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Migration of PVC plasticizers into alcohols

ARTICLE JANUARY 1975

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Migration of PVC plasticizers into alcohols

Emmanuel M. Kampouris, F. Regas, S. Rokotas, S. Polychronakis and M. Pantazoglou
Laboratory of Special Chemical Technology, National Technical University of Athens, Athens 147,
Greece
(Received 14 April 1975,"revised4 July 1975)
The use of labelled plasticizers and radioactivity measurements in conjunction with weight loss, can
give quantitative information on the amount of migrated plasticizer, and on the amount of the
liquid medium that diffuses into the polymer during the migration process. In the case of PVC
plasticized with dibutyl phthalate and dioctyl phthalate and immersed in alcohols, the specimens
soon become heterogeneous due to loss in compatibility between the polymer and the mixtures
of plasticizer-alcohol high in alcohol. These mixtures are formed in the polymer as a result of
continuous migration and diffusion processes. The following factors affecting the migration
process were examined: nature of alcohol, nature of phthalate plasticizer, amount of plasticizer,
molecular weight of polymer, thickness of specimens, presence of epoxy plasticizers, plasticization
process, presence of stabilizers, temperature, and time.

INTRODUCTION
The problem of plasticizer migration is of special interest
in the case of polymers modified with considerable amounts
of plasticizers. Of the common polymers PVC is the one
used in the largest volume as flexible or plasticized PVC.
Therefore any study on the plasticization and migration
processes may be of practical importance for the PVC
industry.
In all applications a plasticized polymer is in contact
with some kind of surrounding medium. Under these conditions the plasticizer must stay in place during the useful
life of the formed plastic item, otherwise it migrates with
the result that (a) the polymer, because of loss of plasticizer, stiffens and becomes less desirable, and (b) the surrounding medium is contaminated by the plasticizer.
Thus there arises the need for a thorough study of factors affecting the migration process, and for a simple and
accurate method of measuring amounts of plasticizer which
may be present in a given medium.
The possible factors which can affect the migration process can be classified in relation to: (a) the polymer, i.e.
nature, molecular weight, crystallinity; (b) the plasticizer,
i.e. ~ature, amount, possible interactions (especially in the
case of mixed plasticization systems); (c) the other components usually present in the plasticized polymer, i.e.
stabilizers, lubricants, fillers; (d) the plasticization process and conditions, and therefore the homogeneity of
the system; (e) the surrounding medium, i.e. nature,
compatibility with the plasticizer, effect on polymer; (f)
the conditions of the test, i.e. time, temperature, type of
contact.
The plasticizer that migrates can be estimated as: the
amount leaving the polymer, or the amount entering into
the liquid. In the first case the amount can be measured
by weight 1 or radioactivity2 loss. In the second case the
amount of plasticizer can be measured by chromatography3,4,
spectrometry s, impulse-polarography6, and radioactivity7,8.
This paper presents the results, obtained by radiometric
and weight loss methods, of a study of the effect of the

840

POLYMER, 1975, Vol 16, November

following factors upon the migration of phthalate plasticizers from plasticized PVC into alcohols: nature of alcohol,
molecular weight of the polymer, nature of plasticizer,
amount of plasticizer, presence of epoxy plasticizers,
presence of stabilizers, plasticization process, thickness of
specimens, temperature, and time..

EXPERIMENTAL

Synthesis of labelled dibutyl phthalate (DBP)

5 mg of labelled n-butahol (1-14C; 0.25 mCi) were
diluted with n-butanol(28 ml) and added to a four-necked
flask containing powdered phthalic anhydride (49 g). The
flask was equipped with stirrer, thermometer, N 2 inlet tube,
and a side condenser. The mixture was heated at 100C
for 1 h, then n-butanol (95 ml) and concentrated sulphuric
acid (0.4 ml) were added, and the mixture was heated at
130C for 3 h. During this period a slow stream ofN 2 was
passed and n-butanol was periodically added to make up
for that distilling. After cooling, the reaction product
was diluted with ether (500 ml) and the ethereal solution
was washed with 10% aqueous sodium carbonate solution,
then with water, and finally evaporated to remove ether
and unreacted n-butanol. The diester was purified by
vacuum distillation (yield 82 g of labelled DBP of radioactivity 4.8 x 103 counts/mg/min). Products with lower
radioactivities were obtained by dilution with pure unlabelled DBP.

Synthesis of labelled d&ctyl phthalate (DOP)

The product was synthesized according to the literature
method s from labelled phthalic anhydride (7-14C) and 2ethylhexanol.

Preparation of specimens
Suspension polymerized PVC was blended at 80C with
the calculated amounts of plasticizers and stabilizers. No

Migration o f PVC plasticizers into alcohols: Eo /14. Kampouris et aL

Table I

Effect of the nature of alcohol upon the migration (mg) of plasticizers from plasticized PVC

Methanol

Ethanol

n-Propanol

Isopropanol

n-Butanol

2-Ethylhexanol

Isobutanol

Time
(days)

DBP

DOP

DBP

DOP

DBP

DOP

DBP

DOP

DBP

DOP

DBP

DOP

DBP

DOP

1
2
4
6
10
15
20
25
30

152
255
344
399
452
484
506
521
528

57
82
110
140
187
228
254
272
282

101
152
265
338
422
470
491
506
514

163
209
274
319
396
464
516
551
575

73
110
175
230
322
401
444
475
497

241
340
450
527
616
627
718
742
751

51
87
147
189
256
308
349
376
392

82
119
153
181
230
275
307
332
354

74
110
181
239
324
387
433
464
485

260
399
518
588
663
705
736
754
762

47
81
138
174
217
252
280
308
332

84
125
163
194
242
288
329
350
371

26
37
54
69
78
115
133
147
161

94
135
178
224
274
325
361
390
412

lubricant was used. For stabilization Ba-Cd (1.5 phr) and

alkyl aryl phosphite (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
160C 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: methanol, ethanol, 96% ethyl alcohol, n-propanol,
isopropanol, n-butanol, isobutanol, and 2-ethylhexanol.
All tests were made in duplicate, the flasks were kept at
temperatures maintained to -+2C, and the specimens were
selected with weight differences not exceeding 100 mg.

Table 2 Effect of the nature of alcohol upon the migration (mg)

of DBP and DOP from plasticized PVC: comparison of the results
after 30 days of immersion
DBP

DOP

Alcohol

II

III

IV

II

III

IV

Methanol
Ethanol
n-Propanol
Isopropanol
n-Butanol
Isobutanol
2-Ethylhexanol

545
538
507
417
493
312

528
514
497
392
485
332

289
227
192
164
202
145

239
287
305
228
283
187

275
582
731
372
745
378

282
575
751
354
762
371

124
317
428
126
420
133

158
258
323
228
342
238

145

161

57

104

396

412

160

252

I = Migrated plasticizer, by radioactivity loss; II = migrated plasticizer by radioactivity of the alcohol; III = weight loss; IV ,= difference II -- III (diffused alcohol)

Measuremen t
The radioactivity of the liquid medium, at a given time
after immersion, was measured by transferring 0.5 ml of
the content of the flasks to a glass measuring vial containing 10 ml of the scintillation solution, shaking to ensure
complete solution, and measuring the radioactivity by
means of a Packard Tri-Carb 3385 liquid scintillation
spectrometer over a period of 10 min. The scintillation
solution was made by dissolving 5 g of 2,5-diphenyloxazole
(PPO) and 300 mg of 2,2'-p-phenylenebis(4-methyl-5-phenytoxazole)(Dimethyl-POPOP) in one litre of 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 solution 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

Effect 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 1 and 2. As the data in Table 1 indicate,
the amount of migrated DBP is high in the case of n-alcohols

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 migration 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 amount of migrated
plasticizer.
As the data in Table 2 indicate, the radioactivity loss
method can give results approximately 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 quantitative information 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 plasticized with DOP.
In most cases the specimens gradually lose their transparency and become opaque to white, during the migration 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

POLYMER,

1975, V o l 16, N o v e m b e r

841

Migration of PVC plasticizers into alcohols: E. M. Kampouris eta/.

hols exhibiting a selective action. As the data in Table 2

indicate, the lower alcohols diffuse faster in PVC plasticized
with DBP, while the higher alcohols do so in PVC plasticized with DOP.

Effect of the amount of plasticizer

Figure I

Formation of a long hole, a number of small ones, and

lines of differentiation in the mass of PVC plasticized with 50 phr
DBP and immersed in ethanol (35)

Table 3 Effect of the amount of plasticizer upon the migration of

DBP from plasticized PVC into ethanol at 30C

Migrated plasticizer (rag)

Time
(days)

20 phr

40 phr

60 phr

2
4
6
10
15
20
25
30
40
50
60
70
80

14
19
25
33
40
46
50
56
60
70
76
85
93

108
159
209
301
352
383
415
438
461
482
498
512
523

451
614
688
757
801
827
852
872
899
924
935
943
947

464

802

1050

371

179

' 103

16
78

9
180

6
517

15

343

430

Initial plasticizer
content (mg)
Final plasticizer
content (mg)
Final plasticizer
content (phr)
Weight loss (mg)
Diffused alcohol
(mg)

separates as a secon(1 phase in the mass. This is shown in

the microphoto of Figure 1.

This effect was examined in the case of k 65 PVC plasticized with 20, 40 and 60 phr of DBP. The temperature
of the test was 30C, the duration 80 days, and the liquid
medium ethanol. The results obtained are given in Table
3. As the data indicate the amount of plasticizer strongly
affects the migration process and the greater the amount
of plasticizer, the greater is the amount lost by migration.
During the course of the process the migration rate was
faster for the specimens plasticized with the greater amounts
of plasticizer. The result was a reversal of the order and
after a certain time the specimen with the greater amount
of plasticizer ends up with the lowest amount. This behaviour can be explained only in cases of high diffusion
rates. In the case examined it is evident that the greater
the amount of plasticizer, the greater is the amount of
diffused ethanol. At the end of the test the specimen
plasticized with 20 phr DBP becomes plasticized with
about 16 phr of a mixture containing 4% ethanol, the
specimen plasticized with 40 phr becomes plasticized
with about 26 phr of a mixture containing 65% ethanol,
and finally the specimen plasticized with 60 phr DBP
becomes plasticized with about 30 phr of a mixture containing 80% ethanol.

Effect of the molecular weight of the polymer

For this test four samples of PVC (k values 55, 65, 70,
and 73 respectively) were ]~lasticized with 50 phr DBP and
immersed in ethanol at 30vC for 60 days. The results obtained are given in Table 4. As the data indicate the molecular weight of the polymer affects migration and the
greater the molecular weight, the lower is the amount of
migrated plasticizer.

Effect of th e th ickn ess of specimens

In some cases ~'H short-time tests led to the conclusion
that the thickness of specimens has little or no effect on
the migration of plasticizers. In this test specimens of k
Table 4 Effect or the molecular weight of polymer upon the migration of DBP from plasticized PVC into ethanol at 30C
Migrated plasticizer (rag)
Time
(days)

k55

k65

k70

k73

2
4
6
10
15
20
25
30
35
40
45
50
55
60

256
330
377
410
435
450
459
464
469
473
476
480
483
486

203
275
327
370
401
419
425
435
440
445
450
453
457
480

156
205
244
285
324
348
360
370
376
381
385
392
398
405

90
135
170
199
235
260
276
284
298
310
319
326
331
335

Effect of the nature of phthalate plasticizer

This effect was examined for both DBP and DOP, two
common plasticizers with differences in molecular weight,
viscosity and volatility. It is often stated, in examining
the tendency of plasticizers to migrate, that the greater the
molecular weight, the greater the viscosity, or the lower
the volatility, the lower is the migration rate a-l. The data
in Table 1 indicate that there is no firm relationship between molecular weight, viscosity, or volatility of plasticizer and the rate of the migration process. Generally only
in the case of contact with methanol does DBP migrate
faster than DOP, while the opposite is true in the other
cases.
The nature of plasticizer affects the diffusion of alco-

842

POLYMER,

1975, V o l 16, N o v e m b e r

Migration of PVC plasticizers into alcohols: E. M. Kampouris et aL

Table 5 Effect of the thickness of specimens upon the migration of
DBP from plasticized PVC into ethanol

Migrated plasticizer (mg)

Time
(days)
1
2
4
6
10
15
20
25
30

3040 mg
317
531
688
738
778
796
814
834
843

Initial plasticizer
content (mg) 1000
Final plasticizer
content (rag) 157
Final plasticizer
content (phr) 7.7

2381 mg

1785 mg

1483 mg

295
442
530
572
599
633
657
675
701

292
386
463
488
502
515
526
538
547

287
338
361
377
406
419
435
447
460

783

578

488

82

31

28

5.2

3.5

3.6

El]Oct of stabilization
This effect was examined for k 65 PVC plasticized with
60 phr DBP or DOP and immersed in 96% ethanol for 30
days at 25C. In the case of non-stabilized PVC, plasticized
with 60 phr DOP, two series of samples were prepared with
different plasticization times, i.e. 7 and 15 rain. The results
in Table 8 indicate that stabilization affects strongly the migration process, and the greater amounts are migrating from
the stabilized specimens. In the case of unstabilized specimens the effect of the plasticization time is greater than in
the case of stabilized ones.

Effect of temperature
The effect of temperature was studied in the case of k 65
PVC plasticized with 50 phr DBP and immersed in ethanol

Table 6 Effect of epoxy plasticizer upon the migration of DBP

and DOP from plasticized PVC into ethanol

Migrated DBP (rag)

ranged from 2.5 to 15 min. As the data in Table 7 indicate,

differences in the plasticization process (due to variations in
plasticization time) affect migration and the greater the working time, the lower is the amount of migrated plasticizer.

Table 7 Effect of the plasticization process upon the migration of

DBP from plasticized DBP ethanol

Migrated plasticizer

Migrated DOP (mg)

(rag)

Time
(days)

0 phr

6 phr

0 phr

6 phr

2
4
6
10
15
20
25
30

186
244
270
302
317
327
333
342

219
269
296
331
360
373
381
384

178
240
282
327
349
360
377
383

223
297
347
402
437
451
460
469

65 PVC plasticized with 50 phr DBP were used immersed

in ethanol at 30C. For higher accuracy the weight of
20 x 50 mm specimens was used as an indication of thickness. The results in Table 5 indicate that the greater the
thickness of the specimens, the greater is the amount of
migrated plasticizer. At the end of the test the major part
of the plasticizer had migrated and the amount remaining
was greater for the thicker specimens.

Time
(days)

2.5 min

5 rain

10 min

15 min

2
4
6
10
15
20
30
40
50
60

230
327
370
421
445
452
462
467
472
477

213
307
352
392
416
430
441
449
459
461

208
280
321
368
392
417
425
431
437
442

202
262
297
335
380
398
415
424
432
437

Weight loss (mg)

Ethanol diffused
(mg)

294

290

273

265

183

171

169

172

Table 8 Effect of the presence of stabilizers upon the migration of

DBP and DOP from plasticized PVC into 96% alcohol

Migrated plasticizer
(rag)

Effect o f the epoxv plasticizer

In examining the effect of epoxy plasticizers upon the
migration of the main (phthalate) plasticizer, specimens
were made from k 65 PVC plasticized with 50 phr DBP or
DOP and 6 phr of epoxy plasticizer (a commercial epoxidized soyabean oil). The specimens were immersed in
ethanol for 30 days at 25C. The results obtained are given
in Table 6. As the data indicate, the epoxy plasticizer affects
migration, promoting that of the main plasticizer. This behaviour seems to be selective: DOP migrates to a greater extent than does DBP.

Time
(days)

II

III

IV

2
4
6
10
15
20
25
30

222
283
333
379
424
451
469
483

80
136
173
227
257
273
282
291

153
228
263
312
358
383
410
425

79
123
164
207
246
276
303
328

67
114
148
175
211
230
251
267

Lffect o f the plasticization process

I = Normally stabilized PVC plasticized with 60 phr DBP; II = unstabilized PVC plasticized with 60 phr DBP; III = normally stabilized PVC plasticized with 60 phr DOP, plasticization time 7 min;
IV = unstabilized PVC plasticized with 60 phr DOP, plasticization
time 7 min; V = unstabilized PVC plasticized with 60 phr DOP,
plasticization time 15 rain

This effect was studied for k 65 PVC plasticized with 50

phr DBP and immersed in ethanol at 30C for 60 days. The
plasticization process generally used in this work was followed with variations in the time of hot working which

POLYMER, 1975, Vol 16, November 843

Migration of PVC plasticizers into alcohols: E. M. Karnpouris et aL

Table 9 Effect of the temperature upon the migration of DBP
from plasticized PVC into ethanol

Migrated plasticizer (rag)

Time
(days)

10C

30 C

60 C

2
4
6
10
15
20
30

54
78
100
132
164
199
213

234
334
388
430
457
473
484

442
530
572
599
633
657
701

at temperatures ranging from 10 to 60C. The results in

Table 9 indicate that the temperature affects strongly the
migration of plasticizer; any rise in temperature increases
drastically the amount of migrated plasticizer. Thus 30
days of immersion at 10C gave the same amount of migrated plasticizer, as 2 days at 30C. Schematic presentation
of the results leads to the conclusion that the relation temperature/amount of migrated plasticizer is not a linear one.
E f f e c t o f time

Examining the effect of time, in all the above cases, we

can conclude that there is no linear relation between the
amount of migrated plasticizer and time, or the square
root of time. Contradictory results in the literature may

844

P O L Y M E R , 1975, Vol 16, November

be explained by the small intervals of time. Generally the

greatest migration rates occur in the first stages of the process. They become then lower and tend to minimize. For
long enough periods the total amount of plasticizer can
migrate, leaving the polymer plasticized, or swelled, by a
mixture containing low amounts of plasticizer.

ACKNOWLEDGEMENTS
The authors wish to express thanks to Dr G. Akoyunoglou
and Mr S. Daousis of the Biology Dept. of N.R.C. Democritos for counting the samples.
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