Vat Lieu Hoc Chuong 3 - Polymer - Ban Chinh

7/27/2019 Vat Lieu Hoc Chuong 3 - Polymer - Ban Chinh

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TRNG I HC CNG NGHIP TP. HCMKHOA CNG NGH HA HC

--oOo--

VT LIU HC NGNH HA

Chng 3

VT LIU POLYMER

Th.S. L Qu Dng

Hc k 2

Nm hc 2011 - 2012


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Dn nhp

Polyme: s quan trng v tc hi i vi isng


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Ni dung hc trong phn ny

1. Cckhinimcbn2. Phntlng polyme

3. S polyme ha

4. Mtsloi polyme thngdng

5. Phlcb sung


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Ti liu tham kho

Slide bi ging

Gio trnh: polyme i cng, Hong NgcCng, nxb i hc Quc Gia tp.HCM


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1.1. Mt s nh ngha c bn Phn loi

Polyme: (t c ngun gcting Hy lp) Poly-meros: aphn

c trng polyme: kch thcphn t ln, c cu trc tilp trong sut chiu dimch. Do m thut ng

cao phn t (macromolecule,giant molecule) thng cdng ng ngha vi polyme


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Monome: l bt kz cht no c kh nng chuyn hathnh polyme (v d nh etylenpolyetylen, acidaminpolypeptid,)

2 monome phn ng vi nhauto thnh dime(lun lun mch thng). Dime li cng vi monometo thnh trime, tetrame, pentame (mch thnghoc vng)

Oligome (oligo ngha l mt t) l cc phn t c thn 10-20 n v ti lp.

trng hp DP (degree of polymeriation) hay chnhxc hn l trng hp trung bnh, hay cn gi l sn v ti lp, hay s n v mt xch cho bit s ccn v ti lp trong mt mch polyme. Nh vymonome c DP=1, dime c DP=2, trime c DP=3

Hai u mch ca polyme gi l nhm cui mch.


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Thng thng ra th polyme c chia ra thnh hainhm: polyme c ngun gc t ha du v polyme tngun c kh nng ti to (renewable), ngoi ra i khicn c mt loi na l polyme phn hy sinh hc(biodegradable)

Polyme c ngun gc t ha du li c chia thnhhai nhm vt liu kt cu v chc nng. Vt liu kt cul thnh phn chnh (kt cu nhn thy c) (vd: ng,mng, hp cha, chai l, tm). Vt liu chc nng lnhng polyme c ng dng nh ph gia tc nhng chc nng c bit, polyme ny l mtphn nh, khng thy c trong h (cht gy keo t,chy ty ra, cht lm c)


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Polyme t ngun c kh nng ti to(renewable) (ch xt c ngun gc sinh hc) Si t xellulox

Nha (t xellulo acetat) Cao su t cy (polyisopren)


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1.2. S lc v lch s pht trin ca polyme

T xa xa: s dng polyme sn c trongthin nhin (qun o: cotton, len, la, lanh,lng th nh : gtrang tr: h phch)

Ni bt nht c th k n protein, khng chl c s ca s sng m cn l polyme utin, l ngun gc ca cc acid amin v nnglng

Vo th k XVI, cc thy th ca Columbus pht hit ra cc th dn Trung M chinhng tri banh bng cao su thin nhin,ng c t nha ca cy Hevea Brailiensis.

Nm 1731, la Condamine dn u onthm him nhn danh chnh ph Php

nghin cu hnh dng tri t, gi v tlu vc Amaon tm vi ph cao su cngi th dn dng lm ng khng thmnc v chai mm do.


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1839: Charles v NelsonGoodyear bit cch bincao su thin nhin thnh mtnha nhit do(thermoplastic) dnh bng cchun nng cao su vi lng nhlu huznh (vi phn trm)

thnh cht c nhit n hicao hn trong mt khongnhit rng hn nhit ban u, hoc c th tr thnhnha nhit rn (vi mt lngS bng 50% so vi lng caosu) (pht hin nm 1951 biNelson Goodyear)

Phn ng ca cao su vi luhuznh nh vy c gi lphn ng lu ha(vulcaniation, theo tn cathn la Vulcan trong thn

thoi La M)


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-Gii Nobel ha hc nm 2000 c trao choAlan J.Heeher, Alan G. Macdiarmid v HidekiShirakawa v polyme dn in. Pht minh ny cgi vi ci tn cuc cch mng trong cht do.


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--Nm 2005: gii Nobel ha hc li c trao cho nhng ngi tmra phng php tng hp hu c v polyme mi (Phng phpROMP ring opening metathesis polymerization do RichardSchrock, Robert Grubbs v Yves Chauvin) m ra hng mi trongvic tng hp nhng dc phm v polyme cao cp.


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Vo th k XIX, bt g, si thc vt, si cotton(cha xellulo) c s l{ bng acid nitric tothnh vt liu c kh nng chy n cao, ngy

nay gi l nitroxellulo


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1.2. S lc v lch s pht trin ca polymeNm Polyme Nhpht minh ngdng tiu biuTrc 1800 Si cotton,len, la,da, giy, nha cy1839 Cao su luha Charles v Nelson

Goodyear, Thomas

HancockVrut xe

1851 Ebonit Nelson Goodyear Cht cchin1860 Xelluloid Hyatt Lc, khung1889 Xelluloz ti to Chardonnet v

Reichenbach Visi, phim nh1892 Tnhn to visco Cross, Bevan,

BeadleVisi

1907 Nha Bakelit Leo Baekeland Giy, vnp1930 polystyren Hermann

Staudinger chi, giadng1938 Poly flocacbon

(teflon)Roy J.Plunkett Mngchng dnh,

cho khng dnh


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Nm Polyme Nhpht minh ngdng tiu biu1946 Nha ABS Thit bin1957 polypropylen Natta Chai ngsa1959 polycacbonat Schnell/Fox CD, knh trong1985 Polyme tinh th

lng Jackson/economy/Jaffe

Thitb in t


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1.3. Hnh dng mch polyme

Ngi ta c th phn loi polyme da vo hnhdng mch phn t, hnh dng ny c xc nhda vo nhm chc ca monome.

C nhiu loi nh l polyme mch thng, polyme

mch nhnh, polyme khu mch, polyme dngthang, polyme dng nhnh cy


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1.3.1. Polyme mch thng: to thnh t mchdi cc nguyn t khung v cc nhm th.Polyetylen l v d n gin nht. Tnh cht lthng tan trong mt s dung mi.


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1.3.2. Polyme mchnhnh: nh l polymemch thng c nhnh.Polyme mch nhnhthng tan c trongdung mi ha tanc polyme mchthng. Tuy nhin nupolyme c nhiu

nhnh th ch trngtrong dung mi chkhng tan hon tonc.


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1.3.3. Polyme khumng (khumch Crosslinkedpolymer): l polyme clinkthahcgiaccmch.Slinkt ngang lin quan ntrng trong dungmicacc polyme ny. Linkt ngang cngnhiuthtrngcngthp. khumngthptonntnhnhinh cao su, khumng cao cthto rachtrncng.


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1.3.4. Polyme dng thang(ladder polymer): gingnhtngi, polyme dngthang gm hai mchchnhnivi nhau unbng

ccnvlinkt ngangdc theo mch. Cththy polyme dng thangcngchchn polymedngmchthngthng

thngvc tan kmhn. Vcbnnhitrttt. Vngthmcthtonnlinkt thang.


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Polyme dngnhnhcy (dendrimer): a ra lnutinnn 1940 bi P.J. Flory, ccutrc khoang rngbn trong(internal voids and channels) ctothnhtphntli(core moiety) vbmtbnngoickht (closely packedsurface groups) caccphntnhnh (branching units)

Vicgnnhngnhmchchottnhlnbmt dendrimem ra nhiukhnngngdngca dendrime


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Polyme dng nhnh cy (dendrimer)


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1.4. Copolyme

Khi ta polyme ha hai hay ba loi monome khc nhau,ta thu c copolyme. Nhvy, copolyme l polymec hai nvtilpkhc nhau trong mch.

Vdnh khi ta cho styren v acrylonitril polyme ha

vi nhau s thu c copolyme


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1.4. Copolyme

1.4.1. Copolyme ngunhin (randomcopolymer): khngcmttrttnocaccnv A v B trong cutrc polyme, tnhcht

ca copolyme tothnhkhcrtnhiuvitnhchtcacc homopolyme tngng


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1.4. Copolyme

1.4.2. Copolyme iuha, tipcch(regular/alternating copolymer): chachuiktip nhau ca hai nv monome. Tnh

chtca copolyme cngkhcrtnhiutnhchtca homopolyme)


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1.4. Copolyme

1.4.3. Copolyme khi (block copolymer): chamt khi ca monome th nht ri li mtkhi ca monome th hai)


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1.4. Copolyme

1.4.4. Copolyme ghp(graft copolymer):

thng c to thnh

bng cch cho phn nghai loi homopolymekhc nhau vi nhau.Copolyme ghp thngc tnh cht ging vitnh cht ca haihomopolyme


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1.5. Tnh iu ha (tacticity) ca polyme

i vi nhng phn t polyme c tm bt ixng, s c 3 loi kh nng tng ng vi trtt cc mono gn vo mch, gi l

Polyme ha isotactic Polyme ha syndiotactic

Polyme ha atactic


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1.5. Tnh iu ha (tacticity) ca polyme

Isotactic: c trng bi s phn b u n cacc nhm th nm mt pha dc theo mch chophp phn t to thnh cu trc dng xon cv c kh nng kt tinh d dng

Syndiotactic: c trng bi cu hnh tip cchnhau. Cc polyme ny cng d kt tinh

Atactic: cc polyme ny khng c cha mt xchiu ha dc theo mch. Do polyme c khnng kt tinh thp


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1.6. Phn loi polyme da vo tnh cht nhit

Thng thng th polyme tnghp c chia ra nh sau Nha (plastic): l vt liu rn

nhit s dng Nha nhit do: vt liu polymer

mm khi b t nng Nha nhit rn: l nhng h ban u

trng thi lng nhng khi gia nhitxy ra phn ng ha hc to thnhcht rn c khu mng cao, nh c bn ha hc cao.

Cao su (rubber): vt liu mm nhit s dng v c kh nngbin dng


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1.7. Danh php polyme

cchunhabi IUPAC(international union of pure andapplied chemistry) vonm 1970.

Cnhiutnkhc nhau do tnhnhthnhtrnnhiungungc

h danh phpkhc nhau vtnthngmi

2 loichnh: danh phpdatrnngungcv danh phpdatrn

cutrc, ngoi ra cnchthngdanh php IUPAC datrncutrc.


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1.7.1. Danh php da trn ngun gc: l hthng danh php n gin v ph bin nht,tn ca polyme c to bng cch thm tip

u ng poly vo trc tn polyme


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1.8.2. Danh php da trn cu trc (phi IUPAC): mt spolyme trng ngng c to thnh t hai loimonome c gi tn theo danh php da trn cutrc. Tn ca polyme c gi tn bng cch dng tipu ng poly khng c khong trng hoc du gch

ngang trc tn ca cu trc c t trong du ngocn


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2. Phn t lng polyme

2.1. Khi nim c bn v phn t lng trungbnh ca polyme Polyme d dng tinh khit nht th cng l hn

hp gm nhng phn t c phn t lng khcnhau.

Thng th phn t lng phn b theo hnh thpchung, do , khi ni n phn t lng ca

polyme, chnh xc, ta phi ni n phn tlng trung bnh.


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2. Phn t lng polyme

2.1. Khi nim c bn v phn t lng trung bnh capolyme Phn t lng trung bnh s: Mn: l tng khi lng cc phn

t polyme c trong mu chia cho tng s cc phn t (hay smol) polyme c trong mu

Phn t lng trung bnh khi: Mw: da tn c s l cc phnt cng ln s chim cng nhiu trong tng s khi lng camu polyme so vi cc phn t nh

Phn t lng trung bnh nht, Mv: cng c th tnh phn tlng ca polyme da vo nht ca dung dch polyme theonguyn tc n gin: cc phn t polyme cng ln lm cho dung

dch cng nht. Tt nhin phn t lng thu c bng cch o nht s khc so vi hai loi phn t lng trung bnh k trn,tuy nhin n ging vi phn t lng trung bnh khi hn.


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2. Phn t lng polyme

2.1. Khi nim c bn v phn t lng trungbnh ca polyme a phn tn/ phn b (polydispersity index PDI):

phn t lng khc nhau lm cho polyme tr nn

phc tp. Khng c gi tr no cho bit thc s bncht ca polyme. Do cn phi bit phn tn caphn t lng


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2. Phn t lng polyme

2.1. Khi nim c bn v phn t lng trungbnh ca polyme Vi sn phm n phn tn (c to thnh t nhng

phn t c phn t lng nh nhau) th cc phn t

c phn t lng trung bnh nh nhau.

Vi polyme a phn tn, phn t lng trung bnhkhi, nht, s tng theo chiu Mn


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2. Phn t lng polyme

2.1. Khi nim c bn v phn t lng trung bnh capolyme Nh vy ta thy: phn t lng trung bnh s hon ton

khng c thc v hu nh khng c mt phn t no cphn t lng nh vy trong mu polyme em o. Do

ta phi quan tm n phn tn, xc nh aphn tn, ta c th dng k thut sc k{ ry phn t SEC(Sie exclusion chromatography) hay cn gi l sc k{ thmgel hoc khi ph MALDI

Nu ch xt n Mn m khng quan tm n a phntn c th dn n sai lm v hu ht cc tinh cht capolyme nh bn chy nht c xc nh ch yuda trn kch thc phn t chim khi lng ln trongmu. Cc tnh cht ca polyme ph thuc ch yu vo cc

phn t c kch thc ln nn ph thuc vo Mw


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2. Phn t lng polyme

2.1. Khinimcbnvphntlng trungbnhca polyme

Sck{ryphn t


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2. Phn t lng polyme

2.2. Mi lin h gia phn t lng v tnhcht ca polyme: tnh cht c trng ca ccpolyme l tnh cht c l{ c c trng bi

phn t lng


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2. Phn t lng polyme

Nu phn t lng thp, khong 1000, polymekhng c bn c hc. bn tng nhanh ti gi tr B ri tng chm ti

gi tr C. B: im ti hn tng ng vi gi tr phn t

lng thp nht cho mt polyme c bnhu dng ln. B c gi tr trong khong 5000ti 10000 ty thuc vo loi polyme khc nhau

A v C cng thay i. ng cong dch v phabn phi (pha bn phn t lng cao hn) khilc tng tc lin phn t gim.


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3. S polyme ha

3.1. Polyme hamchgct do: Lphnng polyme haphbinnht Gct do lmthpcht trung gian c

sl electron vkhngphil ion t do

Phnngxy ra cnhmtschtkhimo (initiator) gct do. Ccphntckhnngphnhytothnhccphntc electron khngghpcpgilgct do

Thngthngcthkthpchtkhimohahcvitcnhnkhimovtl{.


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3. S polyme ha

3.1. Polyme ha mch gc t do: V d v hnh thnh polyme nh c ch gc t do


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3. S polyme ha

3.1. Polyme ha mch gc t do: S tt mch do ghp cp


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3. S polyme ha

3.1. Polyme ha mch gc t do: S tt mch do d ly


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3. S polyme ha

3.1. Polyme ha mch gc t do: S pht trin phn nhnh ca polyme


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3. S polyme ha

3.1. Polyme ha mch gc t do: Ngng phn ng polyme ha mch gc t do

bng cht c ch


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3. S polyme ha

3.1. Polyme ha mch anion: Cht khi mo: ba mnh: n-BuLi, NaNH2, natri

naptalenua,, tc cht Grigard v natritriphenylmetyl

Tm hot tnh: l nhng anion nn monome vinylphi c nhm th rt electron. Hnh di biu thhot tnh gim dn ca mt s polyme


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3. S polyme ha

3.1. Polyme ha mch anion: Qu trnh polyme ha mch anion: bt ngun t

cht khi mo


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3. S polyme ha

3.1. Polyme ha mch cation: Cht khi mo: thic (IV) clorua, bor triflorua v

iod, dn xut hu c kim loi. Thng c dng polyme ha styren,

isobutylen, etyl vinyl ete, turpentin (nha thng). Do cc carbation thng y nhau nn khng th

lm tt mch phn ng polyme ha mch cationbng cch kt hp. Polyme thu c c a

phn tn thp. Phn ng truyn mch cng kh cth xy ra nhit thp nn polyme thu cch c mch thng (khng c nhnh)


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3. S polyme ha

3.1. Polyme ha mch cation: C ch tiu biu


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3. S polyme ha

3.2. Polyme ha bc: c trng: monome bin mt sm trc khi to thnh polyme c

phn t lng ln. Trong hu ht cc sn phm polyme ha bc, monome ch cn li t

hn 1% so vi lng ban u khi polyme mi c trung bnh khong 10n v mt xch.

Theo l{ thuyt, s khc bit ch yu gia phn ng polyme ha mchv bc l cc tinh cht ng hc ca chng Tc phn ng polyme ha bc bng tng tc phn ng gia cc

phn t c kch thc khc nhau, tc l bng tng tc cc phnng sau

Monome + monome dime

Dime + monome trime

Dime + dime tetrame

Trime + monome tetrame

Trime + dime pentame

Tetrame + monome pentame

Trime + trimehexame

So snh gia polyme ha bc v polyme ha


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So snh gia polyme ha bc v polyme hamch

Polyme habc Polyme hamchBt kzhai phn t c th phn ng Phttrin mch ch xy ra bng cch cng

monome vo cui mch c hot tnhMonome cho phnng ht sm Monome luntn ti trong sut qu trnh

phn ng nhng nng c gimPhnt lng ca polyme tng trongsut qu trnh phn ng Polyme phnt lng cao c tothnh smThi gian phnng cng di s lm tngphn t lng, nhng hiu sut thay irt t

Phnt lng v hiu sut ph thuc cch phn ng

Mch phttrin thng chm (t vipht ti vi ngy)

Mch phttrin thng rt nhanh (t vigiy ti vi micro giy)

Tt ccc phn t u c mt trong sutqu trnh phn ng Ch cmonome v polyme c mt trongqu trnh phn ngThng(khng phi lun lun) n v tilp ca polyme c t nguyn t hn so vimonome

Thng(khng phi lun lun) n v tilp ca polyme c cng s nguyn t nhmonome.

Phn bit phn ng trng hp v phn ng


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Phn bit phn ng trng hp v phn ngtrng ngng

Phn ng trng hp: l phn ng to thnhpolymer t cc monomer

Phn ng trng ngng: l phn ng to thnhpolymer v cc phn t nh khc t cc

monomer.


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4. Mt s loi polymer ph bin

4.1. H polyetylen 4.2. Tinh bt v xenllulo

4.3. Cao su t nhin

4.4. Teflon polytetrafloetylen (PTFE)


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4.1. H polyetylen


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4.1. H polyetylen

H PE T trng (g/cm3)HDPE (high density PE): polyetylen t trng cao 0,940 0,965MDPE (medium density PE): polyetylen t trng trung bnh 0,930 0,940LDPE (low density PE): polyetylen t trng thp, mch nhnh 0,915 0,930ULDPE (ultra low density PE): polyetylen t trng siu thp, mch nhnh 0,880 0,915LLDPE (linear low density PE): polyetylen t trng thp, mch thng 0,860 0,926

Loi nha ph bin,, ging nh sp, tr v mt ha hcc phn bit da vo t trngng dng ph bin nht l lm ti nha, bnh ng sa, chitit ng nc, ng mm


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4.2. Tinh btv xelluloz


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4.2. Tinh btv xelluloz

Tinh btlmt polymercarbohydrat (polysaccarit) trong

ccnv monome l glucoznivi nhau thokiuuvoui.Tinh btkhng tan trong nclnhnhng tan tt trong nc

nng.

Xelluloz lmt polyme cphntlnglnvckt tinhcao, khng tan trong ncvdung mihuc. Xelluloz chtan trong dung mickhnngcttlinkt hydronh N-metyl morpholin-N-oxid

h


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4.3. Cao su tnhin Cao su tnhinlmt polyme hydrocacbon

tntididngnhgingnhsa trong

mcy Hevea Brasiliensis. Trong thchinthhai nccbctngun cao su nnphiphttrin cao su tnghp.

Cchylu cao su csdng TrungMv Nam M. Thdn Aztecs nhnthynhngtri banh cao su rtnyvh cho lbanh bqum. Ngi Maya cngto ra ngitmthibng cchnhngchnvohnhpm cao su. Cao su cncdngvoccmcchkhcnhlmn, tay cmcngc.Do thdnChuMkhngbitluha,nhnghdngcphngphphucxl{ cao su v cho ktqutngtbngcchtrong m cao su viccloinhacykhcvncploi nho cbit.

h


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4.3. Cao su tnhin

Brasil thdnbitdng cao su lmvikhngthmnc. cmtcuchuynkrngcmtngichuuutintbrazil vbo nha c mang theo nhngmingvitm cao su khngthmnclm cho mingi kinh ngcvngb

a ra tavlmphthy. Khi nhngcc cao su utinca

tinc Anh, ngi ta thycc cao su cthty (rebbing) vtvitchtrngiyrtttnncgitnlrubber. Ngi

phpgi cao su l caoutchouc ittcaaochu hay cautchuck cathdn, cnghalncmtcacy

4 4 fl


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4.4. Teflon

Polytetrafloetylen, Teflonhay ltnthngmicamthpchtc Roy J.Plunkett (1910 1994)cacng ty DuPont phtminh vonm 1938 vcavothturngnm 1946.

Trong y hc Teflon c

dnglmccbphncthnhnto (nh vantim) do ctht khi othichng.

4 4 T fl


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4.4. Teflon

Teflon hontonkhng tan trong cc dung mihucthngthngvkhngchutcngca axid, bamcnng (do cdnglmbnhphnngcngnh thanh, cnhkhuy). Cthsdng teflon trong khongnhitt -200 ti 260oC. Nctnhcchinrtttvhs ma stnh (csdnglmchokhngdnh, xl{thmvsinhmtrnhdnhvtbn) vkhngbtchy.

Tnhtrca teflon cthcgiithchdatrnlinkt C-F. DoFlo cmin cao nhtnnlm cho linkt C-F rtphncc,viumnmtrn flo. Cclinktnyrtchcchnv do konguynt flo gnstvinguynt carbon dc theo mchchnh.Ccnguynt flo ng vai tr che chn carbon vkhng cho

carbon btncngbicchachtkhc, v flo cngkhng chophnng. Vvy teflon rttr. Nkhngkthpvi oxy nnkhngchyvkhngbnmn. Do ccintbgirtchtnncngkhngdnin. V PTFE khngckhnnghnhthnhlinktviccvtliukhcnnnrttdnh, nhcdnglmbmtchokhngdnh.

4 4 T fl


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4.4. Teflon

5 Ph l b


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5. Phlcb sung

Phn tlng trung bnhs Mncnhnghatngkhilngcaccphnt trongmtmu polyme chia cho tngs mol ccphntc trong mu

=

Vikchthccaphnt polyme phnbkhc nhau ti=1,2,3,4n. Ni: s mol capolyme cphntlng Mi

5 Ph l b


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5. Phlcb sung

Phn tlng trung bnhkhi Mw

= =

Picgilphnkhilngcaccphntcphntlng Mi

5 Ph l b


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5. Phlcb sung

Polyme cphntlngcngln, nhtcancngln. Phntlng trung bnhnhtcthtnhda theo cngthc

= 1

Khi a = 1 thphntlng trung bnhnhtvkhibng nhau


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Vat Lieu Hoc Chuong 3 - Polymer - Ban Chinh