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Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

NHA PHN HY SINH HC POLY (LACTIC ACID) TNG QUAN V NG DNG

Phng Thanh V1, Trn Cng Huyn1, ng Th Cm Tin1 v Phm Ngc Trc Qunh1
1

Khoa Cng ngh, Trng i hc Cn Th

Thng tin chung:

Ngy nhn: 16/06/2015
Ngy chp nhn: 27/10/2015

Title:
Biodegradable Poly (lactic
acid) (PLA): Overview and
Applications
T kha:
Nha nhit do, nha phn
hy sinh hc, tinh bt ng,
poly(lactic acid) PLA
Keywords:
Biodegradable plastic, cornstarch, thermoplastic, poly
(lactic acid) (PLA)

ABSTRACT
Polylactic acid (PLA) is made from a natural resource - corn starch and
formulated from the condensation polymerization of D- or L- lactic acid
or ring opening polymerization of the lactide. It is completely
biodegradable, compostable, and can maintain its mechanical properties
without rapid hydrolysis even in high humidity conditions. In this review,
we study and explain why Poly (lactic acid) is considered as one of the
most environment-friendly biodegradable thermoplastic polyesters with
extensive applications.
TM TT
Nha Poly (latic acid) (PLA) c sn xut t tinh bt ng bng qu
trnh trng ngng D- hoc L-lactic acid hoc m vng Lactide. y l
loi vt liu phn hy sinh hc, c kh nng phn ha v c th duy tr
c tnh k c trong iu kin m cao. Chnh v l do , bi bo ny
s tng hp v trnh bi l do ti sao Polylactic acid li c quan tm
nh vt liu thn thin vi mi trng c kh nng ng dng rng ri
nht hin nay.
ngun gc du m khng phn hy sinh hc.

1 TNG QUAN
1.1 Gii thiu chung

Nm 2002, cng ty Cargill Dow polymers

(LLC) a PLA vo sn xut qui m cng
nghip u tin Nebraska vi cng sut 140.000
tn/nm (Phuong, 2012). c tnh n nm 2015
sn lng tiu th PLA c th t n 500.000
tn/nm v cn c th tng n 1 triu tn/nm n
nm 2020 (Gongzhuling Annual Output, 2014).
1.2 Tnh cht ha l ca PLA

Polylactic acid (PLA) l mt trong nhng loi

biopolymers c s dng ph bin nht hin nay
(khong 200.000 tn/nm) (Johansson, et al., 2012,
Mehta, et al., 2005) do c bn ko cao, gi
thnh thp, trong sut, kh nng tng hp sinh
hc cao. PLA c sn xut t tinh bt bp v y
l ngun nguyn liu c kh nng ti to t qu
trnh sn xut nng nghip, khng nh cc loi
polymer khc c sn xut t nguyn liu du
m. c bit, PLA rt thn thin vi mi trng
bi kh nng phn hy sinh hc cao (phn hy
hon ton t 90 n 180 ngy, ty theo iu kin
phn hy sinh hc) (Phuong, 2012). Chnh v vy,
trong mi nm tr li y, PLA c tp trung
nghin cu v a vo s dng rng ri trn th
trng, thay th cho nhng sn phm polymers c

Poly (lactid acid) (PLA) c cng thc ha hc

l (C3H4O2)n , Mw=0,89-2,98. 106 (Lu L, 1999,
Polylactic acid, 2014).
PLA thuc nhm poly (-hydroxy ester), c
iu ch t ngun nguyn liu c ngun gc t
nhin l tinh bt (a phn t tinh bt bp).
PLA c tnh cht ha l gn ging nh poly

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(ethylene terephtalat) (PET) c tng hp t

nguyn liu ha thch nh cng cao, modun n
hi cao, bn ko t ln, nhng khc vi cc
vt liu polymers c ngun gc du m l PLA c

kh nng phn hy sinh hc cao nn thn thin vi

mi trng (Drumright, et al., 2000, Sawyer,
2003).

Hnh 1: Cng thc cu to ca PLA (CAS: 26100-51-6)

Lu L, 1999, Polylactic acid, 2014

phn trm ca PLLA trong hn hp blended s

nh hng n nhit chuyn thy tinh Tg v
nhit nng chy Tm ca PLA thng mi
(Drumright, et al., 2000, Rasal, et al., 2010).

T hai loi ng phn ca Lactic acid trong

Hnh 2 l D-Lactic, L-Lactic c th iu ch c
ba dng ng phn hnh hc ca Lactide (Auras, et
al., 2011), t thng qua phn ng polymer ha
m vng, to ra ba dng PLA vi tnh cht ha l
c trnh by trong Bng 1: poly (D-Lactic acid)
(PDLA), poly (L-Lactic acid) (PLLA), poly (D,LLactic acid) (PDLLA) (Drumright, et al., 2000,
Xiao, et al., 2012). Qu trnh to thnh Lactide l
mt trong nhng giai on quan trng nht bi
tinh khit quang hc ca Lactide c nh hng trc
tip n sn phm PLA. Trn th trng hin nay,
PLA thng mi l sn phm blend ca PLLA v
PDLLA c tng hp da trn phn ng
polymers ha gia DLLA v LLA (Cargill/ Nature
Works LLC Press Release, 2009). Trong t l

Hnh 2: Hai dng ng phn ca monomer

Lactic acid tng hp PLA
Gupta, et al., 2007, Xiao, et al., 2012

Bng 1: Tnh cht ha l c bn ca 3 dng PLA (Xiao, et al., 2012)

Tnh cht
Kh nng ha tan

PDLA
PLLA
PDLLA
Khng tan trong nc, tan tt trong cc dung mi hu c nh
benzene, chloroform, acetonitrile, tetrahydrofuran (THF), dioxane
Kt tinh
Bn kt tinh
V nh hnh
~180
~180
C th thay i
50 60
55-60
C th thay i
~200
~200
185-200
< 10
C th thay i

Cu trc tinh th
Nhit nng chy (Tm) (oC)
Nhit chuyn thy tinh(Tg) (oC)
Nhit phn hy (oC)
dn di (%)
Thi gian bn hy 370C trong dung
46
dch nc mui thng (thng)
1.3 Phng php chnh iu ch PLA

4-6

1.3.1 Phng php polymers ha trc tip

PLA c th c tng hp t ba phng php

khc nhau nhng ch yu bng phng php
polymers ha trc tip v phng php cationic
ring opening polymersization (ROP) (Hartmann,
et al., 1998, Linnemann, et al., 2003, Xiao, et al.,
2012).

PLA ch yu c tng hp bng phng php

polymer ha Lactic acid thnh PLA c khi lng
phn t thp (vi nghn n vi chc nghn vC)
sau tng phn t khi bng cc tc nhn ko di
mch cho n khi lng phn t mong mun.
Phng trnh polymer ha bng phng php
polymer ha trc tip c th hin trong Hnh 3
(Garlotta, 2001, Xiao, et al., 2012).
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Hnh 3: Phng trnh iu ch PLA bng phng php polymer ha trc tip (Xiao, et al., 2012)
1.3.2 Phng php m vng cationic ring
opening polymersization (ROP)

(Sn(Oct)2) v mt s cht xc tc hu c nh 4(dimethylamino)pyridine (DMAP), N-Heterocylic

carbene (NHC) (Linnemann, et al., 2003) lm xc
tc trong dung dch alcohol iu kin nhit
cao v p sut thp c trnh by Hnh 4.
(Garlotta, 2001, Gupta, et al., 2007, Hartmann and
Kaplan, 1998, Jimnez, et al., 2014, Nieuwenhuis,
1992).

Phn ng to Lactide tri qua hai giai on.

u tin, monome Lactic acid c trng ngng
to thnh oligome. Sau oligome tri qua qu
trnh polymer ha ng thi vng ha to thnh
Lactide. Phng php ROP s dng antimony,
zinc(II), titanium(IV), tin(II) 2-ethylhexanoate

Hnh 4: Phng php ROP iu ch PLA (Linnemann, et al., 2003, Xiao, et al., 2012)
thp (Phuong, 2012), hn na PLA d b thy
phn, tc phn hy thp (Rasal, et al., 2010) v
sn xut PLA trong qui m cng nghip i hi
phi c chi ph cho quy trnh cng ngh cao, do
gi thnh sn phm cao hn so vi cc loi nha c
ngun gc ha thch nh PP, PE, PA,..( gi hin ti
ca PLA trn th trng l 2,6-3,2 USD/kg, trong
khi PP, PE ch c 1,2-1,8 USD/kg) (SE Asian,
2014).

1.4 u v nhc im ca PLA

1.4.1 u im
PLA l loi nha c kh nng phn hy sinh
hc cao vi thi gian phn hy ngn, v vy c th
tit kim c ngun nng lng nht nh x
l PLA. ng thi loi polymer ny c tng
thch sinh hc cao, khng c hi vi c th ngi,
nn c ng dng nhiu trong cc lnh vc c
bit l y sinh. Hin nay, PLA ang l sn phm
c sn xut v ng dng i tr trong cng
nghip vi gi thnh r hn so vi cc loi nha
phn hy sinh hc khc (2-3,2 USD/kg)
(Information from NatureWorks LLC, 2014) vi
bn ko v mun n hi cao (Tensile Strenght
55-75 MP, Youngs modulus 3-4GP) (Lu L, 1999,
PLA monomere (Polylactic Acid), 2014, Polylactic
Acid (PLA, 2014).
1.4.2 Nhc im

2 NG DNG CA PLA
Mc du polylactic acid c nhng u im ph
hp vi xu hng s dng vt liu polymers hin
nay, tuy nhin nhng yu im nh bn ko
thp, kh nng chu nhit km, kh gia cng
phn no hn ch kh nng ng dng PLA. Cng
nh cc loi polymer khc trn th trng, PLA
thng c bin tnh trc khi a vo sn xut
nhm p ng nhng yu cu c th trong tng
lnh vc ng dng. Cc nghin cu gn y cho
thy PLA thng c bin tnh da trn hai
phng php. Phng php th nht l bin tnh b
mt (surface modification) nhm to bm dnh
ca PLA vi vt liu khc. Vt liu bin tnh ny

PLA c nhng hn ch v mt tnh cht nh:

dn di (5-7%) (Information from NatureWorks
LLC, 2014, Phuong, 2012), nhit chuyn thy
tinh thp Tg (60-68oC) dn n kh nng n nh
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biopolymers, c bit l PLA bin tnh l la chn

tt nht trong lnh vc ny.

c ng dng trong lnh vc y sinh (truyn dn

thuc). Phng php bin tnh th hai l trn hp
hoc ha do vi cc polymner khc nhm tng
cng c tnh v kh nng chu nhit ca vt liu.
Phng php ny thng c ng dng trong lnh
vc bao b, ng gi, t, vt liu cch in v
composites) (Gupta, et al., 2007, Jimnez, et al.,
2014, Obuchi, et al., 2011, Phuong, 2012).
2.1.1 Trong k thut m

V d: Trong s cc loi bin tnh, PLA/Poly

(Glycolic
Acid)
v
copolymers
poly (lactic acid-co-glycolic acid) (PLGA) l mt
trong s t polymers c Cc qun l thc phm
v dc phm ca M (Food and Drug
Administration FDA) cho php ng dng lm sng
ngi. Loi copolymers ny c th nghim
thnh cng trong vic ti to cc loi m nhiu
c quan khc nhau nh: bng quang, sn, gan,
xng, van tim c hc (Ilan, et al., 2002).
2.1.2 Trong k thut dn truyn thuc

T nhng nm 1988, k thut cy m ra i v

tr thnh phng php c ng dng ph bin
trong lnh vc y sinh (Drumright, et al., 2000).
Phng php ny gip ti to li cc m sng bng
cch lin kt cc t bo sng vi h thng khung
bng cc vt liu sinh hc, cc t bo c th
sinh si ny n nhanh chng theo cc chiu hng
khc nhau. Vt liu sinh hc ra i m ra con
ng tim nng trong vic thay th cc m sng
v c trong cy ghp ni tng. C rt nhiu loi vt
liu sinh hc c a vo th nghim lm sng,
trong c kim loi, v c nhng chng li c
nhng nhc im ln nh tuy kim loi c c tnh
tt nhng li khng phn hy sinh hc, tch tr
trong c th con ngi gy nhng phn ng bt li
(Mathew, et al., 2005), hay vt liu v c b hn
ch do kh x l c v cu trc xp (Liu, et al.,
2004). Vt liu sinh hc lm h thng khung trong
phi tha cc iu kin sau: tng thch sinh
hc cao, c c tnh thp, c kh nng phn hy
sinh hc, vt liu phi c xp, c tnh v
kch thc ph hp, cc t bo hoc m c th
tng trng v pht trin tt v loi b c cht
c trong qu trnh trao i cht. Chnh v vy

Con ngi lun mong mun tm ra cch

phn phi cc dc cht vo ng c quan mong
mun ti u ha kh nng iu tr ca n cng
nh duy tr cc hot tnh trong thi gian cn thit
v gim thiu nhng tc dng ph ca thuc. Con
ngi th nghim lm sng nhiu nhm cht
khc nhau trong vai tr cht dn truyn thuc nh:
liposome, cc ht nano lipid rn. Tuy nhin, trong
thi gian gn y cc loi polyester phn hy sinh
hc trong c PLA, PGA v copolymers ca
chng ( nh PLGA) c ng dng nhiu trong
lnh vc truyn dn do vt liu c kh nng tng
thch sinh hc cao, kh nng phn hy sinh hc,
bn c hc, kh nng x l nhit v ha tan cao
trong cc dung mi hu c. Bn cnh nhng u
im trn th PLGA li c khuyt im l cu trc
ca chng li thiu i nhng nhm chc nng hot
ha to iu kin tng tc vi cc t bo, v
vy n lm cho hiu qu dn truyn thp v thi
gian lu trong c th khng lu.

Bng 2: ng dng ca mt s loi PLA bin tnh khc nhau trong k thut dn truyn thuc
(Drumright, et al., 2000)
Loi PLA

ng dng

Hiu qu
Tng cng vn chuyn qua nim
Dn truyn cho bnh un vn
PLA- PEG dng ht
mc mi
H tr dn truyn cho thuc insulin xt Kim sot tt nng glucose
PLA-b-pluronic-b- PLA
ming cho bnh i tho ng loi 2
trong mu
Dn truyn cho nhm thuc paclitaxel
Gim sng vim
PLA microsphere
chng ung th
Dn truyn cho nhm thuc 5 FU v
Hon thnh qu trnh gii phng
PEO-PLA copolymers
paclitaxel
thuc
PLA-PEG-PLA copolymers Dn truyn cho nhm thuc 5 FU v Kim sot tt qu trnh gii phng
paclitaxel
thuc
Dn truyn thuc cho qu trnh iu tr C kh nng khng li cc t bo
AP-PEG-PLA
ung th
ung bu
siu
nh,
vi
ht
(MP) v ht nano (NP). Kt qu
V vy, gim thiu hn ch trn, cc nh
th
nghim
cho
thy,
PLGA dng MP v NP l 2
nghin cu th nghim PLA bin tnh di
dng
cho
kt
qu
tt
nht, v vi kch thc siu
nhiu dng bo ch khc nhau: bt vin, vin nang
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nh, chng c th d dng thm thu qua cc mng

t bo, ci thin kh nng dn truyn v vi c
tnh vt l ca ht nano, thi gian phn hy ca
PLGA gim ng k, duy tr c hot cht trong
sut qu trnh vn chuyn (Drumright, et al.,
2000).

trong cc siu th v cc vt gia dng khc nh ly,

mung, a... c bit PLA bin tnh dng
nanocomposites, c c tnh tng, tnh cht chn kh
v chn quang cao so vi PLA thng thng. Bn
cnh , cc loi PLA bin tnh gia cng bng
bentonite, c ph lp silicate v microcrystalline
cellusose c tnh khng tia UV v nh sng kh
kin (thnh phn c hi lm bin tnh cht lng
sn phm ) nn thch hp ng dng lm bao b bo
qun thc phm (Obuchi and Ogawa, 2011).

Ngoi ra, PLA bin tnh cn c ng dng

cy ghp hay ch to cc thit b y t nh thanh
nh hnh, tm, ghim, inh vt, ch t tiu
(Raghoebar, et al., 2006, Roney, et al., 2005)
hay ng dng PLA bin tnh cho phng php iu
tr cho da (nh teo m, so trn khun mt).

Ngoi ra trong bo qun thc phm, vic khng

khun lun c quan tm ch trng, bao b phi
p ng c yu cu v nhng thc phm ti
sng nh tht c, rau c qu, nu tip xc vi
bao b nhim khun s sinh ra hot cht gy bnh.
gii quyt vn , cc nh nghin cu tm
ra loi PLA bin tnh dng composite l hn hp
gia PLA dng nn lin kt vi ht pectin, trn b
mt vt liu s hp th v lu gi nhng hot
cht khng khun, hn ch qu trnh tn cng ca
vi khun ln b mt tip xc gia bao b v
thc phm.

2.2 ng dng trong lnh vc bao b ng gi

So vi cc PLA thng thng vi nhng hn

ch nh gin, n nh nhit thp th PLA bin
tnh khc phc c nhng khuyt im ca
PLA thng thng. Theo cc nghin cu th PLA
bin tnh bng phng php ha do, copolymer
ha v composite c ng dng nhiu trong vic
sn xut mng phim mng ng gi thc phm,
lm khay, hp ng thc n (Hnh 5), ti xch

Hnh 5: ng dng ca PLA bin tnh trong sn phm bao b thc phm
dummy card cm trc tip vo laptop chng bi
bn xm nhp vo. Nm 2006, n cn c ng
dng lm v in thoi cho dng sn phm cellular
phone(Obuchi and Ogawa, 2011).

2.2.1 ng dng trong lnh vc in t

Nm 2002, cng ty Mitsubishi Plastics ch
to thnh cng PLA chu nhit bng k thut phun
v n c a vo ng dng lm v my nghe
nhc Walkman ca cng ty Sony (Obuchi and
Ogawa, 2011).

Nm 2005, Fujitsu bt u ng dng composite

ca PLA vo thit b chng chy trong nh, sau
c cng ty NEC pht trin, s dng 10% si
carbon gia cng, sn phm t c c tnh nng
gp 2 ln so vi s dng thp khng g truyn
thng. Cng nm , Fujitsu cho ra i dng
my tnh xch tay FMV-BIBLO NB80K vi h
thng khung c ch to t hn hp blend
PLA/PC/phosphorus (Obuchi and Ogawa, 2011).

PLA bin tnh dng composite c ng dng

v pht trin rng ri trong lnh vc in t. Nm
2004, cng ty NEC Corp ca Nht s dng vt
liu composite nha nn PLA gia cng bng si
Kenaf (Vic thm si Kenaf gia cng gip tng
cng kh nng chu nhit ca vt liu) lm
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hc vo sn xut qui m cng nghip vi tn

gi Bio-Plex. Loi mng ph ny c th thay th
cho loi mng bng Polyethylene (PE) truyn
thng. Ngoi ra, PLA bin tnh cn c ng dng
lm chu cy, dy buc c chua v mt s vt dng
khc

Nm 2007, Samsung

s
dng
PLA/Polycarbonate bisphenol A (PC) trong vic
sn xut v cc linh kin in t ca mnh nh v
in thoi, v my tnh,... (PC c Tg v kh nng
chu va p cao, v vy khi trn hp s nng kh
nng chu nhit v va p ca vt liu ) (Samsungs
Bioplastics for Automobile, 2014).
2.3 ng dng trong lnh vc t vn ti

3 KT LUN
Trong 10 nm tr li y, PLA pht trin
nhanh chng v dn c ch ng trong th trng
vt liu polymers v ngy cng c cc nh sn
xut v ngi tiu dng la chn thay th cho cc
loi vt liu c ngun gc t du m. Tuy nhin,
nhng ng dng ca PLA bin tnh vn cn gp
nhiu thch thc, tr ngi do mt s im yu v
mt c tnh (nh gin di thp) v cha tht s
ti u v mt k thut ln kinh t. Vic ci thin,
nghin cu v pht trin rng nhng phng php
bin tnh s mang li bc tin mi cho vic ng
dng vt liu phn hy sinh hc PLA bin tnh vo
trong i sng v cc ngnh cng nghip trong
tng lai. Bn cnh , vic ng dng rng ri
nha phn hy PLA bin tnh s gii quyt c
phn no cc vn nhim mi trng gy ra do
cc loi vt liu polymers c ngun gc ha thch.

Hin nay, vt liu composites nn PLA l mt

trong nhng vt liu c a chung v s dng
rng ri trong lnh vc t vn ti. Nm 2003,
Cng ty Toyota ng dng composite nn PLA
v si kenaf sn xut ra lp xe d phng bng k
thut c khun trong dng sn phm Raum v
Prius (Bioplastics, 2014). So vi lp xe thng
thng, sn phm ch to t vt liu mi c kh
nng chu c tc ng bn ngoi cao hn. Bn
cnh , cng ty Toyota nghin cu vt liu
xanh y tim nng cho cc b phn khc ca
xe nh gh ngi, tm tri sn, tay cm (Bioplastics,
2014).
Mt phng php khc c nghin cu l
thm cht n ph hp vo nha nn PLA, kt hp
vi k thut phun khun, cng ty Ford thnh
cng v ng dng composite nn PLA vo ch to
h thng vm xe v tm thm tri cho dng sn
phm U (Auras, et al., 2011).

TI LIU THAM KHO

Auras, R. A., L.-T. Lim, S. E. Selke and H.
Tsuji, 2011. Poly (lactic acid): synthesis,
structures, properties, processing, and
applications. John Wiley & Sons.
Bioplastics, 2014.
http://www.speautomotive.com. (ng nhp
ngy 21/11/2014):
Cargill/ Nature Works LLC Press Release,
2009. http://www.natureworldsllc.com.
(ng nhp ngy 20/11/2014):
Drumright, R. E., P. R. Gruber and D. E.
Henton, 2000. Polylactic Acid Technology.
Advanced Materials: 1841-1846.
Garlotta, D., 2001. A literature review of poly
(lactic acid). Journal of Polymers and the
Environment: 63-84.
Gongzhuling Annual Output, 2014.
http://www.english.jl.gov.cn (ng nhp
ngy 18/11/2014):
Gupta, A. and V. Kumar, 2007. New emerging
trends in synthetic biodegradable polymers
PolyLactide: A critique. European polymer
journal: 4053-4074.

Nm 2007, Mitsubishi ng dng PLA si v

Nylon 6 lm tm tri xe cho cc dng sn phm
ca cng ty (Auras, et al., 2011).
Nm 2012, cng ty t Fiat- Italy, trong d n
Evolution, tin hnh nghin cu pht trin vt
liu polymer xanh nhm thay cho cc b phn
trong t m trc y c sn xut t cc loi
nha c ngun gc ha thch khc. Trong tng
lai, composite nn PLA s c th thay th cho cc
b phn khc ca cc dng xe Eco-friendly vi
con ngi v mi trng (Project, 2014).
2.4 ng dng trong lnh vc nng nghip
Vic s dng mng ph gip tng tc chn
ca cy trng, bo tn m v phn bn, c ch
s tng trng ca c di, nhim nm v cn trng
ph hoi. The FkuR Kunststoff GmbH, Willich hp
tc vi The Fraunhofer Institute UMSICHT,
nghin cu thnh cng mng ph sinh hc t hn
hp blend ca PLA, cht ph gia v mt s
polymers phn hy sinh hc khc. Sn phm ny
c u im l kh nng phn hy chm hn cc
loi mng ph sinh hc khc v kh nng chng
chu vi s thay i ca thi tit. V vy n nm
2005, Oerlemans Plastics a mng ph sinh
48

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Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

Obuchi, S. and S. Ogawa, 2011. Packaging and

other commercial applications. Poly (lactic
acid): Synthesis, Structures, Properties,
Processing, and Applications: 457.
Phuong, V. T., 2012. Sustainable
Biocomposites from Renewable Ressources
and Recycled Polymers. PhD Thesis University of Pisa:
PLA monomere (Polylactic Acid), 2014.
http://www.matbase.com/. (ng nhp ngy
21/11/2014):
Polylactic acid, 2014. http://en.wikipedia.org/.
(ng nhp ngy 20/11/2014):
Polylactic Acid (PLA, p., 2014.
http://www.makeitfrom.com/. (ng nhp
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