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21Chemistry&Chemica landEnvrionmenta lEngineeringCollege,WefiangUniverstiy,
g n a fi e
W 261061,Shandong,China
2Biologica landAgricutlura lEngineeringCollege,WefiangUniverstiy,
g n a fi e
W 261061,Shandong,China r o h t u a g n i d n o p s e r r o C * y e
K words :Polypropylene, Oxidaiton, Natura lanitoxidant, Dihydromyriceitn, Natura lweathering t s e t . t c a r t s b
A . EffectsofRosemary Antioxidanton (R ) ,ao extracted fromRosmarinusofficinalis, onthe f o s e i t r e p o r p e v i t n a d i x o i t n
a polypropylene were evaluated by investigating the difference of s e i t r e p o r p l a c i n a h c e
m and mel tflowability between pre and pos tnatura lweathering tests .For n o s i r a p m o
c purposes ,the effects ofa syntheticphenolic commercia lanitoxidan t(Irganox B215), . d e z y l a n a o s l a e r e
w The results showed tha tthe reduction of mechanica l properties a nd the t n e m e r c n
i of mel tflowability of polypropylene containing R ao were slowe r than tha tof the unstabiilzedreferenceduringtheagingprocess ,whichi mpliest ha tR aoexhibitshighefficiencyasa
r o f t n a d i x o i t n a l a m r e h
t polypropylene .On the other hand ,samples tha tcontained Irganox B215 d e v o r p m i r e h t r u f d e n i a t b
o stabiiltyoverthesamplescontaining R ao during 105days; however ,the s s e n e v it c e f f
e fo R ao lasted longerthan tha tof Irganox B215. R ao has thecharacteristic of being s s e l m r a
h and having high activity, good stabiltiy and abundan tresources to be a good natura l .t n a d i x o i t n a u d o r t n
I citon
) P P ( e n e l y p o r p y l o
P si animportan tthermoplasitcresinwith manydesirablepropertiesincluding s e i t r e p o r p l a c i n a h c e m d o o g d n a e c n a m r o f r e p g n i s s e c o r p t n e l l e c x e , t s o c w o
l (1) .However ,sincethe
s i n i s e
r easilyoxidized ,thereisagrea tneed to decrea setheantioxidaitonofPP. Themos tefficien t s i n o i t a d a r g e d d n a n o it a d i x o d i o v a o t d o h t e m t n e i n e v n o c d n
a the addtiion of antioxidants .The s s e n e r a w a l a t n e m n o r i v n e f o e s a e r c n i e d i w d l r o
w has brough tsomenewerand higherrequirements r
o
f hygienicsafetyt oanitoxidantstha tareaddedi npolymerproductsforfoodandmedicinecontact . t s a l e h t g n i r u d d e v r e s b o n e e b s a h s r e m y l o p n i s e v i t i d d a l a r u t a n f o e s u e h t r o f y c n e d n e t g n i w o r g A l a r e v e
s years )( .2 Nevertheless, many natura lproducts wtih antioxidan tacitvi ty can’t be used in s r e m y l o
p duet ot hei rpoorthermostability. . L s i l a n i c i f o s u n i r a m s o
R ,distributedwidely in European ,used asaspiceforthousandsofyears , s r a e y t n e c e r n i s c i t e m s o c d n a e n i c i d e m , d o o f n i d e i l p p a n e e b s a
h )( . 3 RosemaryAntioxidanton(Rao) ( s d n u o p m o c s d i o n o v a l f d n a d i o n e p r e t , s d i o n e p r e t i d g n i d u l c n i y l n i a
m 4) ,extracted from thestems
, s i l a n i c i f o s u n i r a m s o R f o s e v a e l d n
a havemanypharmacologica lfunctionsinorganisms ,including n o i s n e t r e p y h g n i t i b i h n i , m u t u p s g n i v o m e r , h g u o c g n i v e i l e
r ,protecting liver ,absorbing ultraviole t s e it r e p o r p l a i r e t c a b i t n a d n a n o i t a d i x o i t n a , n o it a i d a
r 5( - )1 . 1 R ao showe d a good therma lstabiltiy 2
w o l e
b 0 0 C° inourpreviousresearch, itt huscouldbeusedi n PP whoseprocessingt emperaturesi s n a h t r e w o
l 1 90 °C. In this report the efficiency of the antioxidan tperformance of R ao and a x o n a g r I h t i w n o s i r a p m o
c B215, whenadded topolypropylene, w asevaluatedby anatura l(outdoor) .t s e t g n i r e h t a e w d n a s l a i r e t a
M Methods
L , . o C l a c i m e h c o r t e P g n a h c g n i x g n a y e u
Y td. ,China) da n Irganox B215 (CibaSpeciatly Chemicals , a
n i h
C ) werepurchasedfromt heGuangzhouChemica lMarke.t f
o s e v a e l d n a s m e t s r e d n e t d e i r
D Rosmarinus oficinalis were mixed with ethano l and .
s n o i t i d n o c x u l f e r t a h 1 r o f d e t c a r t x e y l s u o u n i t n o
c Rao was produced from the collected extrac t 0
4 t a d e t a r o p a v
e C° underreducedpressure . P
P f o s n o i t a l u m r o f e h
T samples are listed in Table 1 .The components were mixed with a h hi -g speedmixerfor10min,andthenextrudedby aco-rotatingtwin-screwextruder E(T -35 ,Keya
. o
C , L .td ,China ,L/D raito is40) ,thetemperaturesfromthehopperto diea tseven differen tzones e
r e
w 180 ,185 ,190 ,190 ,200 ,200 ,190 C° ,respecitvely ,and the screw speed was140 rpm .The s
t e l l e p o t n i t u c s a w e t a d u r t x
e anddriedinavacuumoven .Thedried pelletswereinjeciton molded e
n i h c a m g n i d l o m n o i t c e j n i 1 W F T H a g n i s
u (Ningbo Haitian Plastic Injeciton Machinery Group d
t
L . ,China)withamold temperature o 200 Cf ° toformt es tpartsformechanicalt esting. C
. 1 e l b a
T omponentsofsamples.
e l p m a
S PP(g) Rao(g) IrganoxB215(g) P
P -Blank 2000.0 0 0
P
P -R ao 2000.0 8 .0 0
P
P -IrganoxB215 2000.0 0 8 .0 g
n i r u d d e m r o f r e p s a w g n i r e h t a e w l a r u t a
N 5 months in Guangzhou ,China. PP samples obtained r
e d n
u et h sameprocessing condtiions sa stated above, weremounted ni a wood suppor ton a roof ,
p o
t ta na angle fo 54 °, facing south. Exposed samples were periodically taken ou tand their s
e i t r e p o r p l a c i n a h c e
m da n mel tflowabilityweremeasured . e
h
T tensliestrength (TS)andnotched impac tstrength ( )I S ofthemolded ,weathered P Psamples y
b d e z y l a n a e r e
w a universalt estingmachine(CMT-7503 ,ShenzhenXinsans iCo., L .td ,China)and apendulumimpac ttesting machine (ZBC-4, Shenzhen Xinsans iC , L .o. t , d China) according tothe
s d r a d n a t s M T S
A D638 dan D256 ,respectively.
Cylindrical PP sampleswereusedformeasuremen toft hemel tflowrate (M ) FI using amel tflow t
n e m u r t s n i e t a
r (ZRZ- 040 ,Shenzhen Xinsans iCo., L .td ,China). The ISO 1133 method was .
d e w o l l o f
n o is s u c si D d n a s tl u s e R
T heTS andIS o fthethree standard PP samplesbeforeand during thenatura lweathering tests ea r n
w o h
s inFigs .1and2 .TheTSandISreductionforthePPcontainingR daoa n IrganoxB215were o
l
s w re thantha toft heunstabiilzedreferencesduringt heagingprocess ,whichi mpiledt ha tR daoa n x
o n a g r
I B215 both significantly enhanced et h therma loxidative stabliity fo PP . The TS of al l y
c n e d n e t g n i s a e r c n i n a d e w o h s s e l p m a
s i n theiniita lstageofagi ; ng thentheTSofsampleP -P R ao y
l w o l s d e s a e r c e
d withageingtimewhiletha tofthesamplePP-IrganoxB215 hadalmos tnochange s
y a d 5 0 1 r o
f (Figure )1 .However ,samplePP-Irganox B215 hada similarTSprofileastha tofthe k
n a l
b sampleafter12 0daysoftheoutdoortes.tThistrendcouldalso beseenf ortheIScurves, bu t w ee n’ t sr a obvious as for the TS curves (Figure )2 .I tcan be concluded tha tIrganox B215
s s e c c u s t a e r g d e t a r t s n o m e
d yb maintainingt he ST performanceduringtheperiodof1 5 y0 d s ha w ile o
a
R aw sl esseffectivethanIrganoxB215 ;however,t heeffectiveness fo R aolastedlongerthantha t f
0 30 60 90 120 150 0
2 4 2
8 2
2 3
6 3
)a
P
M(
ht
gn
ert
S
eli
sn
e
T
) d ( e m i T k
n a l B
5 1 2 B x o n a g r I
o a R
g i
F u 1 .Tre ensilestrengthvs .ageingt imeofPP.
0 30 60 90 120 150
0 . 1
5 . 1
0 . 2
5 . 2
0 . 3
5 . 3
0 . 4
) d ( e m i T
k n a l B
5 1 2 B x o n a g r I
o a R
m/
Jk
(
ht
gn
ert
S t
ca
p
mI
de
hct
o
N
2 )
g i
F u 2 .Ire mpac tstrengthv as. geingt imeofPP.
Thefluidityofthermoplasticscan berepresentedb ytheirme fl t lowindex(MFI) , i tcouldhavea e
s a e r c n i t n a c i f i n g i
s during theaging processdue to adecreasein polymer molecularweight. T he n
i e g n a h
c molecularweightofthePP samplesvaried differenltyduringthenatura lweatheringtests n
o d e s a
b thetypeofaddtiives ,asshownbytheMFIresultsin gF .i 3 .TheMFIofsamplePP-Blank e
s a e r c n
i d rapidly with aging time ,while tha tof PP with Irganox B215 and Rao were almos t t
n a t s n o
c up to 105 days ,afterwhich theMFIofsampleP -P Irganox B215 increased silghtly .Seen m
o r
f theMFIresul,t both Irganox B215and Rao proved effectivefortheantioxidaiton ofPP ,and d
e w o h s o a
0 30 60 90 120 150 0
5 0 1
5 1
0 2
k n a l B
5 1 2 B x o n a g r I
o a R
)ni
m/
g(
R
F
M
) d ( e m i T
g i
F u 3 .re M FIvs .ageingt imeofPP. r
o f n o s a e r e h
T theanitoxidan tactivityofR aois ti sabliityt oscavengefreeradicals ,chelatemeta l n
o r t c e l e r o s m o t a n e g o r d y h e t a n o d d n a , s n o it a
c s. The main components of R eao a r rosmanol , l
o s o n r a c d n a d i c a c i s o n r a
c idenitfied by L - SC M in our previous research (Figure )4 ,which are s
d i o n e p r e
t with adjacen t hydroxide groups. Many investigations have proved that rosmanol , l
o s o n r a c d n a d i c a c i s o n r a
c possess antioxidan tproperties .The key factor f or the antioxidative n
o i t c n u
f i t s hedistinctive chemicalstructure ,whichisreferredtoasstructure-acitvityrelationships (12) .In thepractica lapplication, there is no need to separateand purify each componentin Rao ,
h c i h
w showed a in mproved performancein anitoxidan tcapacity when theywereu d se togetherfor e
h
t synergisticeffec t(13). OH
HO
O O
OH
OH
HO
O O
OH
HO O
g i
F u 4. re Chemica lStructureofrosmano,l carnosicacidandcarnosol.
n o is u l c n o
C s
l a r u t a
N weatheringt ests w ee r performedt oi nvesitgatet heUVstabliityofPPsampleswtihR aoand x
o n a g r
I B215 .Thereduction ofmechanica lpropertiesa nd theincrement ofmel tflowabiltiy ofPP g
n i n i a t n o
c R ao were s w rlo e than for the unstabliized references during the aging process ,which t
a h t s e i l p m
i R aocanbeusedasanatura lantioxidantinplaceofsyntheticantioxidants forpolymers.
] 3
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