Migration of PVC Plasticizers Into Alcohols
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See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/236584005
Migration of PVC plasticizers into alcohols
ARTICLE · JANUARY 1975
CITATION
1
READS
141
5 AUTHORS, INCLUDING:
Fotis Rigas
National Technical University of Athens
129 PUBLICATIONS 943 CITATIONS
SEE PROFILE
Available from: Fotis Rigas
Retrieved on: 04 April 2016
https://www.researchgate.net/profile/Fotis_Rigas?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_7https://www.researchgate.net/?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_1https://www.researchgate.net/profile/Fotis_Rigas?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_7https://www.researchgate.net/institution/National_Technical_University_of_Athens?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_6https://www.researchgate.net/profile/Fotis_Rigas?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_5https://www.researchgate.net/profile/Fotis_Rigas?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_4https://www.researchgate.net/?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_1https://www.researchgate.net/publication/236584005_Migration_of_PVC_plasticizers_into_alcohols?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_3https://www.researchgate.net/publication/236584005_Migration_of_PVC_plasticizers_into_alcohols?enrichId=rgreq-fbfb1a2a-c4b2-4af0-bd7d-814f38e2c8a0&enrichSource=Y292ZXJQYWdlOzIzNjU4NDAwNTtBUzoxMDI0MDQyMzgzNDgyOThAMTQwMTQyNjQ4MjAxMw%3D%3D&el=1_x_2
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M i g r a t i o n o f P V p l a s tic i ze r s in t o a l c o h o l s
E m m a n u e l M . K a m p o u r i s F . R e g as S . R o k o t a s S . P o l y c h r o n a k i s a n d M . P a n ta z o g l o u
Laboratory o f Special Chem ical Technology, National Technical University of A thens, Athe ns 147,
Greece
(Received 14 A pr il 1975, evised4 July 1975)
Th e use of labe l led p las t ic ize rs and radioac t iv i ty measurements in conjunc t ion w i th w e ight loss can
g i v e q u a n t i t a t i v e i n f o r m a t i o n o n t he am oun t of migra ted p las tic ize r and on t he am oun t o f t he
l i qu id m ed ium tha t d i f fuses i n to t he po l ym e r du r i ng t he migrat ion process. In the case of PVC
plast ic ized wi th d ibu t y l ph tha la te and d ioc ty l phtha la te and immersed in alcohols the spec imens
soon become he te rogeneous due to loss in c o mp a t i b i l i t y b e t w e e n t h e p o l y me r a n d t he m ix tu res
o f p l a s t i c i z e r - a l c o h o l h igh in a lcoho l . These mix tures a r e fo r me d in the po lym er as a resu l t o f
con t i nuous migra t ion and d i f fus ion processes . The fo l lowing fac tors a f fec t ing the migra t ion
process were examined: na ture of a lcohol na ture of phtha la te p las t ic ize r am ou nt of p las tic ize r
m olecu la r w e i g h t o f po lym er th ickness o f specimens presence of ep ox y plast ic izers plast ic izat ion
process presence of s tab i l ize rs tem pera ture and t ime .
I N T R O D U C T I O N
The problem of p las t ic izer migra t ion is of spec ia l in te res t
in the c a se o f po lym e rs mod i f i e d w i th c ons ide ra b le a mou n t s
o f p l a st i ci z e rs . O f the c om mo n po lyme rs PV C i s t he one
used in the la rges t volum e as f lexib le or p las t ic ized PVC.
The re fo re a ny s tudy on the p l a s ti c i z at ion a nd mig ra t ion
p roc e ss e s ma y be o f p ra c t i c a l impor t a nc e fo r t he PV C
indus t ry .
In a l l appl ica t ions a p las t ic ized poly me r is in con tac t
w i th s ome k ind o f s u r round ing me d ium . U nde r the s e con -
di t ions the p las t ic izer mus t s tay in p lace during the useful
l i fe of the formed plas t ic i tem, o therwise i t migra tes wi th
the resul t th a t (a ) the p olym er, because o f loss of p las tici -
zer , s t i f fens and be com es less des irable , and (b) the sur-
round ing me d ium i s c on ta m ina te d by the p l a s ti c i ze r .
Thus there a r ises the need for a thorough s tudy of fac-
tors a ffec t ing the migra t ion process , and for a s imple and
a c c u ra t e me tho d o f me a s u ring a mo un t s o f p l a s ti c i ze r w h ic h
may be present in a g iven medium.
The poss ib le fac tors which can a ffec t the migra t ion pro-
cess can be classified in relation to: (a) the polymer, i .e .
na ture , molecular weight , c rys ta l l in i ty ; (b) the p las t ic izer ,
i .e . ~a ture , am oun t , poss ib le in te rac t ions (espec ia l ly in the
case of mixe d plas t ic iza t ion sys tems); (c ) the o t her com -
ponents usua l ly present in the p las t ic ized polymer, i .e .
s tabi lizers , lubricants , f i l le rs; (d) the p las t ic iza t ion pro-
c es s a nd c ond i t ions , a nd the re fo re the hom oge ne i ty o f
the s y s t e m; (e ) t he s u r round ing me d ium, i .e . na tu re ,
c omp a t ib i l i ty w i th the p l a s t i c iz e r , e f fe c t on po lym e r ; ( f )
the c ond i t ions o f t he t e s t , i .e . t ime , t e m pe ra tu re , t ype o f
c on ta c t .
The p las t ic izer tha t migra tes can be es t imated as : the
a mo un t l e av ing the po lym e r , o r t he a mou n t e n te r ing in to
the l iquid . In the f i rs t case the amo unt can be measured
by weight 1 or radioac t iv i ty 2 loss. In the sec ond case the
a mo un t o f p la s t ic i z e r c a n be me a s u re d by c h roma to g ra phy 3,4,
s p e c t r o m e t r ys , impulse-polarography6, and radioac t iv i ty7,8.
This paper presents the resul ts , obta ined by radiometr ic
a nd w e igh t lo ss me thod s , o f a s tudy o f t he e f fe c t o f t he
fol lowing fac tors upon the m igra t ion o f phtha la te p las tic i-
zers f rom plas t ic ized PVC into a lcohols : na ture of a lcohol ,
mo le c u la r w e igh t o f t he p o lym e r , na tu re o f p l a s t ic i z e r,
a mo un t o f p l a s t i ci z e r, p re s e nc e o f e pox y p l a s t ic i z er s ,
presence of s tabi lizers , p las t ic iza t ion process , th ickness of
s pe c ime ns , t e mpe ra tu re , a nd t im e . .
E X P E R I M E N T A L
Synthesis o f labelled dibutyl p hthalate (DBP)
5 mg of labe l led n-butaho l (1-14C; 0 .25 mCi) were
d i lu t e d w i th n -bu ta no l (28 ml ) a nd a dde d to a fou r -ne c ke d
f l as k c on ta in ing pow de re d ph tha l i c a nhydr ide (49 g ) . The
flask was equipped with s t i r re r , ther mo me ter , N 2 in le t tube ,
and a s ide conde nser . The mix ture was hea ted a t 100°C
fo r 1 h , t he n n -bu ta no l (95 ml ) a nd c on c e n t ra t e d s u lphu r i c
a c id (0 .4 ml ) w e re a dde d , a nd the mix tu re w a s he a te d a t
130°C for 3 h . During th is per iod a s low s t ream of N 2 was
passed and n-bu tanol was per iodica l ly added to mak e up
for tha t d ist il ling. Afte r cool ing , the reac t ion prod uct
w a s d i lu t e d w i th e the r (500 ml ) a nd the e the re a l s o lu t ion
w a s w a s he d w i th 10 a que ous s od ium c a rbona te s o lu t ion ,
the n w i th w a te r , a nd f ina l ly e va po ra t e d to r e move e the r
a nd un re a c te d n -bu ta no l . The d i e s t e r w a s pu r if i e d by
vacuum dis t i l la tion (y ie ld 82 g of labe l led DBP of radio-
a c t iv i ty 4 .8 x 103 c oun t s /mg /m in ) . P roduc t s w i th low e r
radioac t iv i t ies were obta in ed by d i lu t io n with pure un-
labe l led DBP.
Synthesis of labelled d ctyl phthalate (DOP)
The p ro duc t w a s s yn the s iz e d a c c o rd ing to the l i t e ra tu re
m etho d s f rom labe l led phtha l ic anh ydride (7-14C) and 2-
e thy lhe xa no l .
Preparation o f specimens
Sus pe nsion po lym e r i z e d PV C w a s b le nde d a t 80°C w i th
the ca lcula ted amo unts o f p las t ic izers and s tabi l izers . No
8 4 0 P O L Y M E R 1 9 7 5 V o l 1 6 N o v e m b e r
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M i g r a t i o n o f P V C p l a s t ic i z e r s i n t o a l c o h o l s : Eo /14 K a m p o u r i s e t a L
Table I
E f f e c t o f t h e n a t u r e o f a l c o h o l u p o n th e m i g r a t i o n m g ) o f p l a s t i c i ze r s f r o m p l a s t i c i ze d PVC
2 - E t h y l -
M e t h a n o l E t h a n o l n - P r o p a n ol I s o p r o p a n o l n - B u t a n o l I s o b u t a n o l
h e x a n o l
T i m e
d a y s )
D B P D O P
D B P D O P D B P D O P D B P D O P D B P D O P D B P D O P D B P D O P
1 1 5 2 5 7 1 0 1 1 6 3 7 3 2 4 1 5 1 8 2 7 4 2 6 0 4 7 8 4 2 6 9 4
2 2 5 5 8 2 1 5 2 2 0 9 1 1 0 3 4 0 8 7 1 1 9 1 1 0 3 9 9 8 1 1 2 5 3 7 1 3 5
4 3 4 4 1 1 0 2 6 5 2 7 4 1 7 5 4 5 0 1 4 7 1 5 3 1 8 1 5 1 8 1 3 8 1 6 3 5 4 1 7 8
6 3 9 9 1 4 0 3 3 8 3 1 9 2 3 0 5 2 7 1 8 9 1 81 2 3 9 5 8 8 1 7 4 1 9 4 6 9 2 2 4
1 0 4 5 2 1 8 7 4 2 2 3 9 6 3 2 2 6 1 6 2 5 6 2 3 0 3 2 4 6 6 3 2 1 7 2 4 2 7 8 2 7 4
1 5 4 8 4 2 2 8 4 7 0 4 6 4 4 0 1 6 2 7 3 0 8 2 7 5 3 8 7 7 0 5 2 5 2 2 8 8 1 1 5 3 2 5
2 0 5 0 6 2 5 4 4 9 1 5 1 6 4 4 4 7 1 8 3 4 9 3 0 7 4 3 3 7 3 6 2 8 0 3 2 9 1 3 3 3 6 1
2 5 5 2 1 2 7 2 5 0 6 5 5 1 4 7 5 7 4 2 3 7 6 3 3 2 4 6 4 7 5 4 3 0 8 3 5 0 1 4 7 3 9 0
3 0 5 2 8 2 8 2 5 1 4 5 7 5 4 9 7 7 5 1 3 9 2 3 5 4 4 8 5 7 6 2 3 3 2 3 7 1 1 61 4 1 2
lubricant was used. For stabilization Ba-Cd (1.5 phr) and
alkyl aryl phosphit e (0.5 phr) type stabilizers were used.
The dry blend was then plasticized by hot working for 7
min in the mixing head of a Brabender Plasticorder at
160°C and 30 rev/min. The plasticized mass was then
formed by hot rolling to a sheet from which specimens of
20 x 50 mm were cut.
Immersion
Each of the specimens was immersed in 250 ml of the
liquid medium contained in a 300 ml glass-stoppered
Erlenmeyer flask. The following alcohols were used as
liquids: methan ol, ethanol, 96 ethyl alcohol, n-propanol,
isopropanol, n-butanol, isobutanol, and 2-ethylhexanol.
All tests were made in duplicate, the flasks were kept at
temperatu res maintained to -+2°C, and the specimens were
selected with weight differences not exceeding 100 mg.
Measuremen t
The radioactivity of the liquid medium, at a given time
after immersion, was measured by transferring 0.5 ml of
the co nten t of the flasks to a glass measuring vial contain-
ing 10 ml of the scintillation solut ion, shaking to ensure
complete solution, and measuring the radioactivity by
means o f a Packard Tri-Carb 3385 liquid scintillation
spectrometer over a period of 10 min. The scintillation
solution was made b y dissolving 5 g of 2,5-diphenyloxazole
(PPO) and 300 mg of 2,2'-p-phenylenebis(4-methyl-5-phenyt-
oxazole)(Dimethyl-POPOP) in one litre o f toluene. From
each flask, two samples were taken thus each quoted result
represents the average of four measurements. Corrections
were made for background and quenching.
The radioactivity loss was calculated from radioactivity
measurements of the specimens before and after immersion.
In both cases about I0 mg of the specimens were dissolved
in 1 ml of tetrahydrofuran, 10 ml of the scintillation solu-
tion were added, and the radioactivity was measured in the
usual way. Efforts were made to obtain representative
samples; all measurements were made in fivefold and the
average obtained.
RESULTS AND DISCUSSION
Effec t o f the nature of alcohols
This effect was examined at 257C using k 65 PVC
plasticized with 50 phr DBP or DOP. The results obtained
are given in Tables and 2. As the data in Table indicate,
the amount of migrated DBP is high in the case of n-alcohols
Table 2
E f f e c t o f t h e n a t u r e
o f a l c o h o l u p o n t h e
m i g r a t i o n m g )
o f D B P a n d DOP f r o m p l a s t i c i ze d PVC: co m p a r i so n o f t h e r e su l t s
a f t e r 3 0 d a y s o f i m m e r s i o n
D B P D O P
Al co h o l I I I I I I IV I I I I I I IV
M e t h a n o l 5 4 5 5 2 8 2 8 9 2 3 9 2 7 5 2 8 2 1 2 4 1 5 8
E t h a n o l 5 3 8 5 1 4 2 2 7 2 8 7 5 8 2 5 7 5 3 1 7 2 5 8
n - Pr o p a n o l 5 0 7 4 9 7 1 9 2 3 0 5 7 3 1 7 5 1 4 2 8 3 2 3
I s o p r o p a n o l 4 1 7 3 9 2 16 4 2 2 8 3 7 2 3 5 4 1 2 6 2 2 8
n - B u t a n o l 4 9 3 4 8 5 2 0 2 2 8 3 7 4 5 7 6 2 4 2 0 3 4 2
I s o b u t a n o l 3 1 2 3 3 2 1 4 5 1 8 7 3 7 8 3 7 1 1 3 3 2 3 8
2 - E t h y l -
h e x a n o l 1 4 5 1 61 5 7 1 0 4 3 9 6 4 1 2 16 0 2 5 2
I = M i g r a te d p l a s t i c i ze r , b y r a d i o a c t i v i t y l oss ; II = m i g r a te d p l a s -
t i c iz e r b y r a d i o a c t i v i t y
o f t h e
a l co h o l ; I I I =
w e i g h t l o s s ;
IV ,=
d i f f e r -
e n c e
I I - - I I I d i f f u se d a l co h o l )
and much lower with iso-alcohols. In both cases the greater
the molecular weight of the alcohol, the lower is the amount
of plasticizer. In the case of DOP the greater migrat ion rates
also occur with n-alcohols, but the effect of the molecular
weight of is different. Now the greater the molecular weight
n- or iso-alcohols, the greater is the amou nt of migrated
plasticizer.
As the data in Table 2 indicate, the radioactivity loss
method can give results approx imately the same as
obtained by measurements of the radioactivity of the
liquid medium. Comparison between the results obtained
by the weight loss method and that of the radioactivity of
the liquid, for both DBP and DOP, indicates that in no case
can the weight loss method be used for the measurement
of the amount of migrated plasticizer. Correlation of the
results of the two methods, supposing no other matter
except plasticizer is migrated, can give quant itative infor-
mation on the amount of the alcohol diffused into the
polymer, during the migration process. In no case can the
amount of diffused alcohol be related with the molecular
weight. The only clear observation is that n-alcohols
diffused in greater amounts than iso-alcohols both in the
case of DBP and DOP. It also holds true that the lower
alcohols diffused faster in PVC plasticized with DBP,
while the higher alcohols diffused faster in PVC plasti-
cized with DOP.
In most cases the specimens gradually lose their trans-
parency and become opaque to white, during the migra-
tion process. This can be explained by the fact that the
plasticizer alcohol mixture, which plasticizes the polymer,
becomes gradually a non-solvent for the polymer and
P O L Y M E R , 1 9 7 5 , V o l 1 6 , N o v e m b e r 8 4 1
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Migra t ion o f PVC p las tic izers into alcoho ls : E M Kam pour is e ta /
hols exhib i t ing a se lec t ive ac t ion . As the da ta in Table 2
indica te , the lower a lcohols d i f fuse fas te r in PVC plas t i c ized
wi th DBP, whi le the h igher a lcohols do so in PVC plas t i c i -
z e d wi t h DOP.
Figure I
F o r m a t io n o f a lo n g h o le , a n u m b e r o f s m a l l o n e s , a n d
l in e s o f d i f f e r e n t ia t io n in t h e m a s s o f P V C p la st ic i ze d
w i t h 5 0 p h r
D B P a n d im m e r s e d in e t h a n o l ( × 3 5 )
T a b l e
E f f e c t o f t h e a m o u n t o f p la s tic iz e r u p o n t h e m ig r a t io n o f
D BP
f rom plast ic ized
P V C i n t o e t h a n o l a t 3 0 ° C
Mig rated plastic izer ( rag)
T i m e
( da y s) 2 0 p h r 4 0 p h r 6 0 p h r
2 1 4 1 0 8 4 5 1
4 1 9 1 5 9 6 1 4
6 2 5 2 0 9 6 8 8
10 3 3 301 757
1 5 4 0 3 5 2 8 0 1
2 0 4 6 3 8 3 8 2 7
2 5 5 0 4 1 5 8 5 2
3 0 5 6 4 3 8 8 7 2
4 0 6 0 4 6 1 8 9 9
5 0 7 0 4 8 2 9 2 4
6 0 7 6 4 9 8 9 3 5
7 0 8 5 5 1 2 9 4 3
8 0 9 3 5 2 3 9 4 7
Init ial plasticizer
c o n t e n t ( m g ) 4 6 4 8 0 2 1 0 5 0
Final plasticizer
c o n t e n t ( m g ) 3 7 1 1 7 9 1 0 3
Final plasticizer
c o n t e n t ( p h r ) 1 6 9 6
W e ig h t lo s s ( m g ) 7 8 1 8 0 5 1 7
D i f f u s e d a lc o h o l
( m g) 1 5 3 4 3 4 3 0
separa tes as a secon(1 phase in th e m ass . Thi s i s show n in
t h e m i c r o p h o t o o f
Figure 1
Effect of the nature of phthalate plasticizer
T h i s e f f e c t w a s e x a m i n e d f o r b o t h D B P a n d D O P , t w o
c o m m o n p l a s t ic i z e rs wi t h d i f f e r e n c e s in m o l e c u l a r we i g h t ,
v i s c o s i ty a n d v o l a t i li t y . I t i s o f t e n s t a t e d , i n e x a m i n i n g
t h e t e n d e n c y o f p l a s ti c i ze r s t o m i g r a t e , t h a t t h e g r e a t e r t h e
m o l e c u l a r we i g h t , t h e g r e a t e r t h e v i s c o s i t y , o r t h e l o w e r
t h e v o l a t i li t y , th e l o we r i s th e m i g r a t i o n r a t e a - l ° . Th e d a t a
in Table 1 indica te tha t there i s no f i rm re la t ionship be t -
ween molecular weight , v i scos i ty , or vola t i l i ty of p las t i c i -
z e r a n d th e r a t e o f t h e m i g r a t i o n p r o c es s . Ge n e r a l l y o n l y
i n th e c a s e o f c o n t a c t wi t h m e t h a n o l d o e s DB P m i g r a t e
f a s t e r t h a n D OP, wh i l e t h e o p p o s i t e i s t r u e i n t h e o t h e r
cases.
Th e n a t u r e o f p l a s t ic i z e r a f f e c t s th e d i f f u s i o n o f a l c o -
Effect of the amount of plasticizer
Th i s e f f e c t wa s e x a m i n e d i n t h e c a s e o f k 6 5 PVC p l a s -
t i c iz e d wi t h 2 0 , 4 0 a n d 6 0 p h r o f DBP. Th e t e m p e r a t u r e
o f t h e t e s t wa s 3 0 °C, t h e d u r a t i o n 8 0 d a y s , a n d t h e l i q u id
m e d i u m e t h a n o l . Th e r e s u l t s o b t a i n e d a r e g i v en i n
Table
3 . As th e d a t a i n d i c a t e t h e a m o u n t o f p l a s ti c i z e r s t r o n g l y
a f f e c t s th e m i g r a t i o n p r o c e s s a n d t h e g r e a t e r th e a m o u n t
o f p l a s ti c i z e r, t h e g r e a t e r i s t h e a m o u n t l o s t b y m i g r a t i o n .
Du r i n g t h e c o u r s e o f t h e p r o c e s s t h e m i g r a t i o n r a t e wa s
f a s t e r f o r t h e s p e c i m e n s p la s t i ci z e d wi t h t h e g r e a t e r a m o u n t s
of p las t ic izer . The resu l t was a reversa l of the orde r and
a f t e r a c e r t a i n t i m e t h e s p e c i m e n wi t h t h e g r e a t e r a m o u n t
o f p l a st i c iz e r en d s u p wi t h t h e l o we s t a m o u n t . Th i s b e -
h a v i o u r c a n b e e x p l a i n e d o n l y i n c a se s o f h ig h d i f f u s io n
ra tes . In the case exa min ed i t is ev iden t tha t the grea te r
t h e a m o u n t o f p l a s ti c i z e r, t h e g r e a t e r i s t h e a m o u n t o f
d i f f u s e d e t h a n o l . A t t h e e n d o f th e t e s t th e s p e c i m e n
p l a s ti c iz e d wi t h 2 0 p h r DBP b e c o m e s p l a s ti c iz e d w i t h
a b o u t 1 6 p h r o f a m i x t u r e c o n t a in i n g 4 e t h a n o l , th e
s p e c i m e n p l a s t ic i z e d wi t h 4 0 p h r b e c o m e s p l a s t ic i z e d
wi t h a b o u t 2 6 p h r o f a m i x t u r e c o n t a in i n g 6 5 e t h a n o l ,
a n d f i n a l ly t h e s p e c i m e n p l a s t i c iz e d wi t h 6 0 p h r DB P
b e c o m e s p l a s t i c i z e d wi t h a b o u t 3 0 p h r o f a m i x t u r e c o n -
ta in ing 80 e than ol .
Effect of the molecular weight of the polymer
Fo r t h i s t e s t f o u r s a m p l e s o f PVC ( k v a l u e s 5 5 , 6 5 , 7 0 ,
and 73 respec t iv e ly) were ]~last ic ized wi th 5 0 phr D BP and
i m m e r s e d in e t h a n o l a t 3 0 v C f o r 6 0 d a y s . Th e r e s u l ts o b -
ta ined a re g iven in Table 4 As t h e d a t a i n d i c a t e t h e m o l e -
c u l a r we i g h t o f t h e p o l y m e r a f f e c t s m i g r a t i o n a n d t h e
g r e a t e r th e m o l e c u l a r we i g h t , th e l o we r i s t h e a m o u n t o f
migra ted p las t i c izer .
Effect of th e th ickn ess of specimens
I n s o m e c a s e s ~° 'H s h o r t - t i m e t e s t s l e d t o t h e c o n c l u s i o n
t h a t t h e t h i c k n e s s o f s p e c i m e n s h a s li t tl e o r n o e f f e c t o n
the migra t io n of p las t ic izers . In th i s t es t spec imen s of k
Table 4 E f f e c t o r th e m o l e c u l a r w e i g h t o f p o l y m e r u p o n t h e
m ig -
ra t i on o f D BP f rom p las t i c i z ed PVC
i n t o e t h a n o l
a t 3 0 ° C
Migrated plast ic izer
rag)
T i m e
( d a ys ) k 5 5 k 6 5
k 7 0 k 7 3
2 256 203 156 90
4 3 3 0 2 7 5 2 0 5
1 3 5
6 377 327 244 170
1 0 4 1 0 3 7 0
2 8 5 1 9 9
1 5 4 3 5 4 0 1
3 2 4 2 3 5
20
4 5 0 4 1 9 3 4 8
2 6 0
25
4 5 9 4 2 5
3 6 0 2 7 6
30
4 6 4 4 3 5 3 7 0 2 8 4
3 5 4 6 9 4 4 0 3 7 6 2 9 8
4 0 4 7 3
4 4 5 3 8 1
3 1 0
4 5 4 7 6 4 5 0 3 8 5 3 1 9
5 0
4 8 0 4 5 3
3 9 2 3 2 6
5 5 4 8 3 4 5 7 3 9 8 331
6 0 4 8 6 4 8 0 4 0 5 3 3 5
8 4 2 P O L Y M E R , 1 9 7 5 , V o l 1 6 ,
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Table Ef f ec t o f t he t h i c k nes s o f s pec im ens upon t he m ig ra t i on o f
D B P f r o m p l a s t ic i z e d P V C i n t o e t h a n o l
M ig ra t ed p las t i c i z e r (m g)
T i m e
(day s ) 3040 m g 2381 m g 1785 m g 1483 m g
1 317 295 292 287
2 531 442 386 338
4 688 530 463 361
6 7 3 8 5 7 2 4 8 8 3 7 7
10 778 599 502 406
1 5 7 9 6 6 3 3 5 1 5 4 1 9
2 0 8 1 4 6 5 7 5 2 6 4 3 5
2 5 8 3 4 6 7 5 5 3 8 4 4 7
3 0 8 4 3 7 01 5 4 7 4 6 0
I n i t i a l p l as t i c i z e r
c o n t e n t ( m g) 1 0 0 0 7 8 3 5 7 8 4 8 8
F ina l p l as t i c i z e r
c on t en t ( rag ) 157 82 31 28
F ina l p l as t i c i z e r
c on t en t ( ph r ) 7 . 7 5 . 2 3 . 5 3 . 6
ranged f rom 2 .5 to 15 min . As the da ta in
Table 7
indica te ,
d i f f e r e n c e s i n t h e p l a s t i c i z a t io n p r o c e s s ( d u e t o v a r i a t i o n s in
p l a s t i c iz a t i o n t i m e ) a f f e c t m i g r a t i o n a n d t h e g r e a t e r t h e wo r k -
i n g ti m e , t h e l o w e r i s t h e a m o u n t o f m i g r a t e d p l a s ti c iz e r .
El]Oct o f s tabi l iza t ion
Th i s e f f e c t wa s e x a m i n e d f o r k 6 5 PVC p l a s t i c iz e d wi t h
6 0 p h r DBP o r DOP a n d i m m e r s e d i n 9 6 e t h a n o l f o r 3 0
d a y s a t 2 5 °C . I n t h e c a s e o f n o n - s t a b il i z e d PVC, p l a s ti c i z e d
wi t h 6 0 p h r DOP, t wo s e r i e s o f s a m p l e s we r e p r e p a r e d wi t h
di f fe ren t p las t i c i za t ion t imes , i .e . 7 and 15 ra in . The resul t s
in Table 8 indica te tha t s t ab i l i za t ion a f fec t s s t rongly the mi -
g r a t i o n p r o c e s s , a n d t h e g r e a t e r a m o u n t s a r e m i g r a t i n g f r o m
the s t abi l ized spec ime ns . In the case of uns tab i l i zed spec i -
m e n s t h e e f f e c t o f t h e p l a s t i c i z a ti o n t i m e i s g r e a t e r t h a n i n
the case of s t ab i l i zed ones .
Ef fe c t o f t e m pe r a tur e
Th e e f f e c t o f t e m p e r a t u r e wa s s t u d ie d i n t h e c a s e o f k 6 5
PVC p l a s t ic i z e d wi t h 5 0 p h r DBP a n d i m m e r s e d i n e t h a n o l
Table 6
E f f e c t o f e p o x y p l a s t i c iz e r u p o n t h e m i g r a t i o n o f D B P
a n d D O P f r o m p l a s t ic i z e d P V C i n t o e t h a n o l
M ig ra t ed D BP ( rag )
M ig ra t ed D OP (m g)
T i m e
(day s ) 0 ph r 6 ph r 0 ph r 6 ph r
2 186 219 178 223
4 244 269 240 297
6 2 7 0 2 9 6 2 8 2 3 4 7
10 302 331 327 402
1 5 3 1 7 3 6 0 3 4 9 4 3 7
20 327 373 360 451
25 333 381 377 460
3 0 3 4 2 3 8 4 3 8 3 4 6 9
6 5 PVC p l a s t i c i z e d wi t h 5 0 p h r DBP we r e u s e d i m m e r s e d
i n e t h a n o l a t 3 0 °C . Fo r h i g h e r a c c u r a c y t h e we i g h t o f
2 0 x 5 0 m m s p e c i m e n s wa s u s ed a s a n i n d ic a t i o n o f t h ic k -
ness . The resul t s in Table 5 indica te tha t the grea te r the
t h i c k n e s s o f t h e s p e c i m e n s , t h e g r e a t e r is th e a m o u n t o f
m i g r a t e d p l a s ti c i z e r. A t t h e e n d o f th e t e s t t h e m a j o r p a r t
o f t h e p l a s ti c i z e r h a d m i g r a t e d a n d t h e a m o u n t r e m a i n i n g
wa s g r e a t e r f o r t h e t h i c k e r s p e c i m e n s .
Ef fe c t o f t he e po x v p la s t i ci z e r
I n e x a m i n i n g t h e e f f e c t o f e p o x y p l a s ti c iz e r s u p o n t h e
m i g r a t i o n o f th e m a i n ( p h t h a l a t e ) p l a s t i ci z e r , s p e c i m e n s
we r e m a d e f r o m k 6 5 PVC p l a s t i c i z e d wi t h 5 0 p h r DBP o r
DOP a n d 6 p h r o f e p o x y p l a s t ic i z e r (a c o m m e r c i a l e p o x i -
d i z e d s o y a b e a n o il ). Th e s p e c i m e n s we r e i m m e r s e d in
e t h a n o l f o r 3 0 d a y s a t 2 5 °C . Th e r e s u lt s o b t a i n e d a r e g i v en
in
Table 6
As t h e d a t a i n d i c a te , t h e e p o x y p la s t ic i z e r a f f e c t s
m i g r a t i o n , p r o m o t i n g t h a t o f th e m a i n p l a s t ic i z e r. Th i s b e-
h a v i o u r s e e m s t o b e s e l e c t iv e : DOP m i g r a t e s t o a g r e a t e r e x -
tent than does DBP.
L f f e c t o f the p las t ic izat ion process
Th i s e f f e c t wa s s tu d i e d f o r k 6 5 PV C p l a s t ic i z e d wi t h 5 0
p h r DBP a n d i m m e r s e d in e t h a n o l a t 3 0 °C f o r 6 0 d a y s . Th e
plas t i c i za t ion process genera l ly used in th i s work was fo l -
l o we d wi t h v a r i a t i o n s in t h e t i m e o f h o t wo r k i n g wh i c h
Table 7
Ef f ec t o f t he p las t i c i z a t i on p roc es s upon t he m ig ra t i on o f
D B P f r o m p l a s t ic i z e d D B P e t h a n o l
ig ra ted p las t ic ize r
(rag)
T i m e
(day s ) 2 . 5 m in 5 ra in 10 m in 15 m in
2 2 3 0 2 1 3 2 0 8 2 0 2
4 3 2 7 3 0 7 2 8 0 2 6 2
6 370 352 321 297
10 421 392 368 335
1 5 4 4 5 4 1 6 3 9 2 3 8 0
2 0 4 5 2 4 3 0 4 1 7 3 9 8
3 0 4 6 2 4 4 1 4 2 5 4 1 5
4 0 4 6 7 4 4 9 4 3 1 4 2 4
5 0 4 7 2 4 5 9 4 3 7 4 3 2
6 0 4 7 7 4 6 1 4 4 2 4 3 7
W e igh t l os s (m g) 294 290 273 265
E t hano l d i f f us ed
(mg) 183 171 169 172
Table 8
Ef f ec t o f t he p res enc e o f s t ab i l iz e rs upon t he m ig ra t i on o f
D BP and D OP f rom p las t i c i z ed PVC in t o 96 a l c oho l
M ig ra t ed p las t i c i z e r
(rag)
T i m e
(days) I I I I I I IV V
2 222 80 153 79 67
4 283 136 228 123 114
6 333 173 263 164 148
10 379 227 312 207 175
15 424 257 358 246 211
20 451 273 383 276 230
2 5 4 6 9 2 8 2 4 1 0 3 0 3 2 5 1
3 0 4 8 3 2 9 1 4 2 5 3 2 8 2 6 7
I = N orm a l l y s t ab i l i z ed PVC p las t i c i z ed w i t h 6 0 ph r D BP ; I I = un-
s t a b i l iz e d P V C p l a s t i c iz e d w i t h 6 0 p h r D B P ; I I I = n o r m a l l y s t a b i li -
z e d P V C p l a s t ic i z e d w i t h 6 0 p h r D O P , p l a s t ic i z a t i o n t i m e 7 m i n ;
I V = u n s t a b i li z e d P V C p l a s t i c iz e d w i t h 6 0 p h r D O P , p l a s t ic i z a t i o n
t i m e 7 m i n ; V = u n s t a b i l iz e d P V C p l a s t i c iz e d w i t h 6 0 p h r D O P ,
p las t i c i z a t i on t im e 15 ra in
POLY MER 1975 Vo l 16 Novem ber 843
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Migrat ion of PVC plasticizers into alcohols: E M Karnpouris et aL
T a b l e
Ef fec t o f th e tem p er a tu r e u p o n th e m ig r a tio n o f D BP
from p lastic ized PVC in to ethanol
Migrated plasticizer rag)
T i m e
d a ys ) 1 0 C 3 0 C 6 0 ° C
2 5 4 2 3 4 4 4 2
4 7 8 3 3 4 5 3 0
6 1 0 0 3 8 8 5 7 2
1 0 1 3 2 4 3 0 5 9 9
1 5 1 6 4 4 5 7 6 3 3
2 0 1 9 9 4 7 3 6 5 7
3 0 2 1 3 4 8 4 70 1
b e e x p l a i n e d b y t h e s m a l l i n t e r v a l s o f t i m e . G e n e r a l l y t h e
g r e a t e s t m i g r a t i o n r a t e s o c c u r i n t h e f i r s t st a g e s o f t h e p r o -
c e ss . T h e y b e c o m e t h e n l o w e r a n d t e n d t o m i n i m i z e . F o r
l o n g e n o u g h p e r i o d s t h e t o t a l a m o u n t o f p l as t ic i z er c a n
m i g r a t e , l e a v i n g t h e p o l y m e r p l a s t i c i z e d , o r s w e l l e d , b y a
m i x t u r e c o n t a i n i n g l o w a m o u n t s o f p la s ti c iz e r .
A C K N O W L E D G E M E N T S
T h e a u t h o r s w i s h t o e x p r e s s t h a n k s t o D r G . A k o y u n o g l o u
a n d M r S . D a o u s i s o f th e B i o l o g y D e p t . o f N . R . C . D e m o c r i -
t o s f o r c o u n t i n g t h e s a m p l e s .
a t t e m p e r a t u r e s r a n g i n g f r o m 1 0 ° t o 6 0 °C . T h e r e s u l t s i n
Table 9 i n d ic a t e t h a t t h e t e m p e r a t u r e a f f e c ts s t r o n g l y t h e
m i g r a t i o n o f p l a s t i c iz e r ; a n y r i se i n t e m p e r a t u r e i n c r e a s e s
d r a s ti c a ll y t h e a m o u n t o f m i g r a t e d p la s ti c iz e r . T h u s 3 0
d a y s o f i m m e r s i o n a t 1 0 ° C g av e th e s a m e a m o u n t o f m i g r a-
t e d p l a s ti c i z e r , a s 2 d a y s a t 3 0 °C . S c h e m a t i c p r e s e n t a t i o n
o f t h e r e s u l ts l e a d s t o t h e c o n c l u s i o n t h a t t h e r e l a t i o n t e m -
p e r a t u r e / a m o u n t o f m i g r a t e d p l a s t ic i z er i s n o t a li n e ar o n e .
Effect of t ime
E x a m i n i n g t h e e f f e c t o f t i m e , i n a ll t h e a b o v e c a s e s , w e
c a n c o n c l u d e t h a t t h e r e i s n o l i n e a r r e l a ti o n b e t w e e n t h e
a m o u n t o f m i g r a t e d p l a s ti c iz e r a n d t i m e , o r t h e s q u a r e
r o o t o f t i m e . C o n t r a d i c t o r y r e s u l t s i n th e l i te r a t u re m a y
R E F E R E N C E S
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4 Rohleder, K. and Bruchhausen, B. V. Dsch. Lebensm-
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8 4 4 P O L Y M E R , 1 9 7 5 , V o l 1 6 , N o v e m b e r