chapter 1-Introduction 2017-upload-170301 - 서강대학교 …home.sogang.ac.kr/sites/sgpml/testmenu2/Lists/b12... · · 2017-03-06고분자공학CBE3007 Chapter 1. Introduction

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Chapter 1. Introduction

CBE3007고분자공학

[email protected]: R515A

Phone: 02-705-8483

고분자재료연구실

Chapter 1. Introduction고분자공학 CBE3007

l Textbook: R.J. Young and P.A. Lovell,“Introduction to Polymers”, 3rd ed., CRC Press, NY (2011)

l Syllabus: Refer to SAINT.

l 강의자료및 Reading Assignment: http://sgpml.sogang.ac.kr/announcement

l 출석부 사진 (2.5 x 3.0 cm2) 제출: 3월 6일정경환 [email protected]

l Outline: 고분자합성 > 고분자물성 > 고분자가공

강의소개

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TEXTBOOK

고분자재료연구실3


Week 수 업 내 용 1

1Introduction to Polymers

석유화학산업 및 화학산업

2Definition and Nomenclature (Chapter 1)

고분자의 정의, 장l단점, 역사 및 명명법

3Molecular Weight and Its distribution

Degree of polymerization, molecular weight and its distribution

4Intermolecular Forces of Attraction

Intermolecular forces, solubility parameter

5Transition in Polymers I

유리전이온도의 정의, free volume, WLF equation

6Transition in Polymers II

온도에 따른 고분자의 상태변화 및 응용

7Special Application of Polymers

고분자 응용 분야

8 중간고사

Schedule 1

4

3


Week 수 업 내 용 2

9Crystalline Polymers I

Transition between crystallization and melting

10Crystalline Polymers II

Kinetics and model of crystallization

11Characterization of Transitional Behavior

정의 및 특성

12Rubber Elasticity

Factors affecting rubber elasticity

13Mechanical Properties of Polymer

고분자의 기계적 성질, 파괴현상 및 측정법

14설계 I: 고분자의 응용분야에 대한 설계 및 세미나 I

(창의성, 협동능력, 발표력)

15설계 II: 고분자의 응용분야에 대한 설계 및 세미나 II

(창의성, 협동능력, 발표력)

16 기말고사

Schedule 2


QnA

1. 재료의 종류 및 차이

2. 고분자 (플라스틱)란 무엇인가? (연상되는 것?)

3. 왜 고분자 (polymer)인가?

4. 고분자의 특징 (기계적 강도, rod: plastic vs. wood)

5. 고분자의 종류 및 용도

6. 고분자의 문제점

7. 가장 중요한 특성은?

8. 배우고 싶은 것 또는 알고 싶은 것?

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Chapter 1. Introduction to Polymers

1. Petrochemical Industry2. Plastics or Polymers



목 차

1. Petrochemical Industry1) Petrochemical Industry2) Routes to Products3) 화학산업

2. Plastics or Polymers1) Definition of Polymers2) Origin and Progress3) History of Polymers4) Applications

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1. Petrochemical Industry

1) 정의 (석유화학산업)

석유 (나프타) 또는 천연가스 (shale gas)등을 원료로하여 합성수지 (플라스틱), 합성섬유원료, 합성고무 등화학제품을 제조하는 산업

• 생산액 ‘13 (110 조원/제조업 7.4%)

• 에틸렌 생산량: 8,248 천톤/년 (2015년)- 전체 base chemical의 ~ 40%- 세계 5위 (5%)

• 자본집약적/기술집약적 산업

• 산업의 쌀 제공


2) Routes to Products

10

정유 및 석유화학산업 계통도

6


석유화학제품 계통도 I


석유화학제품 계통도 II

2015 생산량 %기초원료 27,014함성수지 13,106 36.4합섬원료 6,973 19.4합성고무 947 2.63중간원료 14,946 41.5합계 35,972

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부가가치 창출



석유화학 전Ÿ후방산업

석유정제공업

(後方産業: Up-stream)

(前方産業: Down-stream)

합성수지56%

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3) 화학산업의 범위



글로벌 화학사업: 5조$

36.3%

35.8%

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4) 한국 화학산업

(조원)


화합물 및 화학제품 생산액

2011년(103조원)

합성수지/ 합성고무 생산액: 43.1 조원 (42.0%)

단위 (백만원)

10


Future of Chemical Engineering

식량문제:• 2025년 세계 인구: 85억으로 예상 (1.7 % 증가율).

• 쌀 생산량: 1985년까지 약 3% 증가, 그 이후 ~1% 증가

지구 온난화 문제: CO2 고정화

Energy (ET or GT): • 화석연료의 대체 에너지 개발 필요 (RE)


1. Specialty2. Flexibility3. Creativity4. Applicability

화학공학자의 요건

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목 차

1. Petrochemical Industry

2. Polymers or Plastics1) Definition of Polymers2) Origin and Progress3) History of Polymers4) Applications


metals ceramics

polymers

Materials • hard and brittle• tough

• rubbery to rigid• light• corrosion-resistant

•기계적성질

•열적성질

•용해성

Materials

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2. Plastics or Polymer

1) Definition of Polymerspolymer: polloi (many) + meros (part)

monomers고분자: 분자량 104 ~ 106

• momomer: one + part• dimer, trimer, tetramer, etc.• oligomer: a few monomer

v macromolecule: large + complex molecule


Polymers

• Natural polymers: from plants and animals, such as rubber, polysaccharides, starch, cellulose and glycogen

• Proteins, nucleic acids and

• some inorganic large molecules

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Boiling Points of Alkanes


Properties of Alkane Series

No of C in Chains

State and Propertiesof Materials

Uses(Dependent on Chain Length)

1 - 4 Simple gas Bottled gas for cooking

5 - 11 Simple liquid Gasoline

9 - 16 Medium-viscosity liquid

Kerosene

16 - 25 High-viscosity liquid Oil and grease

25 - 50 Simple solid Paraffin wax candles

1000 -3000

Tough plastic solid PE bottles and containers

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1) Definition of Polymer

(1) 특징

Ø large size and chain-like structure

Ø long chain and flexible: entanglement

Ø MW distribution and average MW

Ø dynamic• function of time: 시간에 따라 물성이 변함

• 온도를 높이면 변한 물성에 따른 운동을 눈으로 관찰가능

Ø viscoelastic:• function of time and strain rate (변형 속도)

(저분자의 경우: viscosity only)


Structure-Processing-Property Relationships

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(2) 장점

Ø mechanical properties: tough vs. waxØ light to replace metal∴ emission 감소와 연료 절약

Ø processability at low T (200~300 ℃)

Ø low price, 내부식성

Ø molecular tailoringØ low energy required to produce on volume basis

∴ 금속의 1/10 정도의 에너지로 packing 가공 가능



(3) 단점

Ø 내열성문제

ex) 범용고분자 < 100 ℃

engineering plastics < 100~350 ℃

Ø 공해문제: 시각적 공해 recycling

우리나라 쓰레기의 10% 차지 (주로 package용)

ex) 스티로폼: 98% 공기 + 2% PS

부피가 커서 압축하여 처리하는 등 쓰레기 처리가 어려움

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Use Temperature


Polymer Pyramid

C&EN, p.23, Feb. 29, 2016

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내열성 · 기계적 특성 우수: 금속 대체 (고부가가치)

Engineering Plastics (EP, ENPLA)


PEEK

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자동차

산업용 구조물

잡화용 소비재

전기·전자기기

EP의 주요용도


슈퍼 EP의 특성

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슈퍼 EP의 응용분야


슈퍼 EP의 시장구성

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4) General View on Plastics

l Cheap and nasty

• Poll neutral 15%

no view 25%

essential and approved 35%

opposed 25%

l plastic packaging but poor image of plastics

l Plastic as a term of abuse

• Plastic smile, Plastic bread, Plastic operation

• Plastic에 대한 부정적 인식 반영


3 Major Markets: Packaging

v Automotive

v Building and Construction

v Packaging; • the largest application (26% in Europe)

• 78 MMT (a total value of $ 260B, 2013)• 2X within 15 years and 4X by 2050 (318 BMT)• recycled (39.5%), energy recovery (38.6%), landfill (22%)

• $ 839B in 2015 to $ 998B in 2020

lightweight, shatterproof and eco-friendly solution for premium single-serve wine on the go

For millennials• Plastic is (still) king• Transparency a necessity• Trending now• Packaging personified

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Plastic Packaging

“Waste not, want not”


Public antagonism

recycle

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43

NU

MB

ER O

F GR

ADES w

ith FDA APPR

OVA

L


Plastic Packaging

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2) Classification

l 천연고분자 (natural polymers) ex) wool, cellulose, starch, rubber, diamond, etc.

l 합성고분자 (synthetic polymers)

원유 (crude oil) C4, C5, C6 … C12

v고분자 (유기/무기) • 많은 저분자들이 함께 연결되어 이루어진 거대분자

(macromolecules) • 보통의 저분자화합물에 비해 분자량이 큼• 금속재료나 세라믹과 같은 무기재료와는 다른 성질• 또한 합성수지, 합성고무, 합성섬유 등의 원료

v Plastic: 합성수지 + 성형품

정제


Types of Materials

Materials Advantages Disadvantages Examples Polymers (nylon, silicon, polyester)

ResilientEasy to fabricate

Not strongDeform with timeMay degradable

Suture, blood vessels, hip sockets

Metals (Ti and its alloys, Ag, Au, stainless steels)

Strong, tough, Ductile

May corrodeDenseDifficult to prepare

Joint replacement, dental root implant, pacers, bone plates and screws

Ceramics (alumina, zirconia, hydroxyapetite)

Very Biocompatible

BrittleNot resilient

Dental and orthopaedic implants

Composites (carbon-carbon, bone cement)

Strong Tailor made

Difficult to prepare Dental resin, bone cement

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2) Origin and Progress

(1) Natural Polymers (Organic)

• cotton, wool: labor intensive

• protein: DNA, RNA

• rubber: 천연고무

• polysaccharide: cellulose, starch (monosaccharide)

§ Biopolymers

§ Inorganic

§ MARLBORO


2-3. Origin and Progress

(2) Semi-synthetic Polymer (modification)

A. 천연고무(Natural Rubber, NR) vulcanization• 1820 T. Hancock:

mastication of NR (≥ 106) 가공 용이

• 1839 C. Goodyear: NR에 S8을 첨가하여 탄성을 증가

(점착성 제거)

• 1843 A. Parks: patent for water-proof fabric (which was later sold to C. Macintosh)

• 1844 Goodyear/Hancock: patent for vulcanization(network 구조, X-linking)

• 1851 N. Goodyear: patent for ebonite, vulcanite, hard rubber

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Natural Rubber

• Called India rubber or caoutchouc• Polymer, MW of 100,000 ~ 1,000,000• harvested mainly in the form of the latex from rubber

trees (latex is a sticky, milky colloid)

§Rubber (elastomer): polymer, cis-1,4-polyisoprene §Gutta-percha (rigid latex): specifically trans-1,4-

polyisoprene

Isoprene(2-methyl-1,3-butadiene)


Vulcanization

S8(cyclo-)octa sulfur

less sticky and superior mechanical properties by crosslinking (vulcanization)

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Cellulose Nitrate

B. Nitrocellulose or Cellulose Nitrate

3HNO3+ C6H10O5 → C6H7(NO2)3O5 + 3H2O

nitronium ion or nitryl ion NO2

+

b (1→4) linked D-glucose units

(C6H10O5)n or Cell-OH


Cellulose Nitrate

Cell-OH + HNO3 Cell-ONO2 + 3 H2O

• 1846 C. Shoenbein: 솜 + 질산 gun cotton (explosive)

• 1862 A. Parkes: Parkesine (plasticized nitrocellulose, 경탄성체)1st man-made plastic for ivory: moldable under T and Pcommercially not viable due to high cost of solvent

• 1863 J. W. Hyatt: 1st man-made thermoplastic

Nitrocellulose CelluloidTM

(collodion)

P.Tcamphor

as plasticizer 당구공/초창기 영화필름특수종이: 소진탄피

Cellodion (pyroxylin solution): flammable solution of partially nitrated cellulose in ether or alcohol with a large amount of camphor as additive

Cf. 담배종이: 궐련지 (마섬유/화학펄프)

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Nitrocellulose

also known as cellulose nitrate, flash paper,

flash cotton, guncotton, and flash string

3HNO3+ C6H10O5 → C6H7(NO2)3O5 + 3H2Onitronium ion or nitryl ion

NO2+


Glycosidic bond

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Cellulose

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C. Cellulose triacetate and Cellulose acetate - Cell-OH + 3(CH3CO)2O Cell-O(OCCH3) + CH3COOH

§ cigarette filter

§ wash-and-wear fabric

in H2SO4

hydrolysis

cellulose acetate(< 2 acetyl group/unit)

resistant to weak acids largely stable to mineral and fatty oils as well as petroleumbiodegradable and the raw material is a renewable natural polymer

Cellulose diacetate


Cellulose Triacetate

Acetyl (Ac)acetate

Vinyl acetate

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(Viscose) Rayon

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D. (Viscose) Rayon: 1891 by L.M.H. Bernigaut

- Cell-OH Cell-ONa Cell-CS2ONa (cellulose xanthate: viscose)

ü film (sheet: cellophane) ® packaging film ü fiber by spinning through orificeü sponges

§ physical conversion regenerated cellulose (재생섬유)

§ CS2: 공해문제로 지금은 사용되지 않음(replaced by N-Methylmorpholine N-oxide as solvent)

Cell-OH + CS2 H2SO4

CS2


Rayon: Viscose Method

soluble polymer (viscose)

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Reaction

• 1st step: dissolution in NaOH to form alkali cellulose, [C6H9O4-ONa]n

[C6H9O4-ONa]n + nCS2 → [C6H9O4-OCS2Na]n

• 2nd step: hydrolysis of the xanthate groups [C6H9O4-OCS2Na]2n + nH2SO4 →

[C6H9O4-OH]2n +2nCS2 + nNa2SO4

H2COS2 → H2O + CS2

ROCS2−M+ (R = alkyl; M+ = Na+, K+)


Natural Polymers as Biomaterials

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Difference Bet Polymer and Biopolymer

• are synthesized in living organisms present in biological systems and have a well defined, specific structure, more advance and complex in contrast to other polymers like synthetic polymers.

• three main biopolymers in living systems:- Polysaccharides: joined together 2 monosaccharides (sugars)

to form a glycosidic bond, a water molecule is released and play structural and functional roles in organisms: Glycogen is a storage polysaccharide, whereas cellulose is a component in the cell walls of plant cells

- proteins: are made of polypeptides, which are biopolymers of amino acid monomers

- Polynucleotides (nucleic acids): DNA, RNA• Biopolymers are easily degradable, and renewable: can be

hydrolyzed by enzymes, or else they can be denatured by heating, adding chemicals, or by mechanical forces


a (1→4) linked D-glucose units30% of vegetable matter

Cellulose: Cell-OHPolysaccharide

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polymeric carbohydrate composed of long chains of monosaccharideunits bound together by glycosidic linkages

Cm(H2O)n where 200 ≤ x ≤ 2,500 or (C6H10O5)n where 40 ≤ n ≤3,000

starch and glycogen (storage); cellulose and chitin (structural)

amylopectinamylose

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Properties & Applications of Biopolymers


Polymeric Biomaterials

• Natural polymeric biomaterialsCollagen, Chitosan, Alginate

• Synthetic polymeric biomaterialsPVC, PP, PS, PU

• Degradable polymeric biometrialsPLA, PGLA

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(3) Synthetic Polymers (1907 ~)• broad spectrum of properties• economical tailoring to meet end use requirements

A. 1907 L. H. Bakeland· Bakelite: phenol formaldehyde resin (phenol resin or PF resin)· 1st synthetic thermoset (The Times, Sept. 22, 1924)· used in circuit boards but largely replaced with epoxy resins

and fiberglass cloth

B. 1924 Staudinger’s hypothesis of macromolecules(1953 Nobel prize)

· synthesis, structure and properties of POM and PS· crystallographic study (1960s)

by Mark, Meyer and by Carother’s preparation of PA, Polyester


Phenol Formaldehyde Resin

https://www.youtube.com/watch?v=XGM-yuzHrhg

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C. 1930 idea accepted ® “polymer science” established (~ 1950) by Flory (1974 Nobel prize)(Stone, Bronze, Iron, Steel Ages into current

The Age of Polymers, 합성플라스틱 시대)

D. 1940s 대량생산 (상업화 I)

E. 1950’s Scientific and Industrial Progress · Ziegler and Natta (1963 Nobel prize) · 고분자 합성시대 (상업화 II)

F. 1960’s 내열성 고분자 (상업화 III): 미소우주개발경쟁

G. 1970’s 내열고분자 산업활용, 전도성고분자

H. 1980’s 특수 EP 응용

I. 1990’s 기능성 ® 전자재료 (광, 전기, 분리 특성, 의료용 등)

J. 2000’s 고기능성: Fusion technology (BT, NT, IT, CT/ET, ST)Electric vehicle (EV), Fuel cell vehicle (FCV)


Paradigm Shift in Auto Industry

ICE (H)EV FCV

introduction Growth Maturity Decline

Introduction Growth Maturity

(H)EV

FCV

Up to 90% of total sales

2005 2010 2020 2030 2040

8,000

10,000

6000

4000No

of C

ars

(X 1

04)

2015

35


3) History of Polymers


4) Applications of Polymers

• Current applications:(Consumer Science, Industry, Sports, Agriculture and Agribusiness)extend from adhesives, coatings, foams, and packaging materials to textile and industrial fibers, composites, electronic devices, biomedical devices, optical devices, and precursors for many newly developed high-tech ceramics

• Future applications:(increasingly important role in all aspects of your life) conduction and storage of electricity (PV), heat and light, molecular based information storage and processing, molecular or nanocomposites, unique separation membranes, revolutionary new forms of food processing and packaging, health, housing, and transportation such as EV, FCV, etc.

36


Applications of Polymers


자동차 소재

72

37


경량화 2.0

1.5톤 승용차의 무게를 10% 줄일 경우: 가속 성능 향상, 제동거리 단축, 조향성능 향상 및샤시 내구수명 증가 효과

전기자동차 주행거리


Li Battery: Separator

38


Degussa composite separator


Separator for Li ion Battery

39


미세 다공성 분리막: Separator

PE 습식법 PP 건식법


l bionic climate membrane: breathable l durable, wind and waterproof and therefore

provides protection in all weather

Schoeller Textiles C-change Membrane

40


eVent PTFE membrane

eVent fabric

Water-proof


Applications

전도성섬유CNT

41


Carbon Nanotube (CNT)


§ 특수한 천이 톱날에 감겨 회전을 멈추게 해 사고방지

§ 두께 7 mm의 천 안에 케블라 (kevlar) 특수섬유 사용

§ 가격: 2만4천엔 (약 24만원)

일본의 데상트:

전동 톱날에도 안전 작업복

aromatic polyamide

포레스트 레인저

42



광성진 전투 (1871): 포로가 된 조선 병사 방충, 방수, 투습 기능

마이크론 크기의

탄소섬유

스마트 전투복

베트남전쟁

83

Molecular dagger


http://www.polymersolutions.com/psi-newsletter-archive/april-2014/#stor

The gel around the water (double

membrane) is created from brown algae

and calcium chloride.

Lexus Design Award 2014

Edible Water Bottles

43


• Lego bridge in Wuppertal, Germany to create both the superstructures and decks of bridges

• By Composite Advantage

Plastic Is Bridging the Gap



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chapter 1-Introduction 2017-upload-170301 - 서강대학교 …home.sogang.ac.kr/sites/sgpml/testmenu2/Lists/b12... · · 2017-03-06고분자공학CBE3007 Chapter 1. Introduction