•CSIR 79-1779

MODJ' S FOR THE MIGRATION OF

ADDITIVi."- !N POLYOLEFINS

L. E. Smith, I. C. Sanchez, S. S. Chang, F. L. McCrackin and b. <en'ch

Polymer Science & Standards Division

Center for Material Science

National Bureau of Standards

Washington, D.C. 20234

Progress Report for Period

January 1 - March 31, 1979

Issued July 1979

Prepared for Bureau of Foods

Food and Drug Administration

Washington, D.C. 20201

Interagency Reimbursable Agreement

U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps. Secretary

Luther H. Hodges, Jr., Under Secretary

Jordan J. Baruch. Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Acting Director

Introduction

In addition to continuing our experimental and theoretical program as previously described, during the past quarter we have considered methods of organization and classification which could facilitate the understanding and use of our

program outputs. We have also considered a number of specific technical questions that have been raised by FDA staff. CXir program has focused initially on

the class of polymers best described as polyolefins. These polymers represent

the majority of plastics used in packaging applications and we feel that models

of migration developed for the principal members of the class will be applicable

to most members with only minor modifications. The technical requirement is that

the polymers be equilibrium fluids rather than glasses. This requirement can be

established by a glass transition temperature well below the use temperature or

by evidence of some crystallinity at use temperatures. Using these criteria, a

preliminary classification of polymers based on chemical structure can be developed as shown in Fig. 1.

We have found a formal decision tree to be a useful device to focus attention on the specific technical decisions involved in making regulatory judgments

on indirect additive questions. A simple example of such a decision tree is

given in Fig. 2 where it is presumed that choices of package sizes and suitable

simulating solvents have already been made. The general form of this tree is, of

course, independent of the polymer-migrant system involved but the functional

forms used in the calculations of partition coefficients and diffusion constants

are specific for the class of polymer involved. The determination of the appropriate functions for decisioiu is a principal objective of our \;ork along with an

assessment of the experimental data and methods needed as inputs.

Relation Between Partition Coefficient and Solubility

The second branch in the tree involves an estimation of K^, the partition

coefficient between the polymer and the food simulating solvent. In our Annual

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Figure 1.

POLYOLEFINS

Essential characteristics for treatment as equilibrium fluid:

Tg < --10°C; some crystallinity

Chemical classification (Examples)

(1) linear alkane (HDPE)

(2) branched alkane (PP,PB,PH)

branches straight chain aliphatic, ^ 4 carbons

(3) copolymers of (1) with (2) (LDPE)

(4) copolymers of (1) or (2) with _< 45% vinyl acetate (PE/PVAc)

Polymers_below will_not_generally have essential characteristics

(5)

branched alkane

(a) branches aliphatic > 4 carbons polyheptane, etc.

(b) alicyclic polyvinylcyclohexane

(c) branched poly (4MP)

(d) aromatic PS

(e) heteroatoms PVC, Saran

Notes:

(4) random PE/PVAc copolymers have crystallinity up to 45% VAc

(5a) m.p. ^ 70°C, (C^) may be totally amorphous, class probably commercially

unimportant

(b) T of polyvinylcyclopentane = 75°

E

(c) T between 20° and 40° for poly (4-methyl-l-pentene)

S

(d) PS T > 90°

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(e) PVC T > 60°

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Report (NBSIR 79-1598) we derived an. equation relating to the infinite

oo oo dilution interaction parameters x and Xg^

In K

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where the subscripts p, s and d refer to the polymer, solvent and diffusant.

OO OO For simplicity in what follows we have redefined Xp and Xg so that the size

parameter r^ is absorbed in the definition of the chi parameters (compare with

Eq. 13 of the annual report)

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The most difficult parameter to estimate in Eq. (1) is the diffusant00 solvent interaction parameter Xg» especially if the solvent is ethanol or

00 water. However, Xg can be experimentally obtained from a solubility when the

solubility is very low (say less than 1% by weight) . Let S be the weight

fraction solubility of the diffusant in the solvent phase and let S’ be the

solubility of the solvent in the diffusant. In a two phase mixture of solvent

and diffusant at equilibrium, we have, by equating chemical potentials of the

diffusant in the two phases;

In S + (l-r,/r^)(l-S) +x'!(l-S)^ = as ^ s In d-S') + (l-r,/r )S' +x° S’^ (2a)

d s ^ s

where Xg is the dif fusant-solvent interaction parameter as the concentration

of solvent approaches zero. Now if S is very small. S’ will also be small, so

that to a good approximation, we have (expand In (1-S’) and let 1-S and 1-S ’ = 1)

In S + (l-r,/r ) + X°° ~ ) S’ + ....=: 0 (2b)

d s ^s d s

or

x“ = -In S + r^/r^ - 1 (2c)

Substituting Eq. (2c) into (1), we obtain the result:

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OO Invariably, experimental values of Xp are positive and usually fall in

the range between zero and two.

OO However, larger values of Xp might be expected when:

(1) the d if fusant /polymer combination is polar /non-polar

(2) the diffusant is relatively large in size

(3) the diffusant is relatively volatile.

OO Large Xp are expected if the energetics are unfavorable, as in (1), or when

OO Xp has a large entropic component. The latter becomes more important the

closer the diffusant is to its gas-liquid critical temperature T^. Since, in

general, increases with molecular size, conditions (2) and (3) above tend

to cancel one another to a certain degree.

OO Values of Xp are most easily obtained by inverse phase chromatography.

We have begun experimental work in an evaluation of this technique and our

progress to date is summarized below.

Inverse Gas Chromatography

The technique of inverse gas chromatography (IGC) can be used to obtain

information about thermodynamic interactions and diffusional behavior of

polymer/migrant pairs, as discussed in the previous quarterly report. The

specific retention volume V is a key parameter in describing the equilibrium

distribution of a volatile migrant or probe molecule between the vapor and polymer phase. This quantity is calculated from the following expression:

V

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c T

c •w

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(4)

where At is the net retention time, the period of time that a probe molecule

is delayed in its flow through the column by dissolution in the polymer phase,

the corrected carrier gas flow rate, j a correction for pressure drop along

the column, T^ the column temperature and w^ the total mass of polymer in the

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column. The partition coefficient is directly related to V by the expression:

K = V°p„T /273

g 2 c ( 5 )

where P 2 is the polymer phase density at T^. Several considerations must be

taken into account in the experimental determination A sufficiently low

concentration of the probe must be introduced to avoid saturating the limited

amount of polymer, leading to an abnormally large vapor phase concentration of

the probe and a corresponding anomalous value of the net retention time. If

the surface to volume ratio of the supported polymer film is high, surface

adsorption can make a significant contribution to At. When both bulk and surface

sorption mechanisms occur the measured net retention volume, proportional to

At, is given by the expression:

total poljnner surface area. Carrier gas flow rate can also have an effect on

V . If the flow rate is too rapid then partitioning of the probe molecules

between the polymer and the vapor will be incomplete. A linear extrapolation of

determinations at several flow rates to zero flow rate is usually necessary to

eliminate this influence. The capillary column studies of Lichtenthaler

et al (1) suggest a relationship of the form:

a and b being temperature dependent constants characteristic of each polymersolvent pair. Such a relationship was found to give a good fit to their data

at low flow rates, however, its derivation has limited physical justification.

Initial IGC experiments have employed NBS SRM 1475 high density polyethylene supported on glass beads packed into a copper column. The column

( 6 )

where and are the bulk and surface partition coefficients and a^ the

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'••' ’ 1^;' ' f

' • ''fl •“’*'

:

• L'’-^^ i&9ioo offT >n«K/Xo9 aoqqod a 03oi no b^JioqqUa boaXiCI
was prepared as described by Gray and Guillet (2) but with a slightly lower

polymer loading than in their experiments. The net retention time between a

methane marker and the decane probe was determined from the flame ionization

detector output as a function of decane concentration and carrier gas flow rate

at 70 and 150°C. The net retention time was found to remain constant at 70°C for

decane concentrations below about 2 ppm. Concentrations below this amount were

employed in all subsequent measurements. A linear relationship between V and

and one of the form of equation 7 were used to extrapolate to zero flow rate

and gave retention volumes identical within 3%. The range of flow rates examined

is insufficient to distinguish between the two relations.

Two determinations of were made at 70°C, one before and one after heating

3

to 150®C. Different V values were obtained in each case, 234 and 258 cm /g

g

respectively. This 10% discrepancy could be due to a different percent crystallinity for each determination. Below the melting temperature, only the amorphous

fraction contributes to bulk sorption and any change in the amount of amorphous

material present will affect w^, and in turn V^, as can be seen from equation

(4) . The accuracy of the percent crystallinity determination probably limits the

maximum reliability to which V may be determined below the polymer melting

g

temperature.

3

The limiting V at 150“C was found to be 70.2 cm /g. Previous studies by

s Braun et al. (3) employed two polyethylenes, Marlex 50 and Marlex 6050, and

decane at temperatures from 145 to 153 "C. Interpolation of their results to

3

150°C gives 74.6 and 75.1 cm /g for the limiting V of the two polyethylenes.

g

These two values are identical within the experimental error of the procedure,

about 1 to 2%, but differ from our measured value by about 6%. The discrepancy

is thought to arise from instrumental limitations in our determinations as outlined below.

Several modifications of the apparatus will be undertaken to increase

the accuracy of experiments performed in this laboratory. Column immersion

7
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baths will be added to eliminate temperature variation along the length of the

column, as great as 30°C in some cases, particularly near the injector and

detector zones. Variability of the carrier gas flow rate, typically 5 to 7%

at low flow rates, will be reduced by an improved pressure regulator and mass

flow rate controller. An important parameter for determination of V is the

g

total weight of polymer in the column, w^. As the concentration of polymer

coated onto the glass beads is small, typically 0.5% by weight, precise determination of the polymer loading is critical for obtaining a reliable value of

i W-. The most common methods reported in the literature are gravimetric in

: I L

j nature. Calcination or solvent refluxing are employed to remove the film from

I the beads and the weight of polymer deposited is obtained by difference. The

:

I

ii accuracy of these methods is being evaluated and instrumentation for precise

i

I weighing in inert atmospheres is available for use if the commonly employed

|! procedures are found inadequate.

These improvements in apparatus and technique will allow more reliable

determinations of V and the partition coefficient to be made from IGC exg

periments. The polymer-solvent interaction parameter and its entropic and

enthalpic components will be obtained by study of selected systems at several

,! temperatures. Such results will be useful in evaluating the validity of

j theoretical predictions of the equilibrium thermodynamic treatment described

j| in the previous annual report. Better control of experimental variables will

I facilitate future studies of polymer-migrant diffusion. Gas chromatography will

1

'

also be employed to detect the swelling-assisted release of various oligomers

I from polyethylene which may occur during the course of migration studies with

I

I radiolabeled compounds.

I

j

I The third branch of the decision tree involves a calculation or an ex-

! perimental determination of the amount of diffusion expected during the pro8
IIIiII

I;1fit
|| posed use life. One promising approach to calculation of diffusion constants

Ij

Ij uses a group contribution method to calculate the molar critical volumes of

! polymers and migrants. These values are combined with empirical relationships

for calculating self-diffusion and mutual diffusion coefficients. All three

1

1 of these calculations are currently under evaluation and the technical approach

j

jj is summarized in the following.

|| Estimating Diffusion Coefficients in Polymer Liquids

*i 4

Recently, Fedors has developed an empirical relation for calculating the

i self-diffusion coefficient of liquids. The equation is:

I (V -V)T

i D = 4.5 X 10 . (8)

I nv

'

. c

I 2

I where is the self-diffusion coefficient in units of cm /sec, r| is the

I 3 viscosity in poise and and V are the molar volumes in cm /mole at the

critical temperature and temperature T, respectively. He has shown that this

equation works well for low as well as high molecular weight liquids. For

I non-associating organic liquids the average error is about 4%. Polymer liquids

show a much larger but acceptable deviation. Self-diffusion coefficients for poly

mer liquids are notoriously difficult to measure because they are often very small

Experimental errors are often large. However, even with this difficulty in mind,

calculated self-diffusion coefficients are within a factor of 2 or 3 of the

experimentally observed values for several polymers including polyethylene.

Experimentally determined values of critical volumes required in the above

equation are often unavailable. Of course, this is always true of a pol3nner

I liquid. There are several methods of estimating V^, but the simplest method is

a group contribution method also due to Fedors^. In the Fedors' method:

V = 26.6 +Sv. (9)

C XI

where the v^ are given below:

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Table 1. Atomic

Atom

and Structural

cm^/mole

Contributions to the

Structural Feature

Critical Volume

,"1

cm /mole

C 34.426 3-membered ring -15.824

H 9.172 4-membered ring -17.247

0 20.291 5-membered ring -39.126

0 (alcohols) 18.000 6-membered ring -39.508

N 48.853 Double bond 5.028

N (amines) 47.422 Triple bond 0.7973

F 22.242 Each additional ring

attached directly

to another ring

(that is, biphenyl,

naphthalene, etc.) 35.524

Critical volumes of p6 l3rmers of known molecular weight can be estimated by the

above method. A sample calculation to illustrate the method is given below

for polyisobutylene.

To calculate the mutual diffusion constant, component 1 in com6 7

ponent 2 at infinite dilution we can use the Hildebrand relation ’

:

( 10)

where is the self-diffusion constant of component 1 and and V are

the critical molar volumes of components 1 and 2, respectively. Sridhar and

Potter^ have shown that the Hildebrand equation works relatively well in

simple organic liquid mixtures. They did not investigate its applicability to

diffusion in polymeric liquids.

I For diffusion in a polymeric liquid, we write in a more familiar notation:

I D = D (v /V y (11)

O p \

cp cj

where D is the infinite-dilution diffusion coefficient of the diffusant in

o

j the polymer, V is the critical molar volume of the polymer, is the critical

} molar volume of the diffusant, and D is the polymer self-diffusion coefficient.

P

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Sample Calculation of Self-Diffusion Coefficient for Polyisobutylene

II

6

CH^

M = 1.35 X 10 1 0 CN 1 o

— 1

r)(35‘’C) = 10.4 poise

1 p(35°C) = .914 g/cm^ CH,

6 4

degree of polym = 1.35 x 10 /56 = 2.4 x 10

V = [26.6 + 4(34.43) + 8(9.172)] x DP

cV = 237 X 2.4 X 10^

c

ft 3

V = 5.7 X 10 cm /mole

c

V = M/p = 1.35 X 10 /.914 = 1.48 x 10^ cm^/mole

, . _-9 (1-V/V )T (4.5 X 10'^) (1 - 1.48/5.7) 308

D. T = 4.5 X 10 c_ = K~T7i „ 1/3 (10.4) (5.7 X lo'")-"'^

n

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We are currently testing Eq. (11) using the Fedors’ equations (8) and

(9) to calculate the D^, V^. Experimental polymer viscosity (zero

shear) values which do not include the chain entanglement contribution are

employed. The appropriate viscosity and density data are known for many

common polymers including polyethylene.

Initial results are very encouraging. Equation (11) implies that the

temperature dependence of diffusion in a polymer is dominated by the temperature dependence of the polymer viscosity. Experimentally, this is the

qualitative behavior that is observed as emphasized in our first semi-annual

report (NBSIR 78-1499).

Review of Diffusion Constant Data

Diffusion constants for moderate molecular weight additives in common

“6 “12 2

polymers are generally in the range of 10 to 10 cm /sec. depending on

the temperature. In order to show this range more explicitly, we have compiled a brief review of appropriate literature data. The scope of this review

has been limited to the compilation of diffusion constants (modeled by Fick's

Law) as a function of temperature and activation energies (modeled by the

Arrhenius equation) for migrants in polyolefins. The migrants selected are

organic molecules or molecules with organic components. The emphasis is on

higher molecular weight migrants, however, some low molecular weight substances

are included for reference or when they compose part of a homologous series of

additive materials covering a wide molecular weight range. Only data on two

component systems (migrant and polymer) are included in the tables of this

report.

In the following tables polyethylene has been subdivided into high density

(linear) and low density (branched) materials. The large differences in

diffusion constants for a single migrant in different polypropylene substrates

12
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i

suggest that a similar subdivision between isotactic and atactic polypropylenes

may be advantageous.

As mentioned in our Semiannual Report for 1978, diffusion in polymers is

generally strongly concentration dependent, a fact which is not evident from

the tables. Although the lowest concentration data were usually the ones

chosen for inclusion in the tables, many studies in the literature do not

provide much data on this point. In all cases, these data have received only

preliminary critical appraisal and represent only a part of the available

literature.

I

I

I

I

I

13
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Key to Abbreviations of Methods

I AP Sorption by pressure change measurements

i GR Desorption by weight-loss gravimetry

I GC Peak broadening in inverse phase gas chromatography

RA Radioactive tracer techniques

)

I TL Permeation time lag measurement

I

I IR Infrared microdensimetry

14

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U

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15

DIFFUSION

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(cm

/sec) o

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2,

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Benzophenone

RA

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.0230

.155

34.0

POLYPROPYLENE

(CONT.)

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20

POLYPROPYLENE

(CONT.)

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rs

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POLY

(ISOBUTYLENE)

22

References to Diffusion Data

. 1) I. Auerbach, W. R. Miller, W. C. Kuryla and S. D. Gehman, J. Polym. Sci.,

28, 129 (1958).

2) A. S. Michaels, W. Vieth, A. S. Hoffman and H. A. Alcalay, J. Appl

Polym. Sci. , 13, 577 (1969)

3) J. L. Lundberg, J. Polym. Sci. A, 3925 (1964).

4) J. L. Lundberg, M. B. Wilk and M. J. Huyett, J. Polym. Sci., 51_^ 275 (1962)

5) R. B. Long, Ind. Eng. Chem., Fundam. 445 (1965).

6) J. M. Braum, S. Poos and J. E. Guillet, J. Polym. Sci. (Polym. Lett.)

14, 257 (1976).

7) D, W. McCall and W. P. Slichter, J. Am. Chem. Soc., 1861 (1958).

8) E. K. Evnochides and E. J. Henley, J. Polym. Sci. A2, 1987 (1970).

9) Ibid., A.I.Ch.E.J., 1J_, 880 (1971).

10) D. G. Gray and J. E. Guillet, Macromolecules, 223 (1973).

11) M. Dubini, 0. Cicchetti, G. P. Vicario, and E. Bua, Europ Polym. J.,

3 473 (1967).

12) 0. Cicchtti, M. Dubini, P. Parrini, G. P. Vicario and E. Bua, Europ.

Polym. J., 419 (1968).

13) A. S. Michaels, H. J. Bixler and H. L. Fein, J. Appl. Phys. 3165 (1964)

14) R. K. Eby, J. Appl. Phys., 2720 (1964).

15) R. A. Jackson, S. R. D. Oldland and A. Pajaczkowski, J. Appl. Polym. Sci.,

1297 (1968).

16) M. Johnson and J. F. Westlake, J. Appl. Polym. Sci., 13, 1745 (1975).

17) J. F. Westlake and M. Johnson, J. Appl. Polym. Sci., 13, 319 (1975).

18) J. Klein and B. J. Briscoe, J. Polym. Sci. (Polym. Phys.), 13, 2065 (1977).

23
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j As mentioned in previous reports, the diffusion constant for a migrant

j| should correlate with molecular size and flexibility rather than strictly

I with molecular weight. With this in mind, the general effects of branching

I or the incorporation of ring structures can be predicted in that these

II

I structures are somewhat bulkier relative to the linear structure of the same

i

j molecular weight. Quantitatively, however, these differences are expected

I

I

to be rather minor (less than a factor of 2) except for extreme cases. An

! example of these effects is given in the first table of the diffusion data

where the diffusion of various structural isomers is compared in low density

polyethylene. Increased branching in 3-methyl pentane and neo-hexane lowers

the diffusion coefficient relative to n-hexane as does the incorporation of

a ring structure in the case of cyclohexane.

The experimental determination of diffusion constants generally involves

the analysis of data according to a presumed model. We have previously discussed ideal diffusion models but the possibility of temperature extrapolation

and the scaling of sample thicknesses are of particular interest so we will

discuss these aspects in more detail.

Errors in Temperature Extrapolations

Let the diffusion coefficient of a migrant in a polymer be at a temperature T^ with an activation energy E. Then the diffusion coefficient at a

temperature T

2 may be extrapolated to be:

D

2 = exp[ E/R(l/T^ - l/T^)] (12)

Let an estimated activation energy E + AE in error by AE be used instead of

the true activation energy E. Then the error in the predicted diffusion

coefficient D^' at temperature T^, expressed in percent, is:

D • - D

100 -^r ^ = 100 exp [f (ti - ij]- 100

24
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where R Is the gas constant and the temperature and are in degrees

Kelvin. Notice that the extrapolation error, when expressed in percent, depends

only on the error in the activation energy and on the temperatures; the percent

error does not depend on the activation energy or the diffusion coefficient.

Table 2 gives percent errors of the extrapolated diffusion coefficient for

extrapolations from 80°C to 60, 40 and 20°C for errors AE in the estimated

activation energy of 2, 5, 10 and 15 kcal/mole.

Table 2 shows that accurate values of the activation energy are required

for temperature extrapolation. Thus, if the activation energy is estimated to

within 2 kcal/mole, the diffusion coefficient may be extrapolated for 80 to 20°C

with less than 50% error. However, if the activation energy is only known to

within 10 kcal/mole, the diffusion coefficient may not be extrapolated from 80°C

to even SO^C with less than 50% error.

Table 2. Percent error in diffusion coefficients extrapolated from 80°C to

given temperature.

Error in activation 20*C 40'’C 60°(

energy, kcal/mole

2 44 3i 16

5 77 60 35

10 95 84 58

15 98 93 72

Effect of Thickness on Migration Rate

,2 . The theoretical migration curve for a film is shown versus Dt/2, in fig. 3

and versus /StT^ in fig. 4. A is the area of the film, I is the thickness of

the film and C is the initial concentration of the additive in the film, so the

ordinate is the fraction of the additive that has migrated out of the film in

2

time t. The migration is seen to depend on the ratio t/X . Thus the migration

curves of different thicknesses of film (with other parameters the same) are

25
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.b Jf

, ‘'TO
f •

I 2

' plotted versus t/£ , they should superimpose. This is observed for experimental

I migration curves in the next section. Simpler scaling laws apply if the migration

! is very slow or very fast compared to the times of service.

I

1

' The case of slow migration is illustrated in figure 5. The migration

i

I per unit area is shown versus the square root of the time for three film

j .rhlckn^‘=^ses. The mit^ration is seen to be independent of the film thickness,

I in fact, to be pxupoTLional to the square root of the time, for sufficiently

j

I small times. Equivalently, the sheet may be considered infinitely thick for

sufficiently small times. The condition for the migration to be independent

i

j of film thickness is:

I

i

I I > 3.76 (13)

I

I

I

I Thus, if equation 13 is satisfied for the service and test time of the

I film, migration measured at one film thickness may be used for another film

thickness. In this case, the migration per unit area is given by:

M. _ 4 v^t p (14)

A /tt

For very fast migration, the amount of migration is the total amount of

additive in the film, so:

= IC (15) A

so the migration per unit area is proportional to the thickness of the film.

Eq. 15 will apply within one percent for times

! t > 0.11 i^/T) (16)

I

i

I

! The above results apply for ideal, Fickian diffusion. They probably

I

\ also apply approximately for extraction when the rate of diffusion also depends

!

j on the rate of diffusion of the solvent into the plastic film. This will be

! investigated in the next quarter.

j

I

I 26
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' ‘ ' ‘"' ‘ ' ' “ —
Mt/(ACi)

I

1 .

0 .

0 .

0 .

0 .

0 .

Figure 3 . Migration Curve of a film versus Dt/2,

27

Mt/(A«)

1 .0

0 .8

0 .6

0 .

0 .2

0.0

'} Fig. A. Migration curve of a film versus square root of Dt/Jl“.

28

Mt/A

29

Experimental results that pertain to thickness scaling are given in

the following section dealing with our laboratory measurements of oligomer

migration.

1

i

!

I

1

[

Laboratory Measurements of Oligomer Migration

In the experimental migration work we are looking for the correlations

of migration of adjuvants from polymers into solvents, along with other

factors such as additive concentration, polymer crystallinity, specimen

thickness, etc. In the case of limited solubilities, the equilibrium

partition co-efficient may also be determined.

After the new coding scheme, the following topics are presented:

- methods of extraction

- possibility of eliminating thickness as a variable

- migration of into ethanol/water mixture

- partition coefficients

- search for simulating solvent for food oil

- migration of oligomers from branched polyethylene

- planned work for the next quarter

Coding Scheme

In order to convey more information in the sample coding system,

the following coding scheme is now used in place of the coding scheme

used previously. The sequential coding scheme is described below:

(1) 1st character — solvent type

C = Corn oil

E = Ethanol, with fractional ethanol content following

the letter E to denote the composition of aqueous

ethanol mixtures

H = Heptane

30
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0 = Octadecane

T = Trioctanoin

(2)

2nd character — sample plaque designation (LPE - linear polyethylene,

BPE - branched polyethylene)

% mm

0.01 1 5

0.2 LPE D B F

0.7 LPE C A E

0.7 BPE G

Sample E and F were saturated with C^

3Hgg.

(3) Extraction temperature in °C follows sample plaque designation

(4) Limited volume extraction experiments are followed by a letter

L, otherwise the experiments are carried out as to simulate

infinite solvent volume

(5) Additional experiments with similar conditions are distinguished

by a dash followed with sequential numbers

We are in the stage of finishing all the planned experimental observations

on the migration of from linear polyethylene into various solvents.

Only 8 of the 42 experiments are in their last stages at the present time, the

rest of the experiments have already reached completion. Selected results are

presented in the following section. Complete discussion and correlation of all

42 experiments will probably appear in the next report. The experimental conditions for all 42 experiments are summarized in the following tables:

31
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30 0C30 OA30 OE30

60 OC60 OB60 OE60

OF60

III. C-qH-q into Ethanol/water system

32
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1±0 moO oaoJ: 3'
In Tables I to V, where there is more than one experimental code in one of

the temperature-concentration combinations, they are included to show one of the

following three effects:

(a) reproducibility; HA60-1, HA60-2

(b) thickness variations: HA24L, HA24, HB24

or (c) the differences between limited volume extraction and infinite

volume extraction detailed in another section.

For each table, the experiments listed for the same temperatures are used to

determine the concentration dependence of the migration behavior, which may

include the plasticizing effect of the additive. There are clearly concentration

dependencies of the migration behavior; however, the effect is difficult to

separate from the effect of swelling of the polymer by the solvent, except in the

case of migration of the additive into the bulk additive as solvent.

The temperature dependence may be seen by the experiments listed in each

column denoting the same concentration in each table.

By collecting the experiments at the same temperature and concentration from

different tables, the effect of solvents may be seen.

There are essentially two different methods of extraction mentioned in

the FY78 Annual Report, viz., (1) simulated infinite volume extraction, and

(2) limited volume extraction. A third method was suggested as a variation of

method (2), but has not been applied because of more demanding sample requireHC24, HD24

OE60, 0F60

E.9A60L, E.9B60

E.5A60L, E.5B60L

Methods of Extraction

33
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pli'
ments. For solvents with high solubility or miscibility with the additive,

methods (1) and (2) will give identical extraction results. However, for solvents with limited solubility, method (1) may yield erratic results depending

on whether an equilibrium partition is approached or not before the replenishment

1

1 of the solvent. Therefore method (2) is preferred, in general for both high and

i

j low solubility solvents. Only in the case of known high solubility should method

I (1) be used to simplify experimental procedures. Such agreement may be seen by

!

t'

j comparing the results of pairs of experiments such as (HA24L, H/..24) and (EB24L,

j EB24) shown in last annual report.

At 60°C the solubility of in 90% ethanol is about 3%. Still, fairly

good agreement between the pair of experiments E.9A60L and E.9B60 is obtained by

2

reducing the thickness of the samples by t/£ as shown in Figure E-lA and E-lB,

i as well as in Figure E-IC and E-ID. By extrapolating the data to infinite time,

M for the limited volume extraction is estimated at 0.91 M , whereas M for the 00 O <x>

"infinite" volume extraction reaches 0.99 (Figure E-IE)

A comparison of the extraction methods (1) and (2) for poor solvents may be

|!

I seen from the results for E.5B60 and E.5B60(L) as shown in Figure E-lF. It is

evident that the total amount of extraction is much higher in the case of E.5B60

because of large volumes of solvent being used. However, as stated earlier, the

kinetic meaning of the data depends on whether an equilibrium partition has been

' approached before the renewal of the solvent.

Thickness

t

!

j It was stated previously in the FY78 Annual Report that both the reproducibility (HA60-1, HA60-2) and thickness scaling (HA30, HB30) and (HC24 , HD24)

2

by t/i are good. Even though the nature of sample D is somewhat questionable,

! the results of HC24 and HD24 may be brought much closer together by reducing

34
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2

the data in terms of t/S, . These conclusions may be visualized in a collection

of results for the migration of from LPE into as represented in

2

Figure ° E-2 for M^/M to versus t and in Figure E-3 for M /M versus t/2, . There- to

fore, final data involving samples of different thicknesses should be scaled and

2

represented by t/H in order to provide easier comparison.

By representing data in the form of M^/A, or in terms of PPM as defined in

CFR, versus t, a good correlation of thickness scaling may also be seen as the

initial portions of the curves collapse together as shown later in Figure E-5 for

the cases E.5A60L(1) and E.5B60L(1).

It seems that future experimentation may be simplified by eliminating the

observation of the thickness effect and considering only the four cases similar

to those listed in Tables IV & V. Although the range of thicknesses investigated

is limited to the practical range of 0.2 to 0.7 mm, a future check will be made

on a thick slab to simulate infinite thickness for migration lasting as long as 6

months. For very thin samples, the total content of the film may be used to

decide whether an extraction experiment is even needed.

i ^18^38 into Ethanol/Water Mixtures and Partition Coefficients

At high ethanol content, the migration behavior seems to be Fickian.

1 ^

k

t However, deviation from Fickian behavior increases as the ethanol content is

decreased. At 50/50 ethanol/water composition and below, the amount migrated is

almost linearly proportional to time. These may be seen in a collection of

I results for migration of C^gH^g from LPE into ethanol/water mixtures at 60“C

I

;| in Fig. E-4. The results of HA60, ^^3^23 from LPE into heptane at 60®C, are

! also included for comparison purposes.

;! Below 70% ethanol content, equilibrium partition may be reached due to

the low solubility of C^qH-q at these compositions, as shown approximately in

j lo Jo

' Figure E-4B.

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Three experiments (E.5A60L, E.5B60L and E.5C60L) are represented in Figure

E-5. For each of the three experiments, new solvents are used to repeat the

j extraction experiment after a partitioning of has been reached. The

i

I numbers in parentheses denote the successive renewing of the extraction proI

j cedures. The similarities in the initial behavior from successive extractions

! indicate that a redistribution of additive concentration was achieved before the

I renewal of extracting solvent. The level of initial extraction represented by

the mass migrating per unit area is clearly influenced by the overall additive

i content in the polymer. There is virtually no thickness effect for the initial

i

i migration. The final concentration depends on the partition coefficient, the

j

j total amount of C^gH^g, and the ratio of the volume of the polymer sample to that

I

j of the solvent. The partition coefficient for E.5A60L and E.5B60L, even at

* different successive extractions, are all at about 0.0012.

I The partition coefficient for E.5C60L is, however, about 0.00045. Perhaps

at 0.01% additive level, the labeled additive may not represent most of the

I

j Cj^gHgg present in the polymer. Another possibility is that the dissolution of

other oligomers from the polymer may influence the solubility and therefore the

observed partition coefficient in 50/50 ethanol/water mixture. As detailed in

the FDA Memorandum by Dr. Snyder, linear polyethylene contains about 0.2% of

extractable oligomer content having a MW distribution maximum at about 300.

The advantages of the ethanol/water mixtures as simulating solvent for

oligomers are that the solubilities may be changed by 5 to 6 orders of magnitudes

j by changing the compositions (ref. - quarterly, report , Oct. 1 - Dec. 31, 1978).

I

I However, the same advantageous characteristics are also the cause for concern.

I

I During long term testing some evaporation and change of composition may occur.

!

• • The solubility, and hence the partition coefficient, may be changed drastically

during the course of a long extraction experiment. Therefore, the extraction

36
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«n«xinients in volatile mixed solvent systems require rather exacting experi-

-Tnentiil conditions to avoid the changes in the solvent composition. The type of

1

1 extraction .-vials as shown in the last annual report require at least a flat

i

,

'[ grinding of the vial tops, even better with fine polishing, in order to seal the

extraction vials against teflon gaskets.

^18^38 Corn Oil and Trioctanoin

In searching for simulating solvents as substitutes for food oils, the

natural tendency is to look for some pure triglycerides to avoid compositional

uncertainties. Tributyrin and trioctanoin seem to be readily available. Although tributyrin is much less expensive, trioctanoin is much closer to food oils

in the solubilities for Solubilities of in various food oils as

I well as in certain potential simulating solvents will be presented in the future.

I At 60®C, the migration behaviors of C^^gH^g into corn oil (CA60L) and trioctanoin (TA60L) are very similar to each other (Fig. E-6) . They are also

rather similar to that into 90% ethanol (E.9A60L), although in the case of

E.9A60L, an eventual equilibrium partitioning may be reached. The migration

behavior of C^^gH^g into heptane HA60 is also shown in Fig. E-6 for comparison.

It is obvious that, at about 0.8-0. 9, the rate of migration into heptane is

about ...tim-es faster than that in the other three cases. Thus both trioctanoin

and 90% ethanol could be considered as simulating solvents for food oils instead

of heptane. Their similarities in temperature coefficients and concentration

effects may require more thorough comparisons.

The migration behavior for C^gH^g into trioctanoin is largely Fickian. Some

irregularities in the behavior (deviating from a smooth behavior) were observed

(Figure E-7). This could be the result of insufficient agitation of the viscous

solvent or due to the long term instability of the temperature controller. We

f . have now acquired heating blocks with magnetic stirring devices. The effect of

37
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stirring will be carried out in the near future. A 30“C temperature change from

30 to 60 seems to change the time for extraction by a factor of 30. This is

probably related to the large change in temperature coefficient of the viscosity

of the solvent.

I Migration of from Branched Polyethylene

I

^

I

I We have started migration studies of C^gH^g from branched polyethylene

j

j samples. Preliminary results Indicate that the migration rate of HG60 is about

: 5 times faster than that from linear polyethylene samples HA60 of the same CtoH.,,

j io Jo

j content and thickness and at the same temperature; otherwise the behaviors are

I -7 2

! very similar. The diffusion coefficient is about 4 x 10 cm /sec. as compared

I to 1.6 X 10 ^ listed in the table of literature values. In Figure E-8 it is

i

j obvious that almost all the added C^gH^g was removed in about one hour by heptane

j at 60°C. We will correlate in the future the effects of solvents, and temperature on oligomers in BPE, as well as the effect of crystallinity and with LPE.

I Planned Work for the Next Quarter

Tables of apparent maximum diffusion constants corresponding to the five

tables of the code scheme are now in preparation and awaiting completion of the

experiments. Further work on the migration of C^gH^g from BPE and experimental

work on the migration of from both BPE and LPE will begin in the next

quarter. A plaque of LPE approximately 3 mm thick will be used to demonstrate

experimentally the ’infinite' thickness behavior. We will also explore the

I possibility of using plasma oxidation as a method to determine the concentration

i

I profile of the additive and thereby determine the diffusion constant in the

absence of solvents.
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References

( 1 )

i

( 2 )

I ( 4 ) |

ii (5)

i-

!| ( 6)

R. N. Lichtenthaler , D. D. Liu and J. M, Prausnitz, Macromol., 7^, 563 (1974).

D. G. Gray and J. E. Guillet, Macromol., 129 (1971).

J.-M. Braun, M. Cutajar, J. E. Guillet, H. P. Schreiber, and D. Patterson,

Macromol., 10 , 864 (1977).

R. F. Fedors, AIChE Journal , 25 , 200 (1979).

R. F. Fedors, ibid. , 25 , 202 (1979).

J. H. Hildebrand and R. H. Lamoreaux, Proc. Natl. Acad. Sci. USA , 71 , 3321 (1974).

(7) T. Gridhar and 0. A. Potter, AIChE Journal , 23 , 590 (1977).
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U.S. OEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. NBSIR 79-1779 (FDA)

2.Gov'l Accession No. 3. Recipient's Accession No.

4. TITLE AND SUBTITLE

Models for the Migration of Additives in Polyolefins

5. Publication Date

6. Performing Organization Code

7.AUTH0R(S) L. E. Smith, I. C. Sanchez, S. S. Chang,

F. L. McCrackin, and G. A. Senich

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS rsfreet, City, state, ZIP)

Bureau of Foods

Food and Drug Adminstrat ion

Washington, D.C. 20201

13. Type of Report & Period Covered

14. Sponsoring Agency Code

15, SUPPLEMENTARY NOTES

I

I Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 2.00-woTd or less (actual summary of most significant information. If document includes a significant bibliography or

literature survey, mention it here.) In addition to continuing our experimental and theoretical program as previously

described during the past quarter we have considered methods of organization and classification which could facilitate the understanding and use of our program outputs. We

have also considered a number of specific technical questions that have been raised by

FDA staff. Our program has focused initially on the class of polymers best described

as polyolefins. These polymers represent the majority of plastics used in packaging

applications and we feel that models of migration developed for the principal members

of the class will be applicable to most members v/ith only minor modifications. The

technical requirement that the polymers be equilibrium fluids rather than glasses can

be established by a glass transition temperature well below the use temperature or by

evidence of some crystallinity at use temperatures. Using these criteria, a preliminary classification of polymers based on chemical structure has been developed. We

have found a formal decision tree to be a useful device to focus attention on the specific technical decisions involved in making regulatory judgments on indirect additive

questions. A simple example of such a decision tree is given. The general form of

this tree is, of course, independent of the polymer-migrant system involved but the

functional forms used in the calculations of partition coefficients and diffusion constants are specific for the class of polymer involved. The determination of the

appropriate functions for decisions is a principal objective of our work along with an

.a.s.sessTTip.nt of t he experimental data and methods needed as inputs.

17. KEY WORDS rsix to fwe/ve entries; alphabetical order; capi talize only the first letter of the first key word unless a proper name;

separated by semicolons)

Additives; diffusion; food additives; indirect additives; migration; models;

regulation.

13. AVAILABILITY C Unlimited 19. SECURITY CLASS

(THIS REPORT)

21. NO. OF 1 PRINTED PAGES 1

For Official Distribution. Do Not Release to NTIS UNCLASSIFIED 54

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20. SECURITY CLASS

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