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Cc k hiu......4
Li m u..5
Chng 1. Vt liu Polyme phn hy sinh hc......9
1.1 Phn hu sinh hc......10
1.2 Tc nhn gy phn hu sinh hc11
1.2.1 Vi sinh vt11
1.2.1.1 Nm...11
1.2.1.2 Vi khun11
1.3 Cc loi polyme phn hu sinh hc...12
1.4 ng dng ca polyme phn hu14
1.4.1 ng dng trong y hc..14
1.4.2 ng dng trong nng nghip...14
1.4.3 ng dng trong vt liu bao b....15
Chng 2. Vt liu polyme phn hu sinh hc trn c s blend gia polylactic
axit (dng nguyn cht v dng bit tnh) vi tinh bt sn..17
2.1 Tinh bt (TB).17
2.1.1 Amiloz...18
2.1.2 Amilopectin.....20
2.1.3 S khc nhau gia amiloz v amilopectin.22
2.1.4 Tnh cht ca tinh bt..23
2.1.5 Bin hnh tinh bt........23
2.1.5.1 Phng php vt l......23
2.1.5.2 Phng php ha hc...24
2.1.6 S h ho tinh bt....24
2.1.7 ng dng ca tinh bt.....26
2.2 Tinh bt sn28
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2.2.1 Gii thiu...28
2.2.2 Tinh bt sn28
2.2.3 Qu trnh sinh tng hp tinh bt sn..30
2.2.4 Cng ngh sn xut tinh bt sn31
2.2.4.1 Cc cng on c bn.....31
2.2.4.2 S khi qu trnh sinh tng hp tinh bt sn.....32
2.2.4.3 Mt s phng php bin tnh tinh bt sn.33
2.2.4.4 Mt s sn phm ng dng t tinh bt sn..33
2.3. Phn ng a t...34
2.3.1 Phn ng a t c cn bng...34
2.3.2 Phn ng a t khng cn bng....36
2.3.3 Phn ng ng a t...37
2.3.4. Phng php tng hp polyme, copolyme khi v copolyme ghp.38
2.4 Axit.39
2.4.1 Axit lactic (AL)39
2.4.1.1 Tnh cht vt l39
2.4.1.2 Phng php tng hp.40
2.4.2 Polylactic axit (PLA)...40
2.4.2.1 Lnh s qu trnh tng hp PLA.40
2.4.2.2 Kh nng phn hu ca PLA.......41
2.4.3 Cc phng php iu ch PLA t AL....42
2.4.3.1 Phng php ROP44
2.4.3.2 Phng php trng ngng AL trong dung dch c km theo s
tch loi nc44
2.4.3.3 Phng php ni mch PLA c phn t khi thp thnh PLA c
phn t khi ln bng cc tc nhn ko di mch thch hp. (PLA bin tnh).45
2.4.3.3.1 PLA bin tnh trn c s LA v 1,4 dihydro benzoic axit.46
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2.4.3.3.2 PLA bin tnh trn c s LA v Mandelic axit.....47
2.4.3.3.3 PLA bin tnh trn c s LA vi Methylen diphenyl
diisocyanate (MDI)...48
2.4.3.4 PLA bin tnh trn c s LA vi Maleic anhydrit..49
2.4.3.5 PLA bin tnh trn c s LA v cc diancol khc nhau.49
2.4.4 nh hng ca cc loi xc tc khc nhau n qu trnh tng hp
PLA, PLA bin tnh50
2.4.5 ng dng ca PLA52
2.5 To Blend gia PLA, PLA bin tnh vi tinh bt sn.....53
2.5.1 To Blend...53
2.5.2 C s cho qu trnh phn hu Blend...54
2.5.3 S dng TB trong Blend..54
2.5.3.1 S dng TB nh l cht n.....54
2.5.3.2 S dng TB dng nhit do..54
Chng 4. Nhim v ca ti56
Chng 5. Cc phng php thc nghip....57
Ti liu tham kho....58
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CC K HIU
AL
Axit lacit.
LAL
DLA
D(-)Axit lactic.
PLA
Polylactic axit.
ROP
Trng hp m vng.
AM
Amiloz.
AP
Amilopectin.
TBS
Tinh bt sn.
TB
Tinh bt.
MDI
MA
Maleic anhydrit.
PLLA
Poly-L-Lactic axit.
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LI M U
Cc vt liu polyme t nhin nh si bng, t tm, si gai, si len c s
dng lm qun o, da sinh vt lm giy vit.. gn lin vi cuc sng ca
con ngi c i. Ngi Ai Cp c tm ra phng php iu ch hp cht cao
phn t c s dng lm giy vit. Cng trnh ny m u cho qu trnh gia
cng cc vt liu polyme t nhin v bt u nghin cu v cc hp cht polyme.
n nm 1833, Gay Lusac tng hp c polyeste l polylactit khi un
nng axit lactic v Bezelius a ra khi nim v hp cht polyme. T
polyme chuyn sang thi k tng hp thun tu ho hc, i su vo nghin
cu cu trc, tnh cht, c bit l nghin cu ch to cc polyme mi c nhng
tnh cht u vit p ng nhu cu ca con ngi.
Ngy nay cc vt liu trn c s polyme nh: cht do,cao su, si keo dn,
sn.. gn b mt thit vi mi nghnh, mi lnh vc ca sn xut v sinh hot
ca con ngi do nhng tnh cht u vit ca n ( bn cao, kh nng un do,
dn di, bn ko t cao..) m kh c vt liu no c th p ng c.
Vi s pht trin ca nghnh cng nghip ho du, s nghin cu ch to vt liu
polyme rt c quan tm v ch . c hng trm chng loi vt liu polyme
c sng ch v ng dng cho cc nghnh cng nghip, nng nghip v i
sng con ngi.
Thng qua cc con s thng k, ta mi thc s nh gi ht tm quan trng
ca vt liu polyme. Nu ch tnh ring nm 1996, bnh qun u ngi ti cc
nc cng nghip pht trin s dng 80 100 kg polyme, cn cc nc ang
pht trin l 1-10 kg v con s ny hin nay khng ngng tng ln. Vi
khong 60 70 %, cc sn phm t n gin n phc tp u c lin quan ti
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vt liu polyme Nh vy vi s ra i ca vt liu polyme l mt bc t ph
mi cho cc nghnh ch to vt liu.
i vi nc ta, nghnh gia cng cht do mi c xut hin t nhng nm
1990 nhng hin nay thc s pht trin mnh m. Nm 1990 mc tiu th l
5,7 kg/ngi, n nm 2000 con s ny ln ti 10 kg/ ngi v hin nay l 16
kg/ngi. Lng tiu th nha nhit do nm 2000 l 800.000 tn; nm 2005 l
1.300.000 tn; d kin n nm 2010 l 2.100.000 tn. Nu tnh ring rc thi l
ti nilon ln ti hng triu chic mi ngy. l nhng con s khng l, ni
nn tm quan trng ca vt liu i t polyme vi con ngi.
Tuy nhin bn cnh nhng u im tch cc ca vt liu polyme th nhng
nhc im ca n cng c bc n. Cc polyme hin nay phn ln u c
ngun gc t ho du, mt ngun nguyn liu ang ngy cng cn kit v bt n.
Tnh trng khan him ca du m, cng vi s khai thc cm chng v s bin
ng ca th trng ngy cng y gi du ln cao, t nh hng trc tip
v gin tip n nghnh cng nghip polyme. Mt khc cc vt liu polyme cc
k kh phn hu trong mi trng, chng c th tn ti t hng chc n hng
trm nm trong mi trng t nhin. c tnh mi nm c thm khong 20 30
triu tn rc polyme trn th gii v nu khng c bin php x l hu hiu th
con s ny s ngy cng tng ln. Bn thn rc thi polyme khng t gy ra c
hi nhng s lng rc thi ngy cng tng ln v khng phn hu c s l mi
trng cho cc loi sinh vt, cn trng mang mm bnh sinh si v pht trin lm
nhim mi trng v sc kho con ngi. Vn ny thc s l bi ton kh
vi cc nh khoa hc v mi trng hc, t ra cc phng php x l cht
thi polyme.
Hin nay c 4 phng php x l cht thi polyme:
Phng php thiu t: y l mt phng php c in v rt ph
bin. Tuy nhin vn t ra l trong thnh phn ca polyme cha cc cht nh
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S, Cl, Ckhi t s to ra cc kh c nh: CO2, HCl, H2Sl nhng kh c
gy nhim mi trng v sc kho con ngi. Do , s dng phng php
ny cn phi c thit b thiu t hin i, hon chnh m bo cc yu cu
nghim ngt v cc ch tiu kh thi ra mi trng. Phng php ny cha thc
s c thc hin theo ng cc ch tiu v mi trng do cc trang thit bi thiu
t cn thiu v th s. Do chi ph thiu t cao nn n mi ch c p dng
cho cc cht thi polyme t rc thi bnh vin, y t..
Phng php chn : Phng php ny thng c ng dng cho
cc loi cht thi rn thng thng. Tuy nhin n hon ton khng c tc dng
i vi cht thi polyme v tc phn hu ca polyme rt chm trong t nhin.
Phng php ti ch: Phng php ny cng ang c p dng. Tuy
nhin khng phi tt c cc loi rc thi polyme c th ti ch v s dng c
do cc sn phm ti ch c cht lng thp hn rt nhiu so vi cc sn phm
ban u.
Phng php ch to polyme phn hu: y l mt phng php c
cc nh khoa hc rt quan tm v c nh gi l phng php ti u x l
cht thi rn. Polyme phn hu sinh hc rt phong ph, a dng v c ngun gc
t nhin hoc tng hp v c kh nng to compozit, blend vi cc hp cht t
nhin nh: tinh bt, si tre, bt gl mt hng i rt quan trng.
Trc nhng yu cu ca thc tin t ra mt vn l phi tm ra mt
loi vt liu polyme va m bo bn c l cao, va c kh nng phn hu
trong iu kin t nhin v i t ngun nguyn liu khng phi t du m, c sn
trong t nhin v c kh nng hi phc cao. Hin nay, polylactic axit ni ln nh
l mt polyme phn hu sinh hc c ng dng rt rng ri do c nhng tnh
cht vt tri nh: Polylactic axit c iu ch t ngun tinh bt ( ng, sn),
r ng iu kin t nhin, trong vng 6 thng, hn 90% polyme b phn
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hu. Vi sn lng 140.000 tn/nm ca lin doanh Cargill Dow polymers LLC
v cc cng ty khc, nh du bc pht trin ca polylactic axit.
nc ta vi ngun nguyn liu phong ph, di do v a dng: tinh bt,
tinh bt sn, si tre, bt gl tim nng sn xut vt liu phn hu sinh hc
trn c s polylactic axit hoc blend, compozit ca PLA vi TB, si tre ang l
hng i mi, quan trng trong tng lai gn ca nghnh cng nghip Vit Nam.
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c nhn nhn di tn chung l: Polyme phn hu trong mi trng. S phn
hu ny c xt trn gc c ch phn hu cu vt liu:
- Phn hu sinh hc.
- Chn .
- Phn hu thu phn sinh hc.
- Phn hu quang - sinh hc.
- B gy quang hc.
1.1 Phn hu sinh hc
Theo hip hi tiu chun th nghim v vt liu M (ASTM) nh ngha
phn hu sinh hc l kh nng xy ra phn hu thnh CO2, kh metan CH4,
nc, cc hp cht v c hoc sinh khi, trong c ch p o l tc ng ca
enzym ca vi sinh vt c xc nh bng cc th nghim chun phn nh
c cc iu kin phn hu ca vt liu.
nh gi hon thin cc yu t nh hng n s phn hu ca vt liu
tiu chun ASTM c nghin cu trong cc mi trng khc nhau nh:
trong mi trng t l ASTM D5525, trong mi trng nc l ASTM
D5437, trong mi trng giu dng cht l ASTM D5338..
Phn hu sinh hc l phn hu do hot ng do vi sinh vt gy ra, c bit l
do hot ng ca enzym dn n s thay i ln v cu trc ho hc ca vt liu
do s b gy cc mch v to mi trng ng ho cho vi sinh vt pht trin. V
c bn s phn hu ca polyme phn hu sinh hc cn mt thi gian nht nh
trong mi trng m, c khng kh, c kh nng sinh sn. Tc phn hu ph
thuc vo nhiu yu t nh: hnh dng, kch thc, dy ca vt liu v mi
trng phy hu. Cc sn phm c kch thc mng nh bao b, ti, v hp cn
khong 3 n 6 thng phn hu, trong khi cc sn phm c kch thc dy
nh tm, khay ng thc phm, dao, na..phi mt mt nm phn hu.(2).
1.2 Tc nhn gy phn hu sinh hc.
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1.2.1 Vi sinh vt
C hai loi vi sinh vt gy phn hu sinh hc ng quan tm nht l nm v
vi khun.
2.2.1.1 Nm
Nm l nhng vi sinh vt rt quan trng gy ra s phn hu ca vt liu. S
phn hu l kt qu do cc enzym c sn xut ra t nm, cc enzym ny ph
v hp cht hu c cung cp thc n c trong thnh phn polyme. iu kin
mi trng l rt quan trng cho s pht trin ti u v hot ng phn hu ca
nm nh: mi trng c kh, m cao, nhit khong 50 C cng vi s c
mt ca vt liu cung cp thc n.
Vi hn 80000 chng nm c bit ti th chng nm Fusarium L203
c th nghim v cho hiu qu phn hu ti u cho vt liu ang c nghin
cu di y.
1.2.1.2 Vi khun
Schyzomcetes, mt loi vi khun c vai tr quyt nh trong mi quan h vi
nm, lm suy gim polyme. Hot ng ca vi khun ch n thun l sn xut ra
enzym, ph hu cc hp cht hu c to ra thc n. Vi khun tn ti trong t
dng ym kh hoc hiu kh l tc nhn quan trng lm suy gim vt liu, c
bit nh hng n tui th cy bng, sn phm g, phn hu si.
1.2.1.3 Enzym
Enzym thc cht l xc tc sinh hc c c ch hot ng ging nh xc tc
ho hc. Khi gim nng lng hot ho xung, chng c th tng tc phn
ng. Vi s c mt ca Enzym, tc phn ng c th c tng ln 10 10 ln.
a phn cc Enzym l nhng protin c mch polypeptit cu trc dng phc ba
chiu. Hot ng ca Enzym c lin quan mt thit n cu trc, cu hnh.
Cu trc ba chiu ca emzym c dng gp khc v dng ti, to ra cc vng
b mt vi cu trc bc mt c trng (ngha l c ui aminoaxit c trng) to
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nn b mt hot ng. Ti b mt hot ng c s tng tc gia enzym vi hp
cht nn, dn ti phn ng ho hc, to ra ssn phm c bit.
c s hot ng ti u, enzym phi kt hp vi cc yu t b tr nh cc
ion kim loi: Na, K ,Ca , Mg, ZnCc yu t b tr hu c cng c gi l
coenzym v chng c th thay i v cu trc.
S tip xc ban u gia enzym v cht nn to ra s iu chnh ti u ti
vng hot ho, to nn kh nng lin kt cc i enzym - hp cht ca vt liu.
Thng thng ng tng tc to ra nhng thay i ny khi gn vi enzym.
Enzym c nhiu c ch hot ng khc nhau nhng in hnh l theo c ch
oxy ho sinh hc v thu phn sinh hc.(2).
1.3 Cc loi polyme phn hu sinh hc
Cc loi polyme phn hu sinh hc bao gm:
- Polyme c ngun gc t nhin:
Tinh bt.
Xenluloz.
Algrinat.
Chitin v Chitosan.
Gelatin.
Cc loi polyme t nhin thng c gi thnh r( tinh bt sn c gi 5000
vn/kg ).
- Polyme c ngun gc tng hp:
Polyeste: Poly glycolic axit (PGA), Poly glycolic axit co-lactic axit
(PGA/PL), Polylactic axit (PLA), Polybutylen succinat, Polyhydroxyalcanoat
(PHA).
Polycacprolacton (PCL).
Polyamit.
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Polyuretan polyure: i t polycacprolacton diol, hp cht
diisocyanat.
Polyme mch chnh cha cacbon: Polyvinyl axetat (PVA), Poly
acrylat.
- Cc loi polyme phn hu sinh hc khc:
Poly tan trong nc.
Nha phn hu quang.
Ht ph gia kim sot phn hu.
Polyme c mch chnh d b phn hu.
Cc polyme t nhin c kh nng phn hu cao tuy nhin li c tnh cht c
l km hn nhiu so vi cc polyme tng hp. Do t c ng dng lm cc
loi vt liu m thng c s dng lm thc phm.
Cc loi polyme tng hp c hoc khng c kh nng phn hu sinh hc thi
c gi thnh rt cao, do i t cc ngun nguyn liu ho thch khng c kh nng
ti to.
Do vy nu kt hp 3 yu t: kh nng phn hu sinh hc, kh nng ng
dng lm vt liu v gi thnh kinh t th gii php ti u c a ra l to
blend gia polyme t nhin v polyme tng hp. Gii php ny xut hin theo
hai hng:
- To blend gia polyme t nhin vi polyme tng hp tr.
- To blend gia polyme t nhin vi polyme tng hp ( dng nguyn
thu hoc dng bin tnh) c kh nng phn hu sinh hc.
Trong hai hng i , chng ti la chn hng i th hai trn c s
tinh bt sn v polylactic axit dng tinh khit v dng bin tnh, do blend ny to
ra sn phm c kh nng phn hu hon ton trong mi trng v p ng c
mt s ch tiu k thut ( s c gii thiu phn sau).
1.4 ng dng ca polyme phn hu
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Hin nay polyme phn hu sinh hc tr thnh mt sn phm thng mi
quan trng, c ng dng cho cc mc ch khc nhau ch yu l cho cc lnh
vc: y hc, nng nghip v bao b. Tuy nhin do gi thnh sn phm cn cao v
cc c tnh chuyn dng nn n ch yu c ng dng trong y hc, nhng tim
nng pht trin ng dng trong nng nghip v bao b l rt trin vng.(2).
1.4.1 ng dng trong y hc
Cht do phn hu sinh hc c ng dng lm ch khu t tiu, th
nghim lm m cy phu thut mch mu v chnh hnh, lm m mm dng vin
nang gip nh chm thuc lu di v c kh nng iu khin trong c th. Thut
ng vt liu sinh hc ch nhng vt liu phn hu sinh hc dng trong y hc c
kh nng tng thch sinh hc vi c th con ngi.
Nhn chung vt liu sinh hc c ng dng trong:
Thay th cc m b bnh hoc khng cn kh nng hot ng: lm khp
nhn to, van tim, ng mch, rng gi..
Tr gip m hi phc, bao gm ch khu, hi phc xng gy, gn, dy
chng
Gii phng thuc vo c th: vin nang bao thuc.
1.4.2 ng dng trong nng nghip
Trong nhng nm 1930 1940, mng mng cht do c ng dng trong
nng nghip lm mng ph che t, hom m cyMng cht do ny c tc
dng gi hi m cho t, ngn chn c di pht trin, c tc dng n nh t,
trnh s pht trin ca sinh vt c hi v vy tng tc pht trin cho cy trng.
Cc cht do lm mng phn hu thng dng nh LPDE, polyvinylclorit (PVC),
polybutylen (PB) v copolyme ca etylen-vinylaxetat. Tuy nhin bn thn cc
cht do ny hu nh khng b phn hu trong t sau khi s dng. Do , cc
cht do phn hu sinh hc bt u c s dng rng ri lm mng che ph
cho t nng nghip nh kh nng t phn hu sau mt thi gian nht nh di
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tc dng ca nhit , m, nh sng v cc vi sinh vt trong t m khng hi
cho cc ma v tip theo.
Cc mng mng cht do c th b phn hu quang v phn hu sinh hc.
vt liu c kh nng phn hu quang, ngi ta thng a thm cc cht do hp
cht dibutyl dithiocacbamat st phi hp vi dibutyl dithiocacbamat km. T l
phi trn c iu chnh sao cho khi cy pht trin th cht do bt u b phn
hu.
Vi mng mng phn hu trn c s tinh bt vi polyvinylalcol,
copolyetylen-acrylic axit, polylatic axit b phn hu hon ton bi vi sinh vt
trong t, trong khi st v canxi lm tng s phn hu ca polyetylen.
Polycaprolacton c ng dng lm hom m cy. Trong mi trng t s
phn hu sinh hc xy ra sau 6 thng tn hao khong 48% trng lng, sau mt
nm tn hao 95% trng lng.
1.4.3 ng dng trong vt liu bao b
Polyme phn hu sinh hc c ng dng ch yu lm bao b trong cng
nghip thc phm, vi yu cu m bo c cc tnh cht nh polyme tng hp
nhng c kh nng phn hu cao. Cc loi polyme phn hu sinh hc dng
sn xut bao b ch yu l polysacarit nh: tinh bt, pullulan v chitin chitosan.
Mc phn hu ca mng mng ph thuc vo t l phi trn gia polyme
tng hp v polyme thin nhin, bn cht ho hc ca chng v cng ngh sn
xut.
Pullulan l polyme c tng hp t cc loi nm, c cu to t cc vng
maltotrise ni vi nhau bi lin kt -1,6. y l mt polyme tan trong nc, ng
dng sn xut mng mng trong sut, c th n c v c thm kh thp.
Poly - L lactic axit (PLLA) c tng hp t cc phn ng ngng t axit
lactic, c bn ko t 4570 Mpa, dn di 85105% c kh nng tt sn
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xut bao b nh: ti ng rc, khn v sinh, bao gi v hp ng thc n
nhanh.
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C6H12O6
C6H12O6
(C6H10O5)n
3n H2O
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amilopectin, t l amiloz trn amilopectin khong , cu to t cc mt xch
anhydroglucoz, c lin kt ch yu vi nhau bng lin kt -D-1,4 glucozit.
Nh vy, tinh bt c ngun gc khc nhau cho hm lng cng nh thnh phn
khc nhau, v vy nh hng n cht lng ca sn phm.
Cc chng loi tinh bt.(7,8).
Stt Chng loi
Hm lng
Amiloz
tinh bt,
Amilopectin %
% trng lng
1.
2.
3.
4.
5.
6.
7.
8.
Chui
Khoai ty
Go
Bt sn
La m
Ht mch
Ng
Ht u
kh
90
84
82
80
75
75
73
60-66
20
20
25
20
25
25
29
25
80
80
75
80
75
75
71
75
2.1.1 Amiloz
Amiloz l chui polyme mch thng c khi lng phn t 105 -106 g/mol,
c lin kt bi -D-1,4 glucozit. chiu di trung bnh khong 500 2000 n
v glucoz, ph thuc vo ngun gc v qu trnh ch bin. dng tinh th c
cu trc xon c, d b thoi ho trong nc, c kh nng ho tan trong dung
mi: forman dehyt, cloralhydrat. Phn t Amiloz c mt u kh v mt u
khng kh, cu hnh - glucoz to cho phn t c c tnh mm do hn.
Cu to ho hc ca Amiloz:
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6
6
5
CH2OH
O
1
OH
3
CH2OH
O
OH
OH
OH
G G G G G G G G
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amiloz phc cht, lm gim s trng phng v nht ca hn hp, bo v
hp phn khi s thoi bin.
Cu trc phn t ca amiloz to iu kin cho qu trnh hnh thnh mng
mng, chc v dai. Ngoi ra cc phn t amiloz cn c i lc vi iod v cc
phn t khc nh ru, axit bo, hp cht a nc..Amilz to ra cc phc xon,
phc ny to vi iod mng xanh m, to kt ta vi butanol v cc hp cht u
nc. Da trn c im ny c th dng nhn bit, nh lng s b hm
lng amiloz.
2.1.2 Amilopectin
Amilopectin l polyme mch nhnh, c khi lng phn t 107 109 g/mol,
c lin kt vi nhau ch yu thng qua lin kt -D-1,4 glucozit, ngoi ra cn
c lin kt -D-1,6 glucozit, chnh lin kt ny to ra cu trc mch nhnh cho
Amilopectin. Mi mch nhnh ny cha khong 20-30 mt xch glucoz. Phn t
amilopectin c th cha ti 100.000 n v glucoz v c th hin nh sau:
Cu to ho hc ca amilopectin:
____________________________________________________________________________
20
_________________________________________________________________
_________________________________________________________________
S khc bit gia amiloz v amilopectin i khi l khng r dt, do cc
phn t amiloz c khong 2000 gc glucoz v mt phn nh c nhnh nn n
cng c tnh cht ging vi amilopectin.
Aminoz v amilopectin c th tch ring bit vi nhau theo nhiu phng
php: ho trong dung dch alkol, cc dung dch a nc. Mt trong nhng
phng php thng dng l un dung dch huyn ph nhit 90-100 C.
Amilopectin khng ho tan, amiloz ho tan hon ton.
2.1.3 S khc nhau gia amiloz v amilopectin
Amiloz(AM).
Amilopectin(AP).
Cu trc thng.
n=6006000.
_________________________________________________________________
Tinh bt c cu to dng ht gm cc cu trc amiloz v amilopectin xp
theo lp hng tm, chiu dy mi lp 0,1m, chiu di ht TB l 0,350,7m.
TB c cu trc dng xp do c kh nng hp th nc cao ph thuc vo
tng tc gia nc-TB, TB-TB, TB-phn t khc.
Cc tnh cht TB c th hin:
Kh nng to mng.
Kh nng to si.
Kh nng to bao: bao bc thuc..
Kh nng tng tc vi cc cht khc:
* Gel ho vi protein to sn phm c dn di, cng, tng kh
nng tr nc ca protein, to sn phm c kh nng lu bin, cm quan tt hn.
* Kh nng trng n ca TB.
2.1.5 Bin hnh tinh bt
S bin hnh hay bin tnh TB nhm mc ch:
Tng tnh cht ca TB.
Tng gi tr cm quan ca TB.
To ra cc sn phm mi.
C rt nhiu phng php bin hnh TB:
2.1.5.1 Phng php vt l
Trn vi cht rn tr: do TB c i lc vi nc, do n kh ho tan vo
nc, to s vn cc, do thng trn TB vi cht rn tr, hp cht khng phi
ion: sacaroza..Qu trnh trn ln l tng khong cch gia cc phn t TB c tc
dng hydrat ho TB khng to cc.
Bin tnh bng phng php h ho s b bng mt lng d nc to sn
phm c c trng: kh nng trng nhanh trong nc, bin i chm cc tnh
cht trong qu trnh bo qun, bn nhit thp, c c kh nng gi nc
tt.
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23
_________________________________________________________________
Bin tnh bng gia nhit nhit cao: to Dextrin, ng dng trong h si,
cht c cho thuc nhum, dung mi hay cht mang mu cho thc phm.
2.1.5.2 Phng php ha hc
Bin tnh bng axit: s dng cc axit v c 13%, nhit 50-55C, to
sn phm c i lc gim vi iot, nht gim, p sut thm thu tng, ho tan
cao trong nc m, nhit h ho cao hndo s gim khi lng phn t TB.
ng dng ca TB bin tnh: trong h ho si, lm tng bn, chu mi mn,
tng cht lng giy in.
Bin tnh bng kim: Lm TB c tnh hydrat ho tt hn.
Bin tnh bng cc cht oxy ho nh hypoclorit. To TB c trng cao,
khi lng phn t gim. Dung dch h ho trong sut, mng mng, d ho tan
hn. ng dng trong cng nghip giy, h si, dt..
Bin tnh bng to lin kt ngang: s dng cc axit boric, dipeoxit, ialehyt
vinyl sulfen.. thu c sn phm c cu trc di, dn, cng hn.
Bin tnh bng enzym.
2.1.6 S h ho tinh bt
S h ho tinh bt l qu trnh chuyn ho tinh bt sang trng thi v nh
hnh tng kh nng trn hp. Trong qu trnh h ho, s ph v cc lin kt
hydro ni phn t ng thi hnh thnh cc cu lin kt hydro ngoi phn t. Qu
trnh h ho khng lm thay i thnh phn ho hc m ch lm thay i trng
thi cu trc ca tinh bt, do to ra trng thi v nh hnh.
Tinh bt t nhin c cu trc bn tinh th, t trng 1,5 g/cm, do n khng
ho tan trong nc lnh. Mt khc do c cha nhiu nhm OH nn hp th
nc mnh, trong iu kin p sut thng v m bo ho l 10% 20%.
Tinh bt c kh nng trng n c bit. Khi tinh bt c solvat ho n trng
thi v nh hnh bng cch un nng vi cht ho do ( thng l nc) hoc
bng cch x l tinh bt vi dung mi hu c (nh dimetyl sunfua axit), dung
____________________________________________________________________________
24
_________________________________________________________________
dch kim hay dung dch mui, n s chuyn t trng thi tinh th sang trng thi
v nh hnh, qu trnh ny gi l s h ho tinh bt.
Cu to ca amiloz v amilopectin rt khc nhau nn tinh bt biu hin cc
trng thi vt l khc nhau, ph thuc vo t l v thnh phn ca hai cu t
trong tinh bt.
Ngun gc sinh trng v loi cy s quyt nh s phn b di ca
mch, mc phn nhnh, khi lng phn t v cu trc ca cc ht tinh bt.
Tuy nhin, cc tnh cht ca tinh bt c th thay i c trong mt di rng nh
iu kin gia cng v cc ph gia. S h ho tinh bt s dng alcohol khi lng
phn t thp cng vi nc hin ang l ch ang c quan tm v nghin
cu nhm to ra sn phm blend gia polyme nhit do v tinh bt, vi c tnh
phn hu tt.
Thut ng tinh bt nhit do, tinh bt bin i cu trc hoc tinh bt
nng chy, c s dng nhiu m t s thay i cu trc ca tinh bt trong
qu trnh gia cng vt liu do. S phn hu phn t tinh bt gia cng my n
tng khi ta tng nhit v gim hm lng nc. Nghin cu v qu trnh
chuynt pha v s thay i cu trc ca tinh bt khi thay mt phn H2O bng
glyxerin cc nhit khc nhau. Do glyxerin c hng s in mi thp hn
H2O, do n lm tng nhit h ho ca tinh bt. Glyxerin c nhit
chuyn pha l 80 C, s lm gim nhit chuyn pha ca tinh bt v nh hnh
c hm lng H2O thp. Gii nhit chuyn pha rng ca hn hp tinh bt
polyol c xem nh l s phn nh tnh khng ng nht cao hn v cu trc
km bn hn so vi trng hp khi s dng H2O lm cht ho do.
Do vy cc tnh cht ca tinh bt ho do ph thuc nhiu vo bn cht v
nng cht ho do. Qu trnh bo qun phi rt c quan tm do s nhy cm
ca tinh bt ho do vi m.(6,7).
Cc phng php h ho:
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25
_________________________________________________________________
* TB c nu vi nc c khuy nh: to ra dng bt nho, c nht
cao. Phng php ny ng dng trong cng nghip thc phm hoc cht kt dnh
trong cng ngh giy.
* Dng ni p sut. khi TB c phn tn vi cc cht ho do dng
huyn ph 5-10%. Sn phm thu c sau khi lm kh: cng, chc v hi dn.
* Dng my trc vt: c th gelatin ho TB trong khong rt rng, c bit
TB c m thp 15-20%.
* Dng my trn Mixer- Brabender: To TB rt ng u, c kh nng
trn hp thp.
2.1.7 ng dng ca tinh bt
Tinh bt t lu c coi nh l mt thc phm chnh. Trong khu phn n
ca chng ta, tinh bt chim mt phn tng i ln. Tinh bt ngoi chc nng
chnh l lm thc phm cn s dng lm nguyn liu cho cc lnh vc khc.
Nhng khm ph u tin cho thy rng vo nm 3000 nm trc CN, tinh
bt lm cht kt dnh cho giy ci ca ngi Ai Cp c. Theo Catto v Plinin th
ngi Hy Lp v Roma s dng tinh bt lm trng v tng tnh cng cho
vi lanh.
Nm 1811, Kirchoff khm ph ra phn ng thu phn tinh bt thnh
glucoz. Khm ph quan trng ny t nn mng cho nghnh cng nghip da
trn nguyn liu l tinh bt sn xut ra detroz v dextrin.
Tinh bt lm nguyn liu giy, sn xut cc ho cht khc nh aldehyt,
xeton, cc axit hu c.
Tinh bt lm nguyn liu sn xut ru etylic.
Ngy nay nh phn ng h ho tinh bt, lm tng cng kh nng trn hp
tinh bt vi cc hp cht khc nhm to ra vt liu t phn hu. y l mt ng
dng mi ca tinh bt, n m ra mt hng nghin cu mi, kh nng sn xut
v ch to cc vt liu t hu, gp phn gim gi thnh sn phm v bo v mi
____________________________________________________________________________
26
_________________________________________________________________
trng t cc cht thi polyme khng c kh nng phn hu c ngun gc t du
m, ang cn kit v c gi thnh cao.
Mt s ng dng ca mng c kh nng phn hu trn c s tinh bt:
Vt liu bao gi trong cng nghip thc phm, do mng tinh bt c
xuyn thm thp.
Mng phn hu dng trong che ph t nng nghip do c th b phn
hu thnh sn phm khng c khi tip xc vi t v nh sng.
Tinh bt c s dng lm ph gia cho cht do vi nhng mc ch
khc nhau, tinh bt c dng nh mt cht n cho cc h nha khc nhau
ch to cc loi phim khng thm nc nhng li cho kh xuyn qua, nh vi
mng PE t trng thp.
Tinh bt c ghp vi cc monome ca cht do khc lm mng phn
hu sinh hc hoc cht trng n, siu hp th nc..
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27
_________________________________________________________________
2.2 Tinh bt sn
2.2.1 Gii thiu
Cy sn (Cassava ) l mt cy lng thc u m, m, pht ngun t lu vc
sng Amazon, Nam M, v ngy nay c nhn rng ra ton th gii. Hin nay,
cy sn l mt trong nhng loi cy thc phm quan trng trong c cu lng
thc ca nc ta, ch sau cy la, ng.
Cy sn c nhiu loi: sn ng, sn ngt..L loi cy trng cho nng sut
cao, trung bnh vo khong 5 - 10 tn/ ha, nay tng n 40-60 tn/ha. Vi sn
lng trn th gii 175 triu tn/ nm, vi din tch 14-15 triu hecta.
ng dng ch yu trong nghnh cng ngh thc phm v mt s nghnh
cng nghip khc..
Sn lng sn ca nc ta trong nhng nm gn y.
Stt
1.
2.
3.
4.
5.
6.
7.
Nm
Din tch (ha)
1939
19.500
1958
16.500
1970
85.219
1980
447.000
2000
237.600
2002
337.000
2004
383.600
(Ngun: Nim gim thng k 2004).
Sn lng (tn)
97.230
154.000
635.236
3.978.000
1.986.300
4.438.000
5.572.800
2.2.2 Tinh bt sn
Tinh bt sn c tn khoa hc Manihot utillissimapehl, thuc h
Enphoibiaceace, c kch thc 535m, dng ht trn, c hm lng amiloza
20%, T h ho =5264C.
L thnh phn ch yu trong sn, c s dng ch yu trong cng ngh
thc phm nh lm thc n cho gia sc.. v l ngun nguyn liu ln sn xut
mt s loi ha cht : Cellulose triacetate, Vinyl axetate, nha PVC, Stryeren,
Polystryrence.. do vy cc nc trn th gii lun ch trng v pht trin ngun
tinh bt sn.(7).
____________________________________________________________________________
28
_________________________________________________________________
Sn lng tinh bt sn ca mt s nc trn th gii. (1000 tn ).
35
30
25
20
Quc gia
15
10
5
0
Nigeia
Brazil
Thailand
India
China
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29
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2.2.3 Qu trnh sinh tng hp tinh bt sn
( Tinh bt sn c thnh phn ch yu l ADD- Glucose cu to ln).
Tinh bt
Amylopectin
Amylose
Surose
Sucrose synthase
(1)
UDD glucose,
Frutose
ADP
glucose
(2)
ADP
glucose
UDD glucose
Pyrophosphorylase
Glucose
1- phosphate
ADP
glucose p-
Glucose
1- phosphate
Phospho glucomutase
Phospho glucomutase
Glucose
6- phosphate
Glucose
6- phosphate
Tinh bt cht
Amyloplast
(1)
(2)
_________________________________________________________________
2.2.4.1 Cc cng on c bn
Ra v gt v c loi b t dnh vo c v lp biu b thnh bo v.
No hoc nghin ph v cu trc t bo, lm v thnh t bo gii
phng cc ht tinh bt ring bit m khng b h hi.
Sng hoc trch ly.
Tinh sch loi b tp cht khi hp phn bng phng php lng, lc, ly
tm.
Sy kh loi b m.
Tn bt ng bao.
Yu cu ca TBS (7) :
Thnh
phn
Hm
Nc
70,25
TB
21,45
Protein
Cht
Xelluloz
ng
Tro
1,12
bo
0,4
1,1
5,13
0,54
lng (%)
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31
_________________________________________________________________
2.2.4.2 S khi qu trnh sinh tng hp tinh bt sn
Nguyn liu
Ch, ra
Nc
Bm nghin, no c
sn s cp, th cp
Nc
Ly tm, trch
ly tinh bt
Dch c
2
3
B sn
Sa Tinh
bt
Phn ly tch
tinh bt
C c
Sy kh
ng
Lm ngui
L t u FO
Khng kh
Thu sn
phm
2.2.4.3Mt s phng php bin tnh tinh bt sn
____________________________________________________________________________
32
_________________________________________________________________
Phng php vt l.
Phng php ha hc.
Phng php s dng xc tc l enzyme.
2.2.4.4 Mt s sn phm ng dng t tinh bt sn
a. Maltodextrin. (DE)
* L mt loi polysaccaride khng ngt c cng thc phn t l
(C 6 H 10 O5 ) n .H 2 O ) ,
(C6 H10O5 ) n .H 2O )
Maltodextrin
Phng php sn xut Maltodextrin bng phng php enzyme.
ng dng.
- Sn phm DE 4-7 dng to mng mng d tan v t phn hy c s
dng bc v ko, tri cy, kem, cht n..
- Sn phm DE 9-12 dng trong cng nghip ung, thc n ring cho vn
ng vin th thao, lm ko gum mm, cht tr sy, to hnh..
- Sn phm DE 15-18 dng lm cht kt dnh, tng v cho ung, thnh
phn b sa, c ph ho tan.
b. Cc sn phm xiro
Sn xut bng phng php thy phn tinh bt sn trc tip trong axit
thu c sn phm cha DE 42 (16-24% Dextrose, 12-18 % ng i, 42-61%
ng cao phn t).
ng dng :
____________________________________________________________________________
33
_________________________________________________________________
c s dng nhiu trong cng ngh ch bin thc phm v cc nghnh
cng nghip khc nh :
- Nghnh thc phm : sn xut ko cng, ko carramen, ko do, ko gm,
ln men bia..
. Cng ngh sn xut ung : cng ngh ln men bia Bxungualt i
mch, cung cp ng cho qu trnh ln men, tng v cho sn phm .
. Cng ngh ch bin sa : kem, iu chnh ngt, chy..
- Nghnh dc phm : pha ch cc thnh phn dc tnh, cht mang cho
dung dch dch Xiro ho v cc thnh phn khc..
- Cc nghnh cng ngh khc : sn xut keo dn, cht lm sch khng kh,
nc thm..(9).
2.3. Phn ng a t
Phn ng a t hay ngng t xy ra gia cc hp cht c cha nhm chc
(OH, hydro linh ng, -COOH, -NH2, halogen), qu trnh ny to thnh cc
hp cht mi do s kt hp cc nhm chc trn v cc cht thp phn t nh:
nc, HCl, amoniac, ruTheo c tnh ca qu trnh ho hc ca phn ng a
t, ngi ta chia phn ng a t c cn bng v khng cn bng.
2.3.1 Phn ng a t c cn bng
Phn ng a t cn bng l nhng phn ng nh este ho.. trong cc hp
cht tham gia c mt, hai hoc nhiu hn. Vi cc hp cht u c mt nhm
chc th phn khng tip tc lin kt vi nhau v khng to thnh hp cht
polyme, nh phn ng este ho:
A-x + B-y
A-B +
x-y
( A, B l phn gc ca cc hp cht tham gia phn ng, x,y l nhng nhm chc,
xy l sn phm ph, hp cht thp phn t)
____________________________________________________________________________
34
_________________________________________________________________
Tuy nhin vi phn ng m cc monome tham gia c hai nhm chc tr ln
th qu trnh kt hp l lin tc v lp i lp li, do vy sn phm l cc hp cht
cao phn t.
1.
x-AB-y
1. x-A-x
x-A-x ++ y-B-y
y-B-y -xy
-xy
x-AB-y ++ x-A-x
x-A-x -xy
-xy
x-ABA-x
+
y-B-y
-xy
x-ABAB-y
x-ABA-x + y-B-y -xy x-ABAB-y ...
...
2.
2. x-A-y
x-A-y ++ x-A-y
x-A-y
-xy
-xy
-xy
-xy x-AA-y
x-AA-y
x-AAA-y
x-AAA-y
++ x-A-y
x-A-y -xy
-xy
____________________________________________________________________________
35
_________________________________________________________________
Khi monome ch cha mt nhm chc th khng to thnh polyme
ngay c khi phn ng xy ra hon ton.
Trong phn ng a t cn bng polyme ch thu c khi phn ng xy
ra n cng.
Khi hu nh ton b monome tham gia phn ng th v l thuyt
khng phi tt c cc nhm chc u tham gia phn ng.
S kha mch ca i phn t do cht n nh.
2.3.2 Phn ng a t khng cn bng
Phn ng a t khng cn bng l phn ng c th xy ra kh chm nhit
cao ( phn ng ca dicloetan vi natri kim loi) hoc phn ng din ra nhanh
nhit thp to polyme khi lng thp ( gia axit a chc v hp cht a
chc co hydro linh ng(glycol, diamin..)). Tc cao v xy ra theo mt chiu
l do s c mt ca kim trung ho ngay lp tc HCl to ra, nh phn ng:
N ClCO-R-COCl
+ n HO-R-OH
2n HCl
+
H-[O-R-OOC-R-CO]2n-Cl
_________________________________________________________________
Phng php a t trong nh tng cng tin hnh trn h hai pha trong nh
tng v vng ng hc nh s khuy lin tc, thu c sn phm c khi lng
phn t cao khi phn ng thc hin kh su.
Phng php a t trong dung dch th nng cht tham gia phn ng v
dung mi nh hng ln n tc phn ng v khi lng phn t ca polyme.
c bit trong mi trng demetylfomamit, dimetylsolfoxit.. c kh nng to
phc hot ho vi andehit ca cc axit a chc hoc trung ho HCl thi ra trong
qu trnh phn ng.
2.3.3 Phn ng ng a t
Trong phn ng ng trng ngng ngi ta s dng hn hp diamin vi hai
axit hai nhm chc khc nhau hoc axit hai nhm chc vi hai glycol khc
nhauQu trnh c biu din dng tng qut:
+ y-R-y
x-R-R-y
x-R-x + y-R-y
x-R-R-y
x-R-x
+
+
xy
xy
_________________________________________________________________
V d cho phn ng trng hp ti kt hp n-diisopropylbenzen vi gc t do
ly t phn ng phn r cht khi u.
_________________________________________________________________
Axit lactic (AL), axit 2- hydroxylpropionic, c phn lp u tin vo nm
1780 t sa chua v nc syro mu nu, khng tinh khit bi nh ho hc ngi
Thy in, Scheele. Mt nh ho hc ngi Thy in khc l Berzelius lp
li th nghim ca Scheele v cng i n kt lun AL l mt n cht. ng cng
tm thy AL trong sa ti, tht b v mu ca mt s ng vt. Nm 1839,
Fremy iu ch ra AL bng phng php ln men cc hp cht cacbonhydrat
nh: sucroz,, lactoz, mannitol, tinh bt v dextrin. Nm 1881, AL ln u tin
c sn xut trong cng nghip.(4).
2.4.1.1 Tnh cht vt l
AL l mt axit hydroxyl cacbonxylic n gin nht, c cng thc tng qut
CH3(HO)CHCOOH, gm hai ng phn quang hc l L (+) axit lactic (LAL) v
D (-) axit lactic (DAL).
Axit lactic
L- axit lactic
D- axit lactic
____________________________________________________________________________
39
_________________________________________________________________
AL c M=98,08. Ts= 122C, Tnc= 18C, hng s phn ly K= 1,38 10-4.
nng trn 80%, dung dch AL c d20 =1,2006, n20=1,424; tnc = 52,752,8 C
(dng isome), ts = 125140C; []25= +2,53.(4)
2.4.1.2 Phng php tng hp
AL c iu ch theo hai phng php chnh:
Phng php tng hp t du m:
Du m
Etylen
Axetandehit
Axetonitril
Racemic AL.
Glucoz
Trong hai phng php trn, phng php ln men t ra u vit hn, do sn
phm i t sn phm ho du lun to ra hn hp racemic, gy kh khn cho qu
trnh tinh ch. V vy vic la chn h vi sinh vt thch hp, tng hiu qu cho
qu trnh len men. Bn cnh cn l s li th v ngun nguyn liu ti to.
2.4.2 Polylactic axit (PLA)
2.4.2.1 Lnh s qu trnh tng hp PLA
PLA l mt trong nhng polyme u tin m con ngi tng hp c. Nm
1833, Gay Lussac iu ch thnh cng PLA khi un nng LA. Nhng phi
n nm 1932, c s l lun ca vic tng hp PLA c pht minh bi Wallace
Carothers cha ca polieste hin i. Theo , PLA c to thnh khi un
nng AL trong chn khng. Nm 1954, hng Dupont ang k bn quyn pht
minh ny v t PLA mi thc s c ch trng pht trin.
T nhng nm 1960, ngi ta ch ti tnh tng hp v phn hu sinh
hc ca PLA. Tuy nhin, do gi thnh cao nn n ch c p dng trong nghnh
y t nh: ch khu t tiu, v bc thuc nh chm, mt s chi tit cy ghp tm..
Nhng t thp nin 80, di p ca vn rc thi gy nhim mi trng
ca vt liu bao gi v cc vt liu khc c ngun gc ho du th vt liu d
phn hu PLA bt u c quan tm, ch nhiu hn. Nm 1987, tp on sn
____________________________________________________________________________
40
_________________________________________________________________
xut nng nghip Cargill ca M bt u nghin cu sn xut PLA t tinh bt
ng. n Nm 1992, h bt u sn xut quy m phng th nghim. Do c
nhng kh khn v mt k thut v cng ngh, Cargill lin kt vi Dow
Chemical - mt cng ty rt mnh v polyme hnh thnh lin doanh Cargill
Dow polymers LLC. n nm 2002, nh my sn xut PLA quy m cng
nghip u tin Nebraska vi cng sut 140.000 tn PLA/ nm. Nht bn v
Chu u cng c nhng d n tng t nghin cu sn xut PLA nh FAIR
PL-97-3070.
Vic s dng PLA s gii quyt c trit hai vn cp bch hin
nay: nhim mi trng do polyme bao b c ngun gc du m rt kh b phn
hu v s cn kit ca du m trong tng lai.(4,7).
2.4.2.2 Kh nng phn hu ca PLA
Theo Carothers, bn cht ca qu trnh phn hu PLA chnh l s thu phn
PLA, do PLA l mt polyeste bo. Nc b hp ph lm t cc lin kt este
dn ti s gim lin tc khi lng phn t PLA. Tc phn ng thu phn ph
thuc ch yu vo m v nhit ca mi trng phn hu.
C ch thu phn ca PLA.
____________________________________________________________________________
41
_________________________________________________________________
____________________________________________________________________________
42
_________________________________________________________________
2.4.3 Cc phng php iu ch PLA t AL
Hin nay, c 3 phng php chnh tng hp PLA(11):
Phng php trng ngng m vng lactit (Ring opening
polymerization, ROP).
Trng ngng trc tip AL trong dung dch c km theo qu trnh tch
nc thu c polyme c khi lng phn t ln.
Trng ngng AL thnh PLA phn t khi thp ( vi nghn n vi chc
nghn, vc), sau tng phn t khi bng cc tc nhn ko di mch cho n
phn t khi mong mun.
____________________________________________________________________________
43
_________________________________________________________________
S tng qut cc phng php tng hp PLA(4):
C6H12O6
Glucoz
Sinh khi
(tinh bt, ng..)
Ln men
Tinh ch
D-,
D-, L-lactic
L-lactic axit
axit
hoc
hoc hn
hn hp
hp racemic
racemic
Ti
Ti ch
ch
Trng
Trng ngng
ngng
trc
tip
trc tip (
( n-1)
n-1) H
H22O
O
n = 30 70, Oligome
Lactit
-2
-2 H
H22O
O
Trng
Trng ngng
ngng
m
m vng
vng
(ROP)
(ROP)
H2O
H2O
Trng
Trng ngng
ngng
trong
trong dung
dung dch
dch
____________________________________________________________________________
44
_________________________________________________________________
2.4.3.1 Phng php ROP
y l mt phng php ph bin nht dng iu ch PLA. Phng php
ny c Carother pht hin t nm 1932. Theo , qu trnh tng hp PLA tri
qua 2 giai on:
Giai on 1: Trng ngng AL c oligome phn t khi thp, sau
phn hu oligome ny vi xc tc thch hp to thnh lactit.
Giai on 2: Polyme ho m vng lactit thnh PLA, giai on ny
quyt nh hiu sut v cht lng sn phm.
Phng php ROP s dng cc loi xc tc c kim nh Sn(II)octoat, ZnCl2
v ca cc kim loi khc nh AL, La, Fe, Ti.. cho cht lng sn phm tt v c
chn lc cao vi iu kin phn ng n gin hn.
Cht lng ca PLA ph thuc rt nhiu vo thnh phn ca LA, t l
DLA/LLA trong hn hp. PLA thu c c th dng v nh hnh hon ton,
mt phn v nh hnh, mt phn tinh th hoc gn nh tinh th ho hon ton.
u im ca phng php ROP l cho cht lng sn phm tt, thi gian
phn ng ngn, tng i d thc hin.
Nhc im l gi thnh xc tc cao, khng thu hi c xc tc sau phn
ng nn gi thnh sn phm cao. Nhit phn ng qu cao d sinh ra cc phn
ng ph nh depolyme ha, racemic ha lm gim cht lng sn phm.(13).
2.4.3.2 Phng php trng ngng AL trong dung dch c km theo s tch
loi nc
Theo phng php ny, AL c trng ngng trc tip trong dung dch
to PLA.
Vi vic s dng xc tc ch yu l Sn, Zn, trong dung mi metanol, tch
nc bng xylen v mt s ho cht khc. Do vy cc yu t nh hng n qu
trnh trng ngng nh: nhit , nng , xc tc v c bit qu trnh tch nc
s nh hng rt ln n cht lng ca PLA thu c. c bit, y l phn ng
____________________________________________________________________________
45
_________________________________________________________________
trng ngng do cn tin hnh trong thi gian di v vy m mc nh hng
ca cc yu t trn ti cht lng sn phm l cng r rt. (4).
2.4.3.3 Phng php ni mch PLA c phn t khi thp thnh PLA c
phn t khi ln bng cc tc nhn ko di mch thch hp. (PLA bin tnh)
Phng php ny gm 2 giai on:
Giai on 1: Trng ngng trc tip LA to PLA phn t khi thp (vi
nghn n vi chc nghn vC).
Giai on 2: Da trn c im ca phn t PLA c mt u l nhm
OH, mt u l nhm COOH, do c th ni mch ny vi nhau bng cc tc
nhn ni mch polieste thng dng nh: bis (2 -oxazolin), diisoxianat, bis
epoxy..Cc tc nhn ny phn ng nhanh vi cc nhm hydroxyl hoc cacbonxyl,
ng thi khng sinh ra cc sn phm ph c hi.
Mt s tc nhn khu mch c nghin cu v cho kt qu nh: Maleic
anhydrit (MA), Methylen diphenyl diisocyanate (MDI)..(16).
Cc tc nhn ni mch c khi c cho vo ngay trong qu trnh trn, p
n, do vy lm gim chi ph, thi gian v tng hiu qu ca qu trnh.
Hin nay PLA c tng hp ch yu theo phng php ROP. Tuy nhin,
xc tc c s dng trong phng php ny l kh phc tp, t tin v kh thu
hi, do gi thnh sn phm s cao hn. Mt khc, cc c tnh u vit ca
PLA bin tnh c khng nh ( s c ni n phn sau), do vy phng
php ny rt c tim nng c khai thc v ng dng.
2.4.3.3.1 PLA bin tnh trn c s LA v 1,4 dihydro benzoic axit
1,4 dihydro benzoic axit c cng thc phn t l HOC6H4COOH, cng thc
cu to
____________________________________________________________________________
46
_________________________________________________________________
Khi lng phn t M=138,123 g/mol, t trng d= 1,44g/cm3, Tcm=159 C,
Ts= 211 C.
S bin tnh PLA vi 1,4 dihydro benzoic axit.
____________________________________________________________________________
47
_________________________________________________________________
2.4.3.3.3 PLA bin tnh trn c s LA vi Methylen diphenyl diisocyanate
(MDI)
MDI hay Methylen diphenyl diisocyanate c cng thc phn t l
C15H10N2O2, trng lng phn t l 250,3 g/mol, Tcm= 40C, Ts= 314C, tn ti
dng tinh th hoc lng mu vng sng, mi thm ( ngng thm ca MDI l
0,4 ppm, (1 ppm = 10.2 mg/m3)), p sut bay hi 5 10-6 mm Hg 25 C.(16).
S bin tnh PLA bng MDI:
____________________________________________________________________________
48
_________________________________________________________________
Maleic anhydrit c cng thc phn t C4H2O3, khi lng phn t M= 98,06
g/mol, dng tinh th mu trng, t trng d= 1,314 g/cm3, Tcm=53C, Ts= 202C,
dung dch trong nc 40g/100ml.
S bin tnh PLA vi Maleic anhydrit.
2.4.3.5
_________________________________________________________________
phm to thnh do kh nng iu chnh mt s ch tiu k thut ca vt liu:
nhit chy mm (Tg), khi lng phn t (Mw/Mn), cu trc.
Vi hm lng xc tc khc nhau, ti cc nhit khc nhau to ra s
khc bit khi lng phn t ca sn phm trong qu trnh tng hp c
thng k di y.
Stt
Xc tc
Khi
T l D-
Hm
%)
lng
Lactic
lng
Mn
(%mol)
Axit-
tng
lng
hp (C) Mw
(g/mol) (g/mol)
hydroxyl
1.a H3PO3
0.1
180
3800
2400
12.7
50.9
1.b
0.1
200
6500
5800
12.9
21.6
1.c
0.1
220
7800
7700
27.1
16.0
1.d
0.5
200
10600
10400
18.0
11.2
2.a Sn(II)oct 0.1
180
8000
6800
10.5
17.5
2.b
0.1
200
12900
8900
20.6
13.7
2.c
0.1
220
14000
9100
47.9
13.4
2.d
0.5
200
30800
28200
41.7
4.3
3.a ZnCl2
0.1
180
4700
5000
12.6
24.4
3.b
0.1
200
9100
9000
20.7
12.8
3.c
0.1
220
8100
7700
33.8
14.8
3.d
0.5
200
14800
9400
26.2
13.0
4.a H2SO4
0.1
180
31000
28000
5.6
4.3
4.b
0.1
200
30600
29100
9.7
3.9
4.c
0.1
220
32600
29200
8.4
4.2
4.d
0.5
200
20400
18500
6.3
6.3
Kt qu cho thy vic nh gi cc yu t nh hng n qu trnh tng
hp: nhit , hm lng xc tc..Do vic la chn v s dng hiu qu cc
loi xc tc l c ngha rt quan trng.
Mt vn rt c lu ti l nh hng ca qu trnh hay thi gian phn
ng n nhit chy mm v hm lng phn cu trc tinh th c tng
hp di y.(17).
____________________________________________________________________________
50
_________________________________________________________________
Stt Sau tng hp
Sau 12h
Sau 24h
Sau 36h
Tg Tm Tinh Tg Tm Tinh Tg Tm Tinh Tg Tm Tinh
C
1.a
1.b
1.c
1.d
2.a
2.b
2.c
2.d
3.a
3.b
3.c
3.d
4.a
4.b
4.c
4.d
34
41
39
41
43
47
44
49
40
44
41
45
th
136
141
%
5.4
5.3
134
148
0.4
39.2
139
9.1
164
154
163
163
50.6
48.7
49.1
52.3
C
37
42
41
43
46
47
45
47
40
45
43
47
48
55
50
50.3
th
137
140
%
5.4
5.3
133
148
133
1.7
46.6
0.3
139
134
9.6
1.2
165
161
163
164
53.0
41.3
49.3
53.9
C
34
42
39
42
30
40
46
48
30
38
41
46
41
56
54
55
th
138
140
%
5.4
5.5
136
147
130
1.2
45.6
0.4
140
134
13.3
1.8
161
153
166
154
57.3
35.4
49.8
52.1
C
37
42
41
44
35
46
46
47
40
44
44
46
57
57
58
56
th
137
141
%
5.6
5.6
131
148
127
1.2
44.2
0.6
139
135
14.2
1.8
158
154
158
154
58.4
35.5
49.4
53.0
_________________________________________________________________
phn b khi lng phn t rng 3600g/mol 32000g/mol, nhit ho thu
tinh 34C - 50C v m ra nhng ng dng khc nhau cu sn phm tng hp.
2.4.5 ng dng ca PLA
PLA c khng nh l mt trong nhng polyme c vai tr quan trng
trong nhng vt liu c kh nng phn hu sinh hc ang c ng dng trn th
gii.
Tn thng mi
ECO&B
ng dng
Qun o, mng ph trong
Hng sn xut
NTT Neomeit
Hokuriku
Horiaki
2.
Ti ng rau v
dng vn phng
Vt liu bao gi
3.
hoa qu
Cc, dao, ra, tha,
Minima Technology
4.
ti, khay..
Hp ng thc
Janpan
Daito Mechatronics
5.
phm, hp giy.
V hp ng
vn phng
Vt liu bao gi
Office Media
thc phm.
(Ngun: http://www.bpsweb.net/02_english/03_new_e/mark_syouhin/mark_shouhin_03.html).
_________________________________________________________________
2.5.2 C s cho qu trnh phn hu Blend
Mc phn hu ca Blend ph thuc vo hm lng TB c trong hn hp.
Do c s cho qu trnh phn hu l s mt s ng b trong cu trc ca vt liu,
do khi chn xung t cc tc nhn gy phn hu: vi sinh vt, nc, nm.. s tn
cng vo TB trc tin, gy s trng v phn hu TB, t to ra cc khuyt
tt, rng xp, gy suy yu tnh cht ca mng nh: bn ko t, gin di,
bn x t, bn va p gim mnh, dn ti cu trc ca vt liu s tip tc b
phn hu mt cch tch cc. Ngoi nn PLA b phn hu thng qua cc nhm
este hoc cc nhm chc khc cn c s gp mt ca qu trnh oxy ho phn ng
vi mui kim loi c sn trong t to cc peroxit, hydroperoxit lm tng cng
s phn hu cu trc mch polyme. Qu trnh ny tip tc din ra cho n khi vt
liu c phn hu hon ton.
2.5.3 S dng TB trong Blend
2.5.3.1 S dng TB nh l cht n
TB c s dng trong Blend c tc dng nh cht n c tc dng lm tng
kh nng phn hu cho vt liu. Nhng do TB c tnh u nc, nhit chy cao
hn nhit phn hu nn gy kh khn trong qu trnh gia cng TB vi cc loi
polyme khc, c bit l cc polyme khng phn cc. gii quyt vn ny
Griffin s dng cht bi trn nh sp hoc cht bo bc cc ht TB li lm
chng mt tnh u nc, do lm tng kh nng kt dnh TB vi cc loi nha
khng phn cc nh: polyetylen (PE)..Vi cc cht do phn cc kh nng lin
kt gia TB vi nn polyme l rt cao, tuy nhin do kh nng ht m cao ca TB
ngi ta cho thm mt s cht khu mch nh: PEG, MA, MDI
2.5.3.2 S dng TB dng nhit do
TB dng ht c nhit ho thu tinh (Tg) cao hn nhit phn hu (Td)
do lc tng tc rt ln gia cc mch i phn t to bi cc lin kt hydro. Qu
trnh h ho TB vi cc cht ho do s b gy lin kt hydro gia cc mch i
____________________________________________________________________________
53
_________________________________________________________________
phn t, lm gim Tg xung nh hn Td to ra pha lin tc ca cc phn t
polysacarit. Qu trnh bin i TB thnh dng nhit do, lm tng mc phn
b ca TB vo nn polyme, nhng mc tng hp cn tng thp do cn
phi s dng cc cht tr tng hp.
____________________________________________________________________________
54
_________________________________________________________________
Chng 3. Nhim v ca ti
T nhng u im ni bt vt liu polyme phn hu sinh hc nu trn
v nhng li th v ngun nguyn liu TBS, chng ti xin c xut nhim v
ca ti l:
* Nghin cu ti u phng php ch to Polylactic axit (PLA) v PLA bin
tnh.
* To Blend trn c s tinh bt sn (TBS) v PLA, PLA bin tnh.
Tm ra t l v tng hp ti u.
Nghin cu la chn cht khu mch khc nhau.
nh hng ca iu kin tng hp n cht lng ca sn phm.
* Ch to mu.
* ng dng cc phng php nghin cu tnh cht v kh nng phn hu ca
mu nh: SEM, TGA, TMAqua mu c chn trong mi trng t
hoc c gia tc. T nh gi mc nh hng ca cc thng s k thut:
bn ko, gin di, bn nhit, bn cu trc, tn tht trng lng
nh gi tnh cht v mc phn hu ca vt liu.
____________________________________________________________________________
55
_________________________________________________________________
____________________________________________________________________________
56
_________________________________________________________________
____________________________________________________________________________
57
_________________________________________________________________
15. The Use of Difirent Diols in Synthesis of Low-Molecular-Weight LacticAcid-Based Telechelic Prepolymers. Journal of Applied Polymer Science, 10171023 (1998).
16. Disprension of Wood Microfibers in a Matrix of Thermoplastic Starch and
Starch-Polylactic Acid Blend. Journal of Biobased Materials and Bioenergy,
(2007), 71-77.
17. Effect of Catalyst and Polymerization Conditions on the Preparation of Low
Molecular Weight Lactic Acid Polymers. Kari Hiltunen.(1996).
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58