MgCl 2 Active species : TiCl 4 Internal electron donor : Phthalate, Diether, etc. Ionic radius Mg Å Ti Å Cocatalyst Activator (cocatalyst) : Al(Et) 3 ; Ti(4+) Ti(3+)-Et External electron donor: R 2 Si(OCH 3 ) 2 ; istacticity

Titanium-Olefin Complex The electrons from olefin

titanium π-orbitals of olefin monomer (ethylene)

slip into the olefin s π- antibonding orbital,

43 Titanium-Olefin Complex The electrons from olefin s π-bonding fit nicely into the empty orbital of titanium π-orbitals of olefin monomer (ethylene) The electrons from one of the filled orbitals can slip into the olefin s π- antibonding orbital, making the titanium-olefin complex stronger (back donation)

44 Propylene Insertion Mechanism Propylene >5,000 units/ti*/sec Polymer >1 개 (Mw 20 만 )/Ti*/sec

45 Stereoregularity of Z-N Catalysts Prochirality of adsorbed propylene

46 Stereoselective propylene insertion re-enantioface si-enantioface polymer chain C ED ED Cl Mg Ti Mg propylene Ti Corradini et al. Acc. Chem. Res. 2004

bridge Bridge Mode on (110) and (100) Zip Mode on (110) MgCl

47 Adsorption of Internal Donors on MgCl 2 Three types of adsorption modes on MgCl 2 surface Chelate Mode on (110) bridge Bridge Mode on (110) and (100) Zip Mode on (110) MgCl 2 support zip chelate (110) bridge Correa et al. Macromolecules 2007

48 Catalyst & Polymer Morphology Replication of catalyst morphology Porous catalyst 20s 5min 2hrs Non-porous catalyst

49 Fragmentation of catalyst particle

50 6 sec(1.8g-pp/g-cat) 1 min (10-14 g-pp/g-cat) 30 min (450 g-pp/g-cat) Dark spots : catalyst fragments

51 Monomer diffusion effect Idealized simulation to demonstrate the effect of particle morphology on mass transfer resistance R r C CBulk C, CBulk : Monomer concentration r : Distance from particle center R : Radius of the particle III II Rp(r) = k(t)*c(r, t) I III : Intrinsic activity of a very porous particle (no diffusion limitation)

53 올레핀중합촉매 1. Ziegler-Natta 촉매 2. Metallocene 촉매

54 Metallocene Complexes? Ferrocene Sandwich structure (G. Wilkinson & R. B. Woodward, 1952)? Metallocene catalysts for polyolefins Ferrocene 6e - d6e - 6e - 18e - (stable) M = Ti, Zr, Hf

Historical development of metallocene catalysts Professor Walter Kaminsky (University of Hamburg) 1952 Ferrocene (Fisher & Wilkinson) 1973 Addition of small amount of water increased activity (Meyer

55 Historical development of metallocene catalysts Professor Walter Kaminsky (University of Hamburg) 1952 Ferrocene (Fisher & Wilkinson) 1973 Addition of small amount of water increased activity (Meyer & Breslow) 1977 Discovered MAO (AlMe 3 +H 2 O) and high activity Cp 2 ZrMe2/MAO system (W. Kaminsky & Sinn) 10,000 times increase of catalyst activity Kaminsky Catalyst 1982 C2-symmetry ansa-metallocene (Brintzinger) 1984 Isotactic PP from ansa-metallocenes (John A. Ewen)

56 PE catalyst technoloty Evolution Timeline

57 Examples of Metallocene Catalysts For polyethylene LLDPE, POE For polypropylene C 2 -symmetry (ansa-metallocene) Isotactic PP Cs-symmetry Syndiotactic PP

58 Stereoselective insertion of monomers rac-et(ind) 2 ZrCl 2 (ansa-metallocene)

59 Cocatalysts for Metallocenes MAO (methylalumoxane) Borane & Borate Plausible structures of MAO

Narrow MWD Broad MWD Homogeneous comonomer

optical property Heterogeneous comonomer

60 Metallocene vs. Ziegler-Natta Polyethylene Isotactic Polypropylene Metallocene Ziegler-Natta Metallocene Ziegler-Natta Narrow MWD Broad MWD Narrow MWD Broad MWD Homogeneous comonomer distribution High dart impact strength & optical property Heterogeneous comonomer distribution More insertion errors Lower hexaneextractable Less insertion errors Higher Tm and higher flex. modulus

61 한화토탈의촉매기술 촉매개발및상업적용사례

62 Polyolefin R&D Product & application Process R&D Catalyst

63 한화토탈의촉매기술개발 핵심요소기술 공정운전성 Morphology 생산성 Activity Support, I/D Support Catalyst Design I/D, E/D Isotacticity 물성 공정운전성 (MI 조절 ) H2 response I/D, E/D Support, I/D I/D, E/D Mol. wt Distribution 가공성물성 C2 =, C4 = response I/D (Internal Donor) E/D (External Donor) 제품범위 (random, ter, block)

Theoretical Approach for Catalyst Design Computational Calculation (DFT) DMol3 program included in Material Studio Cluster model to describe (110) and (100) surface of MgCl2 support Spin-unrestricted

64 Theoretical Approach for Catalyst Design Computational Calculation (DFT) DMol3 program included in Material Studio Cluster model to describe (110) and (100) surface of MgCl2 support Spin-unrestricted electronic state to calculate Ti 3+ electronic state Prediction of catalytic activity and isotacticity from internal and external donors structure Design of new internal donors Development of new high performance catalysts

65 Prediction of catalyst activity Background

66 Phthalate Donors Chelate mode ΔE ad =-42.7kcal/mol Zip mode ΔE ads = kcal/mol

67 Prediction of isotacticity

68 각공정별특화된고성능촉매기술 HDPE LLDPE PP (Hypol) PP (Spherizone) Z-N 촉매 고활성 Z-N Z-N 촉매 담지형 Metallocene CMR-free Z-N 고성능 Z-N 1 일반 HDPE 용고활성촉매 2 미분체형 PE 용촉매 (morphology 우수 ) 1 고투명, 고장력필름용 metallocene 촉매 2LDPE-like LLDPE 용 Met 촉매 1 고활성 / 고입체규칙성촉매 (25 μm, 球形 ) 2Non-phthalate PP 촉매 1 고활성 / 고입체규칙성촉매 (70 μm, 球形 ) 3UHMWPE 용촉매

69 촉매문제에의한공정트러블사례 (Pilot Plant) 촉매 morphology 불량 (BD, fines), 과반응

70 고성능 PP 촉매 (excellent activity and morphology) Catalyst particles Polymer

/ 년 - LDPE/EVA 40 만톤, HDPE/LLDPE 30 만톤, PP 72 만톤 R&D 분야촉매 ( 중합, 화성

72 한화토탈 (Hanwha Total Petrochemical Co., Ltd) 매출 (2015): 8.3 조원 에틸렌생산능력 : 109 만톤 / 년 주제품 : 합성수지, 기초유분 / 화성제품, 석유제품 합성수지 142 만톤 / 년 - LDPE/EVA 40 만톤, HDPE/LLDPE 30 만톤, PP 72 만톤 R&D 분야촉매 ( 중합, 화성 ) 수지제품복합수지공정화성 / 에너지선행기술 대산석유화학단지한화토탈 한화종합화학 LG화학롯데케미칼현대오일뱅크 여수석유화학단지 울산석유화학단지

2013.. ....c04....

2013.. ....c04.... 플라스틱뉴스 _ 봄 발행인 편집인 발행처 주 소 전 화 팩 스 방한홍 한화케미칼 대전광역시 유성구 가정로 76 042/865/6400 042/861/2611 인쇄처 학예 COM. 전 화 042/625/1821 인 쇄 2013. 3. 발 행 2013. 3. 등록번호 서울 바 00407호 등 록 1972. 5. 20 본지는 한국도서잡지윤리위원회의 실천요강을 준수합니다.