NAT L INST. OF STAND & TECH R.I.C. MBS

Puhli * cations

A-i-l-irB-!— fl D

AIBSSFi 78-1499 A1110M S37bm

An Evaluation of Existing

Models Describing the Migration

of Additives in Polymers

I. C. Sanchez, S. S. Chang, F. L McCrackin and L E. Smith

Polymer Science & Standards Division

Center for Material Science

National Bureau of Standards

Washington, D C. 20234

Semi-annual Report for Period

September 1, 1977 - March 30, 1978

Issued July 1 978

Prepared for Bureau of Foods

Food and Drug Administration

Washington, D.C. 20201

Interagency Reimbursable Agreement

-QC —100

. U56

78-1499

NBSifi 78-1499

* * 1 AN EVALUATION OF EXISTING

MODELS DESCRIBING THE MIGRATION

OF ADDITIVES IN POLYMERS

witmastdartis

6RC 10 0

, DC U

!. C. Sanchez, S. S. Chang, F. L McCrackin and L. E. Smith

Polymer Science & Standards Division

Center for Materia! Science

National Bureau of Standards

Washington, D.C. 20234

Semi-annual Report for Period

September 1, 1977 - March 30, 1978

issued July 1 S78

Prepared for Bureau of Foods

Food and Drug Administration

Washington, D.C. 20201

Interagency Reimbursable Agreement

Mi55 £&pr' > /vt3s i R ^iir isqa.

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

Dr. Sidney Herman. Under Secretary

Jordan J. Saryeh, Assistant Secretary for Science end Technology

fyATIONAL BUREAU OF STAWDAflDS. EmM Ambler, Director

AN EVALUATION OF EXISTING MODELS

DESCRIBING THE MIGRATION OF

ADDITIVES IN POLYMERS

I. C. Sanchez

S. S. Chang

F. L. McCrackin

L . E . Smi th

Report to: Bureau of Foods

Food and Drug Administration

Covering the period September 1, 1977

to

March 30, 1978

SUMMARY

The objective of this work is the development of mathematical models that describe the migration of a variety of

small molecules in polymers that have applications in food

contact uses. In the most general cases, these models will

be able to predict the amount of additive migration given

any particular time and temperature history. These models can

serve as the technical basis for more efficient regulatory

methods under existing frameworks or in the design and implementation of new indirect additive regulations or policy.

The existing data on additive migration applicable to

food contact uses have been surveyed and organized for reference.

Existing models describing additive migration into foodsimulating solvents have been surveyed and evaluated. From

these considerations four main conclusions can be drawn:

1) At a given temperature above the glass transition

of the polymer, diffusion in the polymer is

invariably proportional to the concentration

gradient of the diffusing species. The concentration gradient is the rate of change in concentration

with distance in the polymer.

2) Diffusion in polymers below their glass transition

is complex and difficult to generalize.

3} Above the glass transition temperature, the temperature

dependence of diffusion is primarily determined by the

properties of the polymer and relatively independent of

the size and shape of the diffusant.

4) The temperature dependence of the diffusion is

strong and non-Arrhenius. This means that a plot

of the logarithum of the diffusion constant versus

the inverse of the absolute temperature will generally

be non-linear.

To model migration of minor constituents from a polymeric

film to a food simulating solvent requires knowledge of (1) the

equilibrium distribution of a migrant between polymer and solvent

phases, i.e., the distribution or partition coefficient K and

(2) the diffusion coefficient D of the migrant in the polymer.

This is the minimum amount of information required to describe

polymer/migrant/solvent system. For a polymer at a temperature

above its glass transition temperature, knowledge of K and D

allows one to calculate migration as a function of time and as

a function of temperature if the temperature variation of K and

D are also known.

l
We have shown that the distribution coefficient is

related to the migrants' chemical potential in the polymer

and solvent and have demonstrated how K and its temperature

dependence can be calculated using recently developed

theories of the chemical potential. Our preliminary calculations have been very encouraging. Additionally , K is

amenable to experimental determination by utilization of gas

chromatographic techniques.

Existing theories of the diffusion coefficient can be

characterized as being correlative rather than predictive.

We have formulated a new theory for D which promises to be

more predictive than existing theories. This new theory is

based on the thermodynamic theory of fluctuations and depends

oni (1) the shape and size of the diffusant, (2) the polymerdiffusant intermolecuiar interactions, and (3) the isothermal

compressibility of the polymer.
TABLE OF CONTENTS

Page

INTRODUCTION ..... ........ 1 SURVEY OF MIGRATION DATA APPLICABLE TO FOODCONTACT USES ......... 3

Introduction .... ....... 3

Key to Abbreviations .............

Ordered Index to Available Data ........ 7

Literature References ........ 15

REVIEW AND EVALUATION OF AVAILABLE MIGRATION

MODELS ........ 33

Introduction ................. 33

Distribution Coefficients ........... 34

Diffusion Constants ..... 42

General properties ...... 42

Diffusion above Tg ............ 44

Diffusion below Tg ....... 47

References ............. 53

PRELIMINARY CLASSIFICATION OF ADDITIVE TYPES .... 55

INTRODUCTION

The effective regulation of indirect food additives

arising from the migration of substances from plastic

packaging materials involves three main technical questions

:

1) What substances are present in the packaging

material that can migrate into foods?

2) To what extent and at what rate can these

substances be reasonably expected to migrate

into the food?

3) What are the physiologic consequences of the

ingestion of these quantities of these substances by the public?

The first of these questions can generally be answered

by consideration of the synthesis and fabrication steps of the

packaging material supported by straightforward analytical

methods. The third question is a complex toxicological problem

which at present can only be answered with case by case testing

and even then is subject to considerable debate. The second

question , however, is a measurement problem capable of general

resolution and is the subject of this FDA-sponsored work.

The objective of this work is the development of mathematical models that describe the migration of a variety of

small molecules in polymers that have applications in food

contact uses. In the most general cases, these models will

be able to predict the amount of additive migration given

any particular time and temperature history. The models will

be designed to require a minimum of laboratory data determined

for the particular polymer-migrant system.

These models will serve several purposes. They can serve

as a basis for the classification of polymers and additives

into groups with similar migration behavior for regulatory

purposes. They can reduce or eliminate the need for extensive

extraction data to qualify new polymer-additive systems for

food contact uses. For example, a change in a packaging process

-]-
requiring a higher filling temperature could be considered on

the basis of an extrapolation from existing data without the

need for additional laboratory work.

Physical models of migration can allow a relatively rapid

estimate of maximum exposure of the public to any criven additive

or additive type. These estimates can guide public policy and

provide a quantitative basis for toxicological assessments of

risk. Finally, physical models or description of migration

behavior can provide the technical information for a comprehensive

review or adjustment of the total regulatory framework covering

indirect food additives.

The first steps in the development and assessment of such

models are given in this report. The first section presents

a preliminary survey of migration data applicable to food contact

situations that are available in the current literature. The

second section surveys available models describing migration

and evaluates their present and potential utility.

- 2-
SURVEY OF MIGRATION DATA APPLICABLE TO FOOD CONTACT USES

INTRODUCTION

The following literature survey collects and organizes

available data on migration rates of low molecular weight

species from polymeric matrices that have primary applicability to food contact situations. Only data that apply to

food contact situations have been included. References that

are useful in formulating and testing general models of

migration will be added as the need arises. References prior

to 1970 are also not explicitly included as these papers are

adequately referenced in the cited, later work.

The ordered index is sorted first by type of polymer,

then by the nature of the migrating species, and then by

solvent. The abbreviations used are explained in the following

section. The remarks primarily refer to the type of data

presented and the time and temperature interval for which

data are available.
KEY TO ABBREVIATIONS

o.^s^^PQLYMERS******

ARS ACRYLC NITR ILE/E

AdS/MA ABS/MA/MMA CGPO,

CA CELLULOSE ACETA

E/P ETHYL. ENE/PRCPYL

t/PHAC ETHYLENE/PHENYL

£/ VAC ETHYLENE/V INYL

EPXR EPCXY RESIN

HP FLUORCPCL YMER

S

MFR MELAMINE FORMAL

N6 NYLON 6

NR NATURAL RUBBER

PA P CL YAM IDES

PAN POLYACRYLGMTkl

PAT POLYACETAL

pa d PCLY BUTADIENE

POMS POLY 0 I METHYLS IL

PE polyethylene

PES POLYESTER

PM A

PM M A

PM P

POM

PP

PPHAC

PR

PS

PU

PVC

PVC/ABS

PV DC

SAN

SBR

SR

V/ APB

ACETATE

ACETATE

RESIN

POLYMETHACRYLATE

PCLY { M ETHYE METHACRYLATES

POL Y i 4— METHYLPENTENE— 1

i

PCLYOX Y METHYLENE

PCLYPRCPYLENE

POLYPHENYL ACETATE

PHENOL IC RESIN

POLYSTYRENE

POLYURETHANE

POYL ( V I NLY

POLY ( V INYL

SILICONE

VINYL ACi

CHL C RI DE ) CHL C RIDE ) / AB S

I DEN E CHL OR ID E ) R YLU N I TRI LE

TADI E NE RUB EE R

UDHE R

ATE/ V I NYL P YR RO H'JTYL ETHER

* *****MI GRANTS******

ABC

AC A

AHA

AN

HOG

BHA

ACETYL TR I BUT YL C I TR A TE

RCTO NIC A C ID E c TE RS

0-4- HYD RC X YANT H R A GU I NONE

N ITR ILE

ENE CL I GC MER

UT YL -4- HY DRO X Y A N I SCLE

- 4

-
out

tJPOG

HPO

H5T

OTA

E)T AC

CAST

Cl>

08P

DBS

OB SN

DC DA

DHA

DHBP

DNP

OOP

DO SN

DTCT

DTP

HCHO

HE B P

HM BP

HO BP

HXD

MGST

MM A

MM BP

MSN

MW

NAAQ

ODE

OH BP

PAP

Po

PH

t ADM IUM

01 BUTYL

C SBUT YL

D I BUTYL

2 . e-u i-tert-butyl-p-ckescl ; ignul; advastab ah

BUTYL FHTHALYL HUTYLGI.YCCLATE

BENZCPFENONE DERIVATIVES; DA S7 I B- 24 4 . - 256 *-? 8 • BUTYL STEARATE

3ENZ0TKI AZCLE-FHLNOLS J TIMJVIN P; TINUVIN 320

C HLGRCBENZDTF I AZOLE-PHENOLS i TINUVIN 326“» TINJVIN 3? 7

CALCIUM STEARATE

P I G ME IN T S

PHTHALATE

SEBAC ATE

TIN C C M POUNDS

DICYANCIAM I DE

1 * 4— DI HYOROXYAMHR AQU INCNE

2 • 4- D I HYDRCXYBENZOPHENCNE

OINCNYL PHTHALATE

0 IOC T YL PHTHALATE

DIOCTYL TIN COMPOUNDS

N-DCTR IACCTANE

D I DGOECVL — 2 „3 e -THI CPRCPIGNATh

i-GXYBENZOPHCNONt l CAST 13 24?

!NGNC» UV ABSORBER MOB 5 ADVASTAB

JCNE; ADVASTAB 46; CYASQkB UV531

DECANE

IUM STEARATE

METHYL

4 — MET H YL— 6 — TER T—BUT YL PHE NQL i l 2246

METHYL TIN COMPOUNDS

M SCRC W AX

4 — M TRC— 4

* — AM I NCAZO BENZENE

N-OCTACECYL-D IE THANUL AMINE

N-OCT A DEC YL-B-( 4 “—HYDROXY — 3 * 5*— DI — T—6'J T YL PHE N YL » PROPIONATE

PCLY AD IPATE

LEAD

PHENOL

ESTERS

C EH YD t

OXY-4 -C 2

» - ET H

CXY-4 -M E T hOX Y

CXY -4 -C C T C XY a DEC AN £

IUM S TE A R A TE

ME TH AC R Y L AT E ETH YL EN E - O I S -

T I N CC MR C UND

45

RP AL KYL FHTHAL

A

TE S

RSE AL KYL SULFON

I

C AC I D

S STYREN E

SA STEARI C ACID AM IDE

SN T I N CC MPCUNDS

ST P DI STEA R YL T H I CD IPRO

TBC 4 » 4 9 — I HI 0-8 I S - ( 6-TTCP TR ICRE SGL PHC SPhATt

TEP TR I ETH YL PH C S PH ATE

TU TR IGL YCER 2 DES

1 1 02 T I TAN I UM DICX I D L

TNPP TR I S- I NGN YL PH EN YL I TTB 1 9 3 « 5— TRIMETH YL -2.

4

VAC VI NYL ACETATE

VC V I NYL C HL GRIDE

WAX PA RAFF IN WAX

XY Z BE NZ EN e; chlo KG BENZ

N- AL KANE

ZNST Z I NC S TEAR ATE

ADVASTAB PS802J ANT IOXYDANS AS

.RE SOL); ADVASTAB 4 15; SANT ON 3

X

PHOSPHATE; ADVASTAB TNPP

« 4 » 6-TR I Si 3 , 5— D I — T—BUT YL— 4— HYDROXY BENZYL, i

LTHYLENE GlYCQL; ETHYL EH TEH ITHANOl.

- 5 -
AQ AQUEOUS SOLUTIONS OF SALTS; DETERGENTS; E T C

3L BLCOD

DP DAIRY PRODUCTS

ETON ETS-ANCL

ET20 DIETHYL ETHER

FHC FLUORCH YD ROC ARSON

HC HYDROCARBONS

H20 WATER

HQ AC ACETIC ACID

MEOH METHANOL

MF MEAT AND FAT

NH N— HEPTANE

OIL OIL! FAT AND SIMLANT

ROH ALCOHOLS

R20 ETHERS

TG INDIVIDUAL TRIGLYCERIDES

VEG VEGETABLE

# *****METHCDS******

CA CHEMICAL ANALYSIS

COLOR CCLOR IMETRY

GC GAS CHRGMATCGR APHY

GM GRAV IMETRY

PHOTO PHOTOMETRY

POLAR PCLARC GRAPhY

RAD RADI CANAL YS I

S

SECT SECTIONAL ANALYSIS

SPEC SPECTROSCOPY

TLC THIN LAYER C HRC M ATOR GR APH

Y

******F<EMARKS******

AC ACTIVITY COEFF

APP APPA RATUS/METH

CMT CORREL AT ICN/MO

CP CONCENTRAT ION

D DIFFUSION CCEF,

EN I EXTRACT NOT ID

GR GRAPHS

H* ACTIVATION EKE

K PARTITION CCEF

MiC MIGRANT CONCEN

NC NC COMPOSITION

NKD NO KINETIC DAT

NS NC SURFACE ARE

NTT NC TEMPERATURE

I C IENT

CO

DEL/THEORY

GRADIENT PROFILE

F IC I ENT

FNT IF I EC

R G Y

F IC I ENT

T RAT I C N

AA INFORMATION

OR TIME INFORMATION
PHR

PT

SO

SECT

SQL

UNITS

PAPTS PER HUNUPEQ PARTS CF PC.SIN

pc CM TEMPEPATUPE

SCRPT ICN-OESQPPT IQN

SECTICNAL CBSEPVATICN

SOLUBILITY

C-CELCIUS; D-DAY; H-HOJR; M-MQNTH, W-WEEK Y- YEAR

ORDERED INDEX TO AVAILABLE DATA

POLYMER M 1 GRANT SOLVENT METHOD REMARKS (DATA POINTS AT TEMPERATURE/TIME) REFERENCE

ABS ABC ETCH NKDj TO 80C/70 50 124

ABS ABC H2C NKD « TO 80C/TO SO 124

ABS AN AO gr: RT/ TO 2C qd 144

ABS AN H20 GRZ RT/ TO 2600 1 44

ABS BST ETOH NKD • TO ©OC/TO 50 . 124

ABS BST H2C NKD, TO 80C/TO 50 1 24

ABS S AQ gr: RT/ TO 2000 } 44

AOS s ETOH NKD, TO 80C/TO 50 124

ABS S H2C NKD, TO 80 C/7 0 50 1 24

ABS s H2Q Gk: RT/ TO 2000 144

ABS XVZ INTER-POLYMER, APP, 70C/TO 13200 S 1 2 CA OOP ET 20 GC NKD, TO 96C/T0 130 10

CA OOP HC GC NKD , TO 98C/7Q 100 10

CA OOP OIL GC NKD, TO 98C/TO IOD 1 0 CA OOP TG GC NKD, TO 98C/70 100 10

CA XYZ 1 00

E/P HXD 0 141

EPXR CMT 99

FP HCHO H2C NKO, 0-90C/I-100 I 22

MFR HCHO H2C NKD 32

NR CTCT D 141

NR tel AX TO 2800 1 9

NR XYZ GM BLOOM l 56

NR XYZ D.' CMT, SMEAR 14 4 PA CD ETOH e oc/6H 1 90

PA CO E T 20 8CC/6H 190

PA CO H2C 8CC/6H 190

PA CD HOAC 80C/6H . 1 90

PBO HXD C, CMT 1 39

PBD HXD 0, CMT, SMEAR 140

PBO HXD 0 14 1 POMS OTCT 0 141

PE EHA E T 20 GC NKO, TO 98C/T0 iOD 10

PE BHA HC •GC NKD. TO 98C/T0 IOD 1 0 PE EHA OIL GC NKO, TO 98C/TO 100 1 V PE eHA TG GC NKO, TO 98C/T0 100 1 0 PE EPD ETOH 45C/2.10D, 70C/2H, 100.121C/0.5H 1 66

PE EPD H20 45C/2.100. 70C/2H, 1 50 , 1 2 1 C /C' • 5H 1 68

PE SPD HOAC 4SC/2.10D. 70C/2H. 100, 12IC/C.5H 1 66

PE BPD OIL 45C/2.10D, 7JC/2H, 1C 3. 121C/0® 5H 1 68

PE E7AC ETCH TLC NKD, 45C/10D 1 70

PE ETAC HC TLC NKD. 45C/1CD 1 70

PE ETAC HC GR: 4D-65C/TG 600 1 1 0

PE ETAC H20 TLC NKO. 45C/10D 170

7

-
PE ETAC HO AC TLC NKD, 45C/100 1 70

PE etAC 0 IL POLAR 4.20-25C/1.2. 3.6M, 45C/10D.6M 1 66

PE ETAC OIL TLC NKD. 45C/10D 1 70

PE ETAC OIL GR: 4D-O5C/T0 60D 1 1 8 PE CO ETOH 80C/6H 1 <30 PE CD ET2C ecC/6H 1 90

PE CO H20 ECC/EH 1 90

PE CD HO AC A 3C/6H 190

PE DHBP H2C RAD CMT, 0, 44— 75C/TO 1 OOOH 1 77

PE D CP INTER-POLYMER. APP, 70C/TQ 1320D 1 1 2 PE DTP RAD C. H*. CMT, SMEAR, 20-7BC 73

PE HEUP ETOH 45C/2.10D, 70C/2H, 1 00 » 1 2 1 C/0 . 5K 1 6B

PE HEBP H20 45C/2.1J0. 70C/2H. If 0 , 1 2 1C/0. 5H 1 68

PE HEBP H 0 AC 4 5 C/ 2,100, 70C/2H, ltj, 121C/0.5H 1 68

PE HEBP OIL 45C/2.10D, 73C/2H, 100 , I 21C/0.5H 1 68

PE HMBP ETOH TLC NKD. 45C/10D 1 70

PE HMBP HC TLC NKD, 45C/10D 1 70

PE HMBP H2C TLC NKD, 45C/I0D 1 70

PE HM6P HO AC TLC NKC, 45C/I0D 1 70

PE HMBP OIL TLC NKD, 450/ 1 OD 1 70

PE HOBP ETOH 45C/2.10D. 70C/2H, 1 0 0 . 1 2 1C /O* 5H 1 68

PE HCDP H2C RAD D, H*. SMEAR, EXTRACT *)44C/T0 255D 77

PC HCBP H20 45C/2.100, 7 j C / 2 H , 1 C 0 , 1 2 1C / 3 • 5H 1 68

PE HCBP HO AC 45C/2.10D. 70C/2H, l u ), 121 C/0 • 5H 1 68

PE HOBP CIL 45C/2.10D. 7vC/2M, 1 C 0 . 1 2 1 C/0 . 5H 1 68

PE MMBP RAO D, K, 1 NTER— POLYMER 1 3

PE CDE RAD C, H*. CMT, SMEAR. 20— 7 8C 73

PE SA E T 20 RAD 200/600. 65C/5H, GR : 0.5-5H 1 32

PE SA F HC RAD 2CC/43.60D 54

PE SA HC RAD 4-25%DOP. APP, 20C/30.60D, 40C/10D, GR : TO eoc/TO 80 D 46

PE SA HC RAO 20C/43.60D 54

PE S A HC RAD 2CC/6CD, 65C/5H, GR : 0.5-5H 1 32

PE SA MECH RAD 20C/6OD, 65C/5H, GR : 0 . 5-5H 132

PE SA CIL RAD APP, 20C/63D. 65C/5H, GF. : TO 65C/TO 6 3D 39

PE SA CIL RAD 2 0 C/30.600 4 5 PE SA OIL RAD 4-25XD0P. APP. 20C/30.60D, 400/100, GR : TO boc/to BCD 4o

PE SA OIL RAC 65C/2.5H. GR! TO 6H 51

PE SA C IL RAD 20C/33.OJD, GRJ 600 52

PE SA CIL RAD APP, FAT-PENETRATION. 20C/3O.60D, 65C/2.5H 53

PE SA OIL RAD 20C/43.60D 54

PF SA CIL RAD 20C/60D. 65C/5H, GR: 0.5-5H 1 32

PE SA R2 C RAD 4-25-*D0P. APP, 20C/30.600, 40C/10D, GR : TO BOC/TO BOD 46

PE SA R20 RAD 2CC/43. 600 54

PE SA TG RAD 65.B3C/2.5H 36

PE SA TG RAD 2UC/3J , 600 45

PE SA TG RAD 65C/2.5H, GR: TO 6H 51 a u SA TG RAD 200/30,600. GR: TO 60D 52

PE SA TG * RAD APP. FAT-PENETRATION. 20C/30.60D, 65C/2.5H 53

PE SA SURFACE 5)

PE TTB E T 20 RAD 20 C/6>D, 65C/5H, GR : 0.5-5H 1 32

PE TTB FHC RAD 2 JC/43.60D 54

PE TTB HC RAD 4-25*0OP. APP, 200/30*630. 40C/10D. GR : TO 80C/T0 8 3D 46

PE TTB HC RAD 20C/43.60D 54

PE TTB HC RAD 20C/oJD. 65C/5H, GR: 0.5-5H 1 32

PE TTB MECH RAD 2CC/6JD, 65C/5H, GR: U.5-5H 1 32

PE TTB CIL RAD APP, 20C/ 6 jOt G5C/5H. GR : TO 65C/T0 6uD 39

PE TTB CIL RAD 2lC/30 .600 45

PE TTB OIL RAD 4-25XD0P. APP, 20 C/3 0 • 6 OD , 40C/10D. GR : TO B DC/TO 8 30 46

- 8

-
PE Y T0 C 20 RAO 65C/2,5H, GR 1 TO 6H 51

PE TY6 OIL RAO 2CC/30 • BOO * GR: to’ 600 52 ' PE TTS OIL RAD AFP, FAT-PENETRATION, 20C/30,oQD. 65C/2.SH 63

PE TIB OIL KAO 20C/4 3 » 60 0 54

PE 7 TB OIL RAO 2tC/6<jD. 65C/5H, GR : 0,5-SH 1 32

PE TTB R2C RAO 4— 25%D0P s A PP, 29C/30.69D, 40C/1QD, GR I TO 80C/TQ 600 46

PE T TO R2C RAD 20C/43, 600 54

PE TTB TG RAD 6 5, 83C/2 « 5H 38

PE TTB TG RAD 2 LC/ 30 ® 600 45

PE TTS TG RAD 65C/2.5H, GR: TO 6H 51

PE TT0 TG RAD 20C/3C ,600, GR: TO 600 52

PE TTB TG RAD APP, FAT-PENETRAT ION, 200/30,600, 65C/2,5H 53

PE xvz H20 TO 50C/TQ 1 19

PE 66

PE RAO 0, H*, CMT » SMEAR, 20-78C 73

PE OIL FAT-M IGRAT ION 96

PMA CBP EYQH POLAR NKD, 4SC/10D 1 89

OMA obp HC POLAR NK D , 45C/100 1 89

PMA CBP H20 POLAR NKO. 450/ 1 00 1 69

PMA OBP HOAC POLAR NKC, 45C/100 1 89

PMA OOP ETCH POLAR NKD, 45C/IOO l 89

PMA OOP HC POLAR NKO o 45C/10D l 69

PMA OOP H2C POLAR NKO, 45C/10D 1 69

PMA OOP HOAC POLAR NKO, 45C/100 1 69

PMMA HM8P ETCH TLC NKO, 45C/10D 170

PM MA HMBP HC TLC NKO, 45C/IQD 170

PMMA HMBP 020 TLC NKO, 45C/SOO 170

PMMA HM8P HOAC TLC NKO, 45C/100 170

PMMA HMBP OIL TLC NKD « 45C/100 170

PMMA M MA H20 CMT, GR: 37-90C/10H 162

PMMA XVZ SCO

PMP OTP RAD D, H*. CMT, SMEAR, 20-78C 73

PMP RAO D, H* , CMT, SMEAR, 20-78C 73

POM DCDA H20 PHOTO 3 7C/ 1 ,3,5, 70, 1 00C/2H* GR 1 TO 100 97

POM hcho 0.20 PHOTO 37C/1 .3,5, 70, 100C/2H, GR t TO 10D 97

POM MM6P H20 PHOTO 37C/1 ,3,5,70. 100C/2H, GRI TO 1©0 97

PP 8HT NKO, 45C/1Q0 1 67

PP ETAC HC GRI 40-65C/TO 600 i 16

PP ETAC 0 1L GRI 40-6SG/TO 600 1 18

PP QHBP H20 RAO CMT, 0 « 4 4— 75 C/TO 1000H 1 77

PP DTP RAO C, H*, CMT, SMEAR, 20-78C 73

PP HOBP ETCH 4 5C/2 , 1 jD , 70C/2H,- 1 C 0 , 1 2 1C /O. 5K 168

PP HOBP H20 4 5C/2 , 1 00 , 70C/2H, 1 0 ? , 1 2 1 C /O . 5H 163

PP neap HOAC 45C/2 , 100 « 70C/2H. 160. 1 21C/0. SH 163

PP hOBP GIL 45C/2.130, 70C/2H, ICO, 1 21C/0* 5H 16S « PP ODE RAO 0, H*, CMT, SMEAR, 2‘3~76C 73

PP CUSP HC GRI 4 5—6 5C/T0 600 i i a PP OHBP OIL • GR: 40— 6 5 C/TO 600 118

PP RAO 0, H*, CMT, SMEAR, 20-78C 73

PP HCHO nc. 20-aoc 1 65

PR PH NC, 2 9-80 0 165

PS OHT E T 20 GO NKO, TO 98C/T0 100 10

PS 8HT HC GC NKO » TO 90C/TQ 100 SO

PS 8HT OIL GC NKO, TO 98C/T0 100 1 9

PS 8HT TG GC NKO, TO 98C/T0 100 1 3 PS EHT NKO, 45C/1CD 1'67 PS EST ET20 RAD 2CC/60D, 65C/5H, GRI 0.5-5H 132

PS BST F HC RAD 200/43,630 54

- 9-
PS bst PC RAD 4-2SXD0P, APP, 200/30. 60D, 4OC/10D, GR : TO 80C/TO BCD 46

PS EST HC RAD 20C/43.60D 54

PS EST PC KAD 2:C/60D, 65C/5H, GR : 3.5-5H 1 32

PS esT H2C gr: 60 c/ro iy 1 23

PS EST ME. CH RAD 2v,C/6vlD, OEC/5H, OR! ''•.5-5H 1 32

PS BST C 1L RAD APP, 20C/60D, 65C/5H, GR: TO 65C/T0 6 0 D 39

PS BST OIL RAD 2DC/20 . 600 45

PS BST OIL RAD 4-2 EXOOP • APP, 20C/30.60D, 40C/10D, GR : TO 6 DC /TO 8CU 4 6

PS BST OIL RAD esc/2,5H, gr: to en 51

PS BST OIL RAD 200/30,600, GR: TO 60D 52

PS BST OIL F AD APP, FAT-PENETRATION, 23C/30.60D. 6SC/2,5H 53

PS BST OIL RAO 20C/43 , 60D 54

PS BST CIL RAD 20C/6&D, 65C/5H, GR : 0.S-5H 1 32

PS BST R 20 RAD 4-2SXD0P, APP, 20 C/30 1 600, 40C/10D, GR : TO 80C/T0 80 D 46

PS esT R 2 C RAD 20C/43.60D 54

PS BST TO RAD t 5.83C/2, 5H 38

PS BST TO RAD 2C C /3 0 , 60

45

PS esT TG RAD 65C/2.5H, GR: TO 6H 51

C? BST TG F AD 20 C/30. 6 v D , GR: TO 600 52

PS BST TG RAD APP, FAT-PENETRATION, 20C/30.60D, 65C/2.5H 53

PS BST CMT, D, 2 0,40 » 6 OC / 1 0 )D , GR: 10-10CD I 74

PS CC ETCH 8CC/6H 1 90

PS CD E T 20 eoc/tH 1 90

PS CD P2C e 0C/6H 190

PS CD HO AC 80C/6H 190

PS DCP ETCH NKD. TO 8CC/T0 50 1 24

PS DGP H2C NKD , TO 80C/TO 5D 1 24

PS HPBP ETCH TLC NKO. 45C/10O 170

PS HMDP PC tlc NKD, 45C/10O 1 70

PS HMBP P2C TLC NKC, 45C/10D i 70

PS H MB P PO AC TLC NKD, 45C/10D 170

PS HMBP CIL TLC NKC, 45C/100 170

PS HOBP ETCH 45C/2.10D, 70C/2H, 1 00 , 1 2 1 C /O • 5H 1 68

PS HOBP H2C 45C/2.1DD. 70C/2H, 1 00 . 1 2 1C/0. 5H 1 68

PS HOBP HO AC 4£C/2,IiyD, 70C/2H, 1 0 0 , 1 2 1 C / 0. 5H 1 68

PS HOBP 0 IL 4SC/2.10D, 70C/2H, 1 C 5 , 1 2 1 C/0« 5H 1 68

PS H XD C, CMT, SMEAR 1 40

PS PAP l N T ER — POL YMER , APP, 70C/TO 1320D 1 12

PS S AO NTT, 1.3.5D 1 26

PS S DP GC CMT, D. GR: TO 20C/TO 30D 29

PS s ETOH GR: 23-70C/0. 01-720D i 31

PS s H2C GC CMT, D, Gw: TO 20C/TO 30D 29

PS s H2C NTT, 1,3,50 1 26

PS s H2C GR: 60C/TO 1Y 1 2 3

PS c H2C gr: 2 3— 7 0 C / 3 • 0 l — 7 2 0 D 131

PS s H 20 CMT, GR: 37-90C/I0H 1 fc? PS s HCAC NTT , 1,3,50 1 26

PS s HO AC

• gr: 2 3— 7L C/0»01— 720D 131

PS s OIL NTT , 1 , 3, 5D 1 26

PS s OIL gr: 23-7CC /O, 0 1— 720D 131

PS s CMT, 0, 2C , 4G , 6 SC/ t OOD , gr: 10-1000 1 74

PS STP NKD, 45C/1JD 1 67

PS TBC NKD, 45C/1GD 1 67

PS T NP P NKD, 45C/U0 1 67

PS TTB ET 20 RAD 20C/6jD, 65C/5H, GR: O.S-SH 1 32

PS ttb FHC RAD 200/43,600 54

PS TTB HC FAD 4-25XDGP. APP, 20C/30.60D, 40C/10Q. GR : TO 8QC/T0 BOD 46

PS TTB HC RAO 2w»C/43,60D 54

- 10 -
PS T7B HC RAO 200/600* 65C/5H, 0*5-5H 1 PS TTB MECH RAO 20C/630® 65C/5H, GR l 0.5-5K 1 PS TTQ OIL KAO APP, 23C/60D, 65C/5H, GR l TO 65C/T0 600

PS TTB C IL RAO 2GC/3d»60D

PS TTB OIL HAD 4-25XDOP, APP, 200/30,600, A0C/10D, GR % TO 30C/TQ 800

PS TTB CIL RAD £5C/2,5H, GR: TO 6H

PS TTB OIL RAO 2GC/39 , 6uD , GR: TO 600

PS TTB CIL RAD APP « FAT-PENETRATION, 20C/30,60D, 65C/2,5H

PS TIB CIL RAO 2CC/43.600

PS TTB CIL RAO 2CC/600, 65C/SH, GR 1 0,5-5H 1 PS TTB K2C RAD 4-25%00P, APP, 2C C/30, 600, 40C/10D, GR TO aoc/TO 80 D PS TTB R2Q RAO 200/43,600

PS . TTB TG RAD £ 5 » 83C/2 s 5H

PS TTB TG RAO 2CC/30 ,600

PS TTB TG RAO 6 5C/2 , 5H , GR % TO 6H

PS TTB TG RAO 2CC/3G.6DD, GR 1 TO 600

PS TTB TG RAD APP, FAT-PENETRATION, 200/30,600, 65C/'2,5H

PS XYZ H20 TO 50C/T0 Stt 1 PS XYZ i PS XYZ CM7, SO 1 PU CHBP RAO 0, H*, SMEAR, 36-75C/T0 300

PU HGBP RAO C, HA* , SMEAR, 36-75C/TQ 300

PVC ABC ET 20 GC NKO, TC 98C/T0 100

PVC ABC HC GC NKD, TO 98C/T0 100

pvc ASC CIL GC NKD, TO 9 SC/TO 10D

PVC ABC TG GC NKD, TO 98C/T0 100

PVC ABC 20C/1 ,3, 70

PVC ACA OIL 4 ,2G-25C/I , 2. 3, 6M. 45C/100 1 PVC EPBG 2QC/1 ,3,70

PVC ETA ETCH TLC NKD, 45C/10D I PVC ETA HC TLC NKO , 45C/100 l PVC ETA HC GRt 40—65C/TO 600 l PVC ETA H2C TLC NX 0 « 45C/100 1 PVC ETA HOAC TLC NKD, 45C/10O 1 PVC ETA OIL POLAR 4,20-250/1,2, 3. 6M, 45C/iOQ,6M 1 PVC ETA CIL TLC NKO, 45C/100 I PVC ETA CIL GR: 40-65C/TO 600 1 PVC CAST H2C SPEC 5 »50C/2,4,6,8W

PVC CBP ETCH RAD 25C/TO 500

pvc OBP ETCH RAD 2G-60PHR, 1G-65C/1-800

PVC OBP E72Q GC NKD, TO 98C/T0 100

PVC OBP HC GC NKD, TO 98C/TG 1QD’

PVC OBP HC RAO 2J-6GPHR, IO-&OC/2-800

PVC OBP MEGH RAO 2C-60PHR, 1Q-60C/ 1-800

PVC OBP CIL GC NKD, TO 98C/TO 100

PVC OBP CIL RAD 23-63PHR, 10-60C/I—700

PVC OBP ROW RAD 2C-60PHR, 10-60C/1-80D

PVC OBP TG * GC NKD, TO 90C/T 0 IOD

PVC OBP RAD 20-6GPHR, 10-60C/I-70D

PVC CBS 2CC/ 1,3,70

PVC OBSN AQ 5CC/2,4,6W l PVC OBSN ETCH 53C/2 , 4 , 6W 1 PVC CBSN HC 5CC/2 ,4 ,6W l PVC D8SN H20 SPEC 5,500/2,4, 6, 8W

PVC OBSN HOAC 500/2,4 ,6W 1 PVC ONP AO INI, 3B-56C/TC. 120

PVC ONP AO NKO, 20-56C/TO 150 1 PVC ONP AQ EM, 4G-80C/TO 200 l

32

32

39

*5

46

51

52

53

54

32

46

54

38

45

51

52

53

19

CO

72

69

69

1 0

10

10

10

83

67

83

76

70

18

7 J 70

66

70

i a 30

78

80

1C

10

79

80

10

81

80

10

81

o i 25

25

25

30

25

86

82

83

- 11 -
PVC DNP OP E N I » 38-56C/T0 120 36

pvc DSP OP NKD, 2D-S6C/TU 150 182

PVC DNP DP 2G-63C/T0 200, ENI 1 84

PVC DNP OP 43-73C/TO 1 20 , ENI 1 85

PVC ONP H20 ENI, 38—56C/T 0 120 86

PVC ONP H2C NKD, 20-56C/TC 150 1 82

PVC DNP H 20 4C-70C/TO 120, ENI 185

PVC OOP AC £CC/2.4,6W 125

PVC OCP BL GC NS, 4C/5-21D 75

PVC OCP ETOH RAO 25C/T0 500 78

PVC OCP ETCH RAD 2G-60PHR, 10— 60C/1-80D 83

PVC OOP ETOH TLC NKD, 1 —5% DOP , 45C/2D 1 68

PVC OCP ETCH 50C/2,4 .6* 125

PVC DGP E T 20 GC NKD, TO 98C/T0 100 13

PVC OOP ET 20 TLC NKOr 1-5XDCP, 45C/20 188

PVC OCP EC GC NKO , TO 98C/T0 100 13

PVC OOP HC RAD 23-60PHR, 10-60C/2-800 79

PVC OOP HC TLC NKD, 1-5X0CP, 45C/20 1 38

PVC OOP HC 53C/2,4,6» 1 25

PVC OOP H2G GC IC 0C/6H 1 6

PVC OOP H2C RAD GK: 2 2— SO C/5H— 9 00 3 2 PVC OOP H20 TLC NKD, 1-5X0CP, 45C/20 1 86

PVC OOP HC AC 50C/2.4.6* 125

PVC OCP MECH RAD 20-60PHR, 1 0—6 OC/ 1 —SOD 83

PVC DOP OIL GC NKO, TO 98C/T0 100 10

PVC OOP CIL RAD APP, NKO, 0.25-25X, 20C/60D. 40C/10D 40

PVC OOP CIL RAO APP, 0,25— 25XD0P. GR : TO 43C/TO 300 43

PVC DOP CIL RAO 20-60PHR. 10-60C/ 1-700 81

PVC DOP CIL RAD NKD, 92

PVC OCP OIL AFP, CMT, SECT, CP, FAT-M I GR AT I ON , 40C/1 ,2, 4, 9, 16, 250 1 30

PVC OCP RCH RAO 2C-6CPHR, 10-60C/1-80D 8)

PVC OOP TG GC NKO, TO 98C/TC 100 1 3 PVC OOP RAO 2C-6CPHR, 10-60C/1-70D 81

pvc OCP INTER-POLYMER, APP, 70C/TO 13200 1 12

PVC CCSN AQ ENI, 38-56C/TC 120 86

PVC OOSN AQ ENI, 40-80C/TO 200 1 83

PVC OOSN OP ENI, 38— 56C/T 0 12D 86

PVC DC SN OP 2C— tOC/TO 200, ENI 1 84

PVC CCSN OP 4G-70C/TO 1 20 , ENI 185

PVC OOSN ETCH R AO NKO, 2 C C/8 W 91

PVC DCSN ET 20 GC NKO, TO 98C/T0 10D

10

PVC OOSN ET2C R AD 2CC/60D. 65C/5H, GR : 0.5-5H 1 32

PVC OOSN FHC RAD 2D C/43, tOD 54

PVC DCSN HC GC NKD, TO 9 SC /TO 100 13

PVC DC SN HC RAD 4-25XD0P. APP, 20 C/30, 600, 40C/10D, gr : TO 8CC/TO 6 30 46

PVC OCSN HC RAD 2GC/4 3 , 600 54

PVC OOSN HC , RAO 20C/63D , 65C/5H , GR: 0*S-5H 1 32

pvc OCSN H2C SPEC E , 5 JC/2, 4 , b,8W 30

PVC DCSN H2C ENI, 38-56C/TC 120 86

PVC DCSN H2C 4C-70C/TO 120, ENI 1 85

PVC DCSN MECH RAO 2LC/6CD, 65C/5H, GR: 0«5-SH 1 32

PVC OCSN CIL GC NKD, TO 98C/TC 10D 1 3 pvc OCSN CIL RAO APP, 2 DC/ 6 0 0, 65C/5H, GR : TO 65C/TO 630 39

PVC OOSN CIL RAO APP, 0,2 5— 2 5 X 0 0 P . GR: TO 40C/TO 300 43

PVC DCSN CIL RAD 2QC/30 , 600 45

PVC OCSN CIL RAO 4-25XDOP, APP, ' 2?C/3C»6CD, 40C/10D. gr : TO 8 3C/T0 8 30 46

PVC OCSN CIL RAO NKD, 4-25X00P, 4CC/1CD, APP 48

PVC OCSN CIL RAO 65C/2.5H, GR: TO 6H . 51

- 12 -
PVC OOSN CIS. RAD

PVO DOS N OIL RAO

PVC DCSN CIL RAO

PVC DOSN CIL RAO

PVC DCSN C IS. RAO

pvc OCSN CIL RAD

PVC DCSN CIL RAO

PVC OCSN OIL

PVC OCSN R20 RAD

PVC OCSN R2C RAD

PVC OCSN TG GC

PVC DCSN TG RAO

PVC OCSN TG RAO

pvc OCSN TG RAD

PVC OCSN TG RAD

PVC DCSN TG RAD

PVC HMBP ETOH TLC

PVC Hf»8P HC TLC

PVC HMBP F2C TLC

PVC HMBP rC AC TLC

PVC HMBP OIL TLC

PVC MGST H20 SPEC

PVC m Map RAO

PVC MSN H2C SPEC

PVC MSN C IL RAD

PVC MSN CIL RAC

PVC PAP AQ

PVC PAP AG

PVC PAP AQ

PVC PAP OP

PVC PAP OP

pvc PAP OP

PVC PAP OP

PVC PAP H2C

pvc PAP H20

PVC PAP H2G

PVC PB

PVC RSE AG

pvc RSE AQ

PVC RSE OP

pvc RSE OP

PVC RSE OP

PVC RSE H2C

PVC RSE H 20

PVC SN ETCH CCLCIri

PVC SN £7 20

PVC SN HC

PVC SN H2C ’ COLOR

PVC SN HC AC

pvc SN CIL

PVC SN VEG

PVC TEP H2C RAO

PVC T IC2 F2G SPEC

PVC TTB ET 20 PAD

PVC TTQ HC RAO

PVC TTB MECH RAO

PVC TTB CIL RAD

PVC TTB CIL RAD

20C/30.60D, GR1 T AFP, FAT— PENETRAT

20C/43 .600

GR: 2 G-AGC/Oo 1-30

ZC C/6 jO , 65C/5H,

2CC/30D. 4 5 C/ ICC*

NK D * 3, 1C ,20,30,4

4 , 23-25C/ 1,2.3,

4-25SS00P, APP,

29C/43 ,600

NKD , TC 93C/T0 130

6 5, 83C/2 * 5H

2CC/30 ,630

65C/2.5H, GR 1 TO 6H

20C/30.6GD, GRI TO 600

APP, FAT-PENETRATION,

NKD, 45C/1CO

NKC, 45C/10D

NKO , 45C/10D

NKO, 45C/10D

NKO, 450/100

5 ,500/2,4,6,3

D, K, I NTCR— POLYMER

5 , 500/2,4, 6, 6W

20C/30D, 40C/10D,

40C/5-240K

EN I , 38-56C/TC 120

NKO , 2G-56C/7C 150

EN I , 4 j-eoc/To 20 0

EN I , 38 — 5 t;C/7 0 1 2 D

NKD, 2C-56C/TC 150

2C—

SC/TO 200, EN I 46-70C/TO 120, ENI

EN I , 38-56C/T0 120

NKD , 20-56C/TC 150

4G-70C/TO 12D, ENI

NC , 20-80C

EN I . 38-56C/T0 120

EN I , 4V-80C/T0 200

ENI , 38— 56C/T0 120

2C-6JC/TO 200, ENI

40-7GC/TO 120, ENI

EM, 38-56C/T0 120

4 j— 70C/TQ 120, ENI

RT/1-138H, SURFACE-WASH

RT/C .5, 1 » 1 1M

R T /C « 5 , 1 , I 1M

RT/1-133H, SURFACE-WASH

APP, NO. NS, NTT

RT/0.5, l.UM

APP, NO, N£* NTT

Gfi: 2 2—800/ 5H— <5 30

5 ,500/2,4 ,6,8*

200/600, 65C/5H, GR: 0®5-5H

200/600, 650/ 5H , GR: 0.5-SH

2uC/60D, 65C/5H, GRI 0 , 5-5M

APP, 20C/60O, 65C/5H, GR : TO

200/30 ,60 0

52

650/2, 5H 53

54

55

l 3?

15 5

1 56

1 87

gr: to aoc/TO 800 46

54

10

33

45

51

52

650/2, 5H 53

1 70

173

1 70

l 70

1 70

3 3

1 3

30

TO 30 D 42

44

85

i 82

1 83

86

1 82

1 84

13 5 86

1 82

1 85

165

86

1 83

66

I 34

1 85

86

185

34

1 80

1 80

34

I 180

1

1 2 30

1 32

132

1 32

65C/TO 600 39

45

Q 600

ICN. 200/30,600,

O

GR: 0.5-5H

NKO

50/100, 750/20

6M, 4 50 /I CD

200/30,600, 400/10D,

200/30,600,

7 00/0 » 5H , gr:

- 13-
PVC TTB CIL RAD b SC /2 « 5H » GRI TO 6H 51

pvc TTB CIL RAD 22C/30.60D. GR: TO 600 52

PVC TTB CIL RAD APP, HAT-PENETRATION, 20C/30.60D. 65C/2 ,5H 53

PVC TTB CIL RAD 20C/60D. 65C/5H, GRI 0.5-5H 132

PVC TTB TG RAD e 5 , 83C/2 , 5H 38

PVC TTB TG RAO 2 JC/30 .600 45

pvc TTB TG RAD 6 5C/2 » 5H» GP: TO 6H 51

PVC TTB TG RAD 20C/33 . 60D . GR: TO 60D 52

PVC TTB TG E AD APP, F A T— PENETRATION, 20C/3C.6DD. f 5C/2.5H 53

PVC VC ETCH GC NS. 22C/3.6.9, 12 M, GR: TO 49C/T0 1 OY 27

PVC VC ETCH GM SCL. SD, 30—9 OC 7 pvc VC ETCH GR: 23— 7CC/C. 01— 7200 131

PVC VC HC GC NS. 22C/3 ,6,9. 12 M, GRt TO 49C/T0 1 OY 27

PVC vc HC GC K , S/D 1 16

PVC VC H2C GC NS. 22C/3.6.9 »12M, GRI TO 49C/T0 1 OY 27

PVC VC H2C GC K, CMT. SD 62

PVC vc H2C GC K, SD, AC 63

PVC VC H2C GC K , S/O l 16

PVC vc H2C GM SCL, SD. 30 — 9 OC 7 PVC vc H2C MC , 2 3 C / 1 — 1 80 D 5

pvc vc H2C GR: 23-7CC/C. 01-7200 131

PVC vc HO AC GC NS, 2 2 C /3.6.9.12M. GR: TO 49C/TO 1 OY 27

pvc VC HOAC GC K, SC, AC 63

PVC vc HOAC GR: 23— 70C/0. C1-720D 131

PVC vc CIL GC 40C/1 0.20D . RT/35D. GR : TO 160D, CP 93

pvc vc OIL GC NS, 22C/3. 6.9.12M, GR: TO 49C/T0 1 OY 27

PVC vc C IL GC K, CMT, SD 62

pvc vc CIL GC K , S/D 1 16

PVC vc OIL GRI 23-70C/C. C1-720D 131

PVC vc GC AIR, MODEL, GR: TO 38C/T0 30D 26

PVC vc GM C. SD. CMT, 20-90C 8 PVC ZNST H2C RAD GR: 22— 80C/5H—90D 12

PVC ME GC 4 C / 1 .2.8.4D 28

PVDC DCP OIL APP, CMT, SECT, CP. FAT-MIGRATION , 40C/ 1.2. 4,9. 16.25D 130

P VDC ETCH GR: 23— 70C/0.01-720D 1 31

PVDC H2C GRI 22-70C/C ,C 1-720D 131

PVDC HOAC GR: 23-7CC/C . C 1-720D 131

PVDC CIL GR: 23-70C/C. 0 1-720D 131

SAN AN ETCH GR: 23-70C/C , 0 1-720D 131

SAN AN H2C GRI 23-7CC/C. 0 1-720D 131

SAN AN HC AC GR: 23- 7CC/C ,C 1-720D 131

SAN AN OIL GRI 23-7CC/0.C1-720D 131

SBR BCO D 141

SDR HXD C , CMT 139

SDR MW GM BLOOM 1 58

SDR MAX TO 28CD 19

V/APQ VAC H2C 6VC/1H, NKO 20

V/APB VC ETCH • 14

V/APO VC H2C 14

PAN AN H2C GC K, SD. AC 63

PAN AN HOAC GC K. SD. AC 63

PVC/ ABS AN ETCH POLAR NKD , RT/4D 95

P VC/ABS AN H2C PCLAR NKC. RT/4D 95

PVC/ ABS AN HOAC PCL AR NKD, RT/4D 95

PVC/ABS AN CIL PCLAR NKC, RT/4D 95

PVC/ ADS EST ETOh PCLAR NKD, RT/4D '95 PVC/ABS esT H2C PCLAR NKC, RT/4D 95

PVC/ABS bst HOAC PCLAR NKD, RT/4D 95

- 14 -
PVC/ ABS esr C SI PCLAP NKD 9 RT/4D 95

PVC/ ABS OCP ETCH PILAK NKC « RT /40 95

PVC/ ABS OOP H2C POlAk NKC * RT/40 95

PVC/ A3S OCP HC AC PC LAB AKO « RT/40 95

PVC/ ABS OOP C1L P CL AR AKCg RT/40 95

PVC/ ABS s ETCH PCLAR NKD • RT/40 95

PVC/ ABS s H2C P CL AR NKC. RT/40 95

PVC/ ABS s hCAC POLAK NKD 9 RT/40 95

PVC/ABS s Cl L PCLAR NKC t RT/40 95

PAT xvz CIL RAO APP » 40C/10D 1 15

PES xvz H20 TC 50C/TO aw i 1 9

ABS/MA ETCH 3 9-6 EC/ l —70 e NKD 1 79

A8S/MA H2C 39-65C/1-7D* NKD l 79

ABS/MA HO AC 39-6SC/ I-7C. NKD 179

ABS/MA 39-65C/1-70* NKD 1 79

APP 41

APP 49

LITERATURE REFERENCE

Is A dcoc k 9 L. H»

New Test Tells How A <1 d i t ives in Packages Migrate into Food

Package Eng©* VoU 2i» No* 9* pp© 45— 6 (1976)

2« A l f r e y » T ® * Gurnee* E ® F ® « and Lloyd* W « R « Diffusion in Glassy Polymers

J* Polym* Sc i e C» Vol» 12* pp« 249 ( 19661)

3 . Asada. Ta» Inouet

Diffusion in the

Polymer J** V o l •

K©» and Onog i * So

Nylon 12 and Hater System

6# No® 1* pp® 21-29 (1975>

4® Oaydonaite® V ® A © * and Yushkevi chyutei S»S«

Migration of Anti os i dants between Polyethylene and PVC

Plast® Massy* No* 9* pp « 53 ( 1 9 7 5 ) « Inti® Poly© Sc i * Technol®

Vol. 3* No t 2» pp® 70 (1976)

5© Banzer. J © D ® The Migration of Vinyl Chloride Monomer from PVC Pipe into Water

Soc® Plast® Eng® NATEC* Now® 1977* pp© 33—34

6® Bent* F * A ® « and Pinsky® J * Theoretical Investigation of the Mechanism of Transfer of Materials

through Polyethylene

Wright Air Development Centers Technical Report 53—133* P t * 2 ( 1965)

- 15 -
7® Berensi A © R

The Solubility of Vinyl Chloride in Polyivinyl chloride)

Polymer Preprints# Vol® 15® IP* 157 (1574)

8® Berens® A ® R © The Diffusion of Vinyl Chloride in Polyi vinyl chloride)

Polymer Preprints® Vol* 15® pp. 203 (1974)

9© Berenst A® R« « and Can iels» C®A«

Prediction of Vinyl Chloride Monomer Migration from Rigid PVC Pipe

P © l y m © Eng® Sc i « < Vol® 16* No® 5® pp® 52 (1976)

10® Berg ner® K • G ® * and Berg® H®

Migration of Additives from Plastics in Triglycerides Compared

with their Extractabi i i ty by Organic Solvents

Dtsch® Lebensm® — Rundsch®® Vol© 68* No® 9® pp® 28 2— 8 (1972)

11® Bethune® J»L©

Directed Transport of Mo n om er — S a n g 1 e Polymer Systems® Comparison

of the Countercurrent Analog and Asymptotic Approaches

Jo Phys® Chenis * Vol© 74® No® 22. pp. 3337-45 ( 1970)

12® Bloom « P « J o Contribution to the Investigation into the Migration into Li qui a Foods of Auxiliary Substances Used in Plastics Manufacturing

Processing® Part II© Migration of Auxiliary Substances of

Polyi Vi nyl Chloride) into Drinking Water

Dtsch® L e ben sm « — R u n ds c h © * Vol* 72* No® 6® p p* 194—7 (1976)

13© Bobrovskaya® T®S©» Markelov* M S A©« and Semenenko® Eel®

Migration of Dioctyl Phthalate from Plasticised PVC into Water

Plast® Massy® No® 4® pp© 56 ( 1974); Inti© Polyin. Sc i • Technol •« Vol© 1. No. 7® pp. 10 (1974)

14© Boikova® Z ® K © * and Petrova® Lai®

Migration of Vinyl Acetate from Copolymers Based on it

Plast© Massy® No® 12® pp* 43 ( 1 97b ) « Inti. Polym® Sc is Technol*.

Vol* 4® No® 5® pp® 25 (1977)

15® Booher® T®R©« and Stringer* C®D®

Study of Additive Migration from Films to Food by 14f—Labeling

ACS Abstr , « Div® Cry. Coat® Plast®. Vol® 152® pp* T 2 2 (1966)

16® 8 o t r e » Co® D® Antoni* L#» Memoli* A © » and Pallotti , G«

Chemical® Technl copharmac eu t i c a l and Legislative Aspects on the

Transfusion Blood and its Components® Note II© Extraction o Plasticizers from Blood in the Poly (Vinyl Chloride) Container

Pass* C h i m . » Vol© 27® No® 5® pp® 245—8 (1575)

17® Brit. Plast. Fed®* and Brit. Ind© Biol® Res© Assoc©

Plastics for Food Contact Applications® A Code of Practice for

Safety in Use

London® pp. 54 (1569)

18© Bro i twan® A « Y a © « Putilina* L e V © ® and Podval'naya, E»K«

Toxicolgy of Vinyl Acetate-Vinyl Pyrroli done Copolymers

Plast. Massy* No. 12* pp*4E (1976)5 Inti* Polym. Sc£® technol®®

Vol© 4® No© 6* pp® 50 (1977)

an

f

s

- 16 -
1 9 • Brown* D®W®« and

riern^s Law and

Po l y C v i n y L J • p o l y m o 5c i a »

Lowery® R ® E * Diffusion Constants of Vinyl Chloride in

chloride? at High Temperature

Pclym® Chew* Sect*® Vol* 15® pp®2623-39 {1977?

20* Bruck® C*G« vow® Eckert® W.R®. and Rudolph® F®B®

Migration of Vinyl from P VC Packaging

Fette* Seifen® A n s t r i c h e m • » Vol* 76® No* 8® pp® 334— 7 (l c>76?

inti* P o L y m « Sci* Technol*® Vol* 3® No® 1C® PP® 103 C1976?

21* Brucki C • G • Vorrt® Figge® K * * Piater® He® and Wolf® V®

Migration of Plastics—Processing Adjuvant Substances from Films

into Liquid and Solid Fats and Simuianis® IX® Results of

Previous Extraction and Migration Studies

Otsch® LebensiB®- Rundsch*® Vol* 67® No® 12® PP® 44 4—50 (19 71)

22* Chalyukh* A * E

Diffusion of Mononers in Polymers

Vysokomol* Soedin*. Ser® B® Vol® 17® No* 3* pp® 215—19 {1975?

23* Chantrey® Go® and Rattee® 1*D»

Influence of Polymer and Dye Characteristics on Diffusion in

Nylon 66

J« Appl* Polym* Sci « t Vol* 18® No* 1® pp* 9 3 — 193 {1974?

24* Code of Federal Regulations® Title 2i« Food and Drugs

Part 175© Indirect Food Additives! Adhesive Coatings and Components

Part 176* Indirect Food Additives! Paper and Paperboard Components

Part 177® Indirect Food Additives! Polymers

April 1, 1977

25* Chernova® T*V»

Hygienic Evaluation of SNP— 2P Polystyrene Containers Intended for

Packaging Foodstuffs

Vopr. Pitan. ® Vol. 30. No. 5* pp. 56-58 {1971?

26* Crider® L ® B ® * C'Mara« M • M * « and Bowles® R ® L ® A Model for the Diffusion of Vinyl Chloride Monomer from PVC

Under Various Conditions of Storage

Soc* Plast. Eng. NATEC® Nov* 1977, 195-9

27* Daniels® G®A®* and Proctor® DsE®

VCM (Vinyl Chloride Monomer? Extraction from PVC Bottles

Mod* Package* Vol® 48® No* 4® pp* 45—8 (2975)

28* Daun® He® and Gilbert® S*G«

Migration of Plasticizers from Polyiwinyl chloride? Packaging Films

t o M e a t Jm Food Sci®, Vol® 42® No® 2. pp* 561-2 (1977)

29* Davies® U • T « Migration of Styrene Monomer from Packaging Materials in Food®

Experimental Ver i f icat ion of a Theoretical Model

J • Food Technol®, Vol® 9® No e J i p p « 275-83 { 1974

)

30 . Dietz® G « R ® * B anz e r » J a 0 * ® and Miller® tz $ M

Water Extraction of Add i t

i

v e s from P VC Pipe

- 17-
3 1 •

3 2 »

3 3®

3 4®

35®

36.

3 7.

38®

39.

4 0.

41 *

42 •

Soc® Plasto tugs KATECe Nov. 19779 pp« 25—9

Ootreppe-Gfisard« N«

Control of the Migration of Adjuvants of Plastic Materials in

Food Liquids

Tr ib« Cebedeau (Cent® Be lye Etude Coe. E a u x i ® Vol® 25* No® 3 41

pp . 198-20 1 ( 1972 1 Dot 5enko« V©Ae® and Shiba® V©V©

Methods for a Ssni tary-Chemical Evaluation of Polymeric Materials art

Products Made from them in Contact with Foods and Drinks

Gig© San i t » « Vol» 10® pp. 96— 2 C i 9 7 2 ) Downes® T©&®

The Mechanism of the Migration of Oryanoti n Stabilizer from

Polyivi nyl chloride) into Containing Media

Diss. Abstr® lnt«» 0* Val, 33* No® 8* pp® 37J2C Order* No® 73-4740 IIP -”

Downes® T ® to ® ® and Gilbert® S ® G . The Effect of Surface Treatments on the Migration of Organot i

Stabilizer from Polgi vi nyl chloride) Films to Contacting Liquid

Media

Dtsch* Lebensa.- Rundsch.* Vcl. 71® No. 12* pp« 4 2 2— 425 U ° 7 5 < Easterling® R ® E . » Johnson* E ® * and Napier® E ® 4 & « Jr®

Plasma Extraction of Plasticizers from Medical Grade

Poly( vinyl chloride) Tubing

Procs Soc® Exp® Biol® Med** Vol 0 147* No® 2* pp • 572-4 (1974)

Evstatieva® M

Migration of Some Azo Dyes from Prepared Polymer Materials

Kh i g® Zdraveopaz®* Vol. 16* No® 5* pp® 479—82 (1973)

FDA Guidelines for Chemistry and Technology®

Requirements of Food Additives Petitions

Bureau of Science® FDA® HEW (August 1966)

Figge® K . Migration of Processing Aids from Plastic Film into Food Fats

Kunststoffe® Vol. 61® No. 11, pp. 832-8 (1971)

Figge® K © Migration of Additives from Plastic Films into Edible Oils and

Fat Simulants

Food Cosset • Toxicol.* Vol® 10* No® 6® pp® 81 5— 28 ( 1972)

Figge* K . Determination of Total Migration from Plastics-Packaging Materials i n^| Edible Fasts Using a Carbon-14—LaOeled Fat Simulant

Food Cosniet* Toxicol®* Vol. 11* No® o« pp. 9 63—74 (197 3)

Figge® K»

Method for the Determination of the Total weight of All Components

Migrating from Packaging Material into Edible Fats* the So — C alien

Total Migrate* Using Fat Simulant HB 3 0 7— ( 1 4 )

Dtsch. Lebensm.— Rundsch. « Vcl® 69* No® 7* pp. 253—7 ( 197 3)

Figge® K • 4

- 18- m
43 .

44 *

45 .

46*

47 .

48 .

49 .

50 .

51.

52.

Migration °f M e t h y 1 1 In Thioglycclic Acid Esters from Rigid P VC

P a c k a g t ngs into Fat—Containing Foods

Verpsck*-Kundscn« i VoU 26. No. 8® pp* 59—63 ( 1975)

F i g g e » X • Radi oanalyt i c Method for Determining the Passage of Packaging

Ingredientsnt o Foods

J. Radioanal® Chem®, Vol® 32* No* 2* pp. 315— 43 (1976)

Figge* K.< and Pieber® rteC.

Migration of Methyltin Stabilizer Advastab TM 131 FS from Rigid PVC into

Fat Simulant HD 3 L 7 . 11. Migration Behavior of Several c tab i l i zer

Components

Verpack.-Rundsch* * V o l • 26* No. 8® pp. 1 1 — 22 ( 1975)

Figge* K.» Eder® S.R.® a md Pi ater * Ho

Migration of Plastics Processing Additives out of Foils in Liquid

and Solid Fats as uel L as Simulants* XI* Synthetic Triglyceride

Mi (ture as General Fat Simulant

Dtsch. Lebens9i*-Rundsch* , Vol® 66® No® 11® pp® 259—67 ( 1972)

Figge® K«« and Koch® ,J®

Effect of Some Variables on the Migration of Additives from

Plastics into Edible Fats

Food Cosmet. Toxicol.® Vol. 11® No. 6® pp. 975—983 (19735

Figge® K.« and Koch® J.

Determination of the Migration Rate from Plastics onto Nutritional Fats

by means of a C a r bo n— 1 4 — L a b e l e d Fat Simulating Agent

Report AEC-Con f-72-461-l» PP® 12 ( 1973)

Figge® K.» and Koch, J®

Determination of the Total Plastic Packaging Components Migrating into

Edible Cil by Using a C arbon— 14— Labeled Fat Simulant

Fette® Seifen, Anstrichm.® Vol. 77® No. 5® pp® 184-8 (1975)

Figge® K.» and Pi ater , Fi* Methods of Migration and Extraction Studies with 14C—Labeled

Additives® III. Migration of Plastic Additives from Films Into

Liqu id and Solid Fats and Simulated Fats

Dtsch. L e ben s m «— R u n d sc h . ® Vol. 67, No* 1® pp® 9—15 (1971)

Figge® K«« and Pi ater* H®

Migration of Adjunct Materials of Plastics Processing from Films

into Liquid and Solid Fats and Similar Substances. IV® Amounts

of Additives on the Test— Film Surfaces

Dtsch* Leb en sm»— Rundsch.® Vol. 67® No® 2® pp. 4 7— 8 ( 19 71)

Figge® K®» and Plater® H®

Migration of Adjuvants of Plastics Manuf acturing from Films into

Liquid and Solid Fats and Simulated Fats* V* Extraction and

Short— Term Study Data

Dtsch. Lebensm®— Rundsch* Vol® 67® No® 4® pp® 1 1 J — 19 (197 1)

Figge® K®» and Plater® h*

Migration of Auxiliary Materials from Plastic Films into Liquid

and Solid Fats or Fatlike Compounds. VI* Migration and

Long-Term Tests with Liquid Fats and Fatlike Materials

- 19 -
Disc

Q Leben$®»-Rundsch V o i 6 7® No® 5s pp<® 15 4— 61 {19 7 1)

53 .

54.

5 5®

56 a

57

58a

59®

60 *

61 •

62 •

63.

64®

FCgge® K « ® M i graft Ion

VII®

i» i ft fa Dt sch, L e

and Plater ( H ® of Adjuvants Usees in Plasti

Method and Results of Entr

Solid Edible Fats* P e n e t r a ben s ra ®— Ru n d s c h ® * Wot* 67® No

cs Manufacture fro® Films®

action and Migration Enoeri

tion of Adjuvants into Soli

® 7® pp* 235-42 {1971)

m e n t s d F a t si

F a g g e » K « ® Migration

and

and

Qtsch® L e

and Plater® H®

of Auxiliary Manufacturing Substances from Films Into

Solid Fat and Simulants® X® Passage of Additives into

D i-n- Alkane Ethers as well as Into other Organic Liqui

bensta.- Rundseh®. Voi.® 68® No® 1 0 . pp® 3 13 —3 19 {1972)

L t qu a a N— Alkane

d s

Figge® K <® « and Zeman® A®

Migration of Tin Stabilizers fro® Unplasticized PVC Film Into Far — Containing Foods® X—Ray Photo elect ron— Spect roscopic and

Radi oanalyt ical Examination of PVC Surfaces

Kunststof fe. VoU 63® No® 8® pp« 5 4 3 — 5 5> C1973)

Franzket C«® Uhde® k. J. • and Waggon® H®

Migration of Antioxidants and Stabilizers from Plastic Packing

Into Edible Cll

Piaste Kautseh*® VoU 17* No® 5® pp® 327 — 3 U {197 3)

Frawley® J e P « Toxicol© Evaluation of Migration of Food Additives

ACS a b s t r » ® 03 v. Crg® Coating Plast. ( Vo l* 152* T23 (66)

Frisch® H®L®» Wang® T. T. » and Xwel® T.K.

Diffusion In Glassy Polymers II®

J® Potym© Sci® A ® » Vol® 2« No® 7* pp® 879 11969)

Fritz® Wo® and Waggon® H©

Migration of Carcinogenic hydrocarbons from Carbon — Block Stabilized

Plastics into Foods

Ze Gesamte Hyg® Ihre Grenzgeb*. Vol© 19. No© 5. pp® 349—352 {1973)

Ganeva® M«® and Radeva® V®

an Approach and Methods for Determination of Dye Migration from

Plastic P ac king for Food Products

Khig® Zdraveopaz*® Vol® 19® No* 3® pp® 281-5 (1976)

Gardner* K«L«® and Mcnatly® G ® M e Morphology of Polypropylene in Relation to Dye Diffusion

J© Soc© Dyers Colour®® Vol* 93. No. 1® pp® 4-7 {1977)

Gilbert® S « G ® Migration of Minor Constituents from Food Packaging Materials

J* Food Sci. « Vol® 41® No® 4» pp® 955—8 (1976)

Gilbert® S.G. « and Giaein® J»R®

Migration of Indirect Food Additives from Plastic

Packaging Materials! Physical Chemistry Consi derations

Soc. Plast® Eng® NATtC s Nov® 1977® pp® 35-36

Guricheva* Z©G®1 Rudakova® M*N®

- 20 -
Effect of the Composition of Polystyrene Plastics on Migration of Low—

^olecuUi—Weight Substances from them

Plast* Massy* No© IP* pp© 3*5 — 40 (197o)

t» 5 • Curichevdt Z»G®* Krymskaya* i.L«* ku d a k ov a * M * N © * and duKevich* G®M©

To* icclog ica l Evaluation of the Migration of Phthalocyani ne Blue

Dye from Polyethylene

G i q « Pr imen • Poi. i«» Mater® Izdel t t N i k h » No® i® pp® 34 7 —5 4 ( 1969)

66© Gur ichevai Z© G • » Rotenberg* V © V © * and Shaulova* N © S » Migration of Lake Red ZHE from high—Pressure Polyethylene

Gig© San t + * . No© 6® pp® 9 4— 5 (1974)

67© Gutsaiyu l« V • G • « and Samosova « N © S © Migration of Plasticizers from Polyi vinyl chloride) Plastics

into Salt Water Solution

I z v • Akad® Nauk Kaz® S S R » Ser© Khi «• * No® 2 » pp® 95 (1962)

68® Guzeev® V » V ® * Belyakova® L»K®» Khokhlova® M • M » » Fomina® T © A • « and

Lebedev® V # P ® Migration of Low-Molecular weight Plasticizers from Plasticized

Poly (Vinyl Chloride) Into Polyethylene

Plast® Massy® No® 9® pp® 53— c (1959)

69# Hauserjsan* R © G • ® and Johnson® M » Diffusion of Stabilizers in Polymers® III©

2® 4 — Dihydro*ybenzophenone and 2— Hy d ro x y — 4— Oc t o k yb e nz o p h e n on e in

Polyurethanes

J® Appl® Polyra® Sci©« Vole 20® No* 9® pp® 2533-9 (1976)

70© Hearaings D©F«« Collins® J®D®* and Datyner* A®

The Effect of Competitive Adsorption on the Rate of Diffusion

J® Appl® Polym® Sc i ® » Vol® 20® PP© 597—607 (1976)

71# Hill® M* P » L © « Millard® P • L © » and Gwen® M © J © Migration Phenomena in Silicone Modified Polystyrene

ACS Civ© Crg© Coat® Plast® Chern. Pap®» Vol® 34® No® 1® pp® 334—6 (1974

72® Ingle® G * W a Quantitative Aspects of Migration of Food Additives

ACS Crg* Coat® Plast® Chern®® Vol* 152® T21 (1966)

73© Jackson® R©A®» Cldand® S«R®0®* and Pajaczkowski « A©

Diffusion of Additives in Polyolefins

J® Appl® Polym® S c i ® » Vol® 12® pp® 129 7— 1309 (19 6 8)

74© Jaeger® R©J®

Extract ion® Accumulat ion® and Metabolism of Phthalate Ester

Plasticizers from PoLy( Vinyl Chloride) Medical De vices

P h • D * Thesis* Johns Hopkins U n i v ® » pp® 194 (1971)

75© Jaeger® R®J®» and Rubin* R © J # Migration of a Phthalate Ester Plasticizer from PolyC vinyl

Chloride) Dlood Bags into Stored Human Blood and its Localization

in Human Tissues

N. Engl® J. Med®. Vol© 287® No© 22® pp® 1114-8 (1972)

76® Jaeger® R®J®« and Rubin* R©J«

- 21 -
Metabolism® and

7 7©

78 .

7 9©

30 e

3 1©

82

83®

8 4©

85®

86 s

87©

68 *

Plasticizers from Plastic Devices : Extraction

Accumulation by biological Systems

Science® Vo U I 7 C « Ko • 3 9 5 6. p p • 4 6 C — 2 (19 7 0)

Johnsons M © ® and Westlake® J « F © Diffusion of Stabilizers in Polymers© II®

2— Hydroxy — 4 — Cctoxybenzop henone in Polyolefins

J • Appl« Polya. Sci. « Vol© 19. No© 6. pp® 174 5— 54 ( 1975)

Karapouris® E © M * Study of Plasticizer Migration by Radioactive Labeling

Rev© Gen© Caoutch* P l a s t © » Vol» 5 2® No® 4. p p © 2b 9— 92 ( 1975)

Karapourls® E©M®

Migration of Plasticizers Into Petroleum Gils

Eur© Polyin. J®. Vol, 11® No© i L ® pp* 70*5—10 (1975)

Kampouris® EoM©

Migration of Plasticizers from Po ly ( V i ny l Chloride) into Edible Oils

Polya

Eng® Sci®. Vol© lc» No© 1* pp© 59—64 (1978)

Kampourl s < Migration

Polymer®

Karel© M ® ® Migration

Food

MIT C am br

1963

Kataeva© S

Deters! na

Film

Gig® San!

(Eng

E«M,« Regas i F © * Rokotas. Se® Polychronakis. S«

of PVC Plasticizers Into Alcohols

Vol. 16. No. 11® pp© 840-4 (1975)

and kogan® 6©N©

of Substances from Flexible Containers for Heat

s and P a n t a zc

Processed

sidge Civ© of Sponsored Res© Tech©® Report No® 4» Jul 196

« E « ® and Kofanov® V © I © t! on of Cicarbonylic Acid Esters in PolyCvinyl chloride)

Ex tracts

t*« Vol® 36® No© 7® ppa 6 7— 69 (1971); Hyg« San i t .

« TransD* Vol© 36. No© 7 — 9® pp© 81-4 (1971)

Keller® A«A#® Sheldon. A®to©» and Simmons® I©

Fast Extraction Tests for Food- Grade (PolyCVinyl Chloride))

Mod® Packag©. Vol® 48® No# 8® pp© 42—4 (1975)

Keller® A • A « « Sheldon. A » W « » and Simmons® I©L®

Accelerated Extraction Tests for Food— Grade Uctyltin Stabilized PVC

Soc© Plast. Eng*® Tech© Pap.® Vol. 20»« pp© 514—17 (1974)

Kierueler# F®» Evers® K © — w © . and w 1 Idbrett « G » Use of Plastics for Foods© XIV® Simulated Practical Test for Milk

Pipes

Dtsch® Leoensm©— Rundsch®® Vol* o 5 » No© 10. pp© 3 0 5-1 1 (1989)

Kim. J © — \M © ® and I i j i m a » T « Diffusion of Dye Mixtures in Nylon 6® Binary Mixtures of

Disperse Dyes

J« Apple Polym* Sc i® • Vol© 2Q« pp© 1 J 5— 113 (1976) 5— 11 (1969)

Klein. J © Diffusion of Long Molecules through Solid Polyethylene

I© Topological Constraints

- 22 -
J © Polyas Set e » Polyjn « P h y s « Sect©® VoU lb, 2057-64 (1977)

89® Klein® J© and Briscoe® B * J © Diffusion of Long Molecules Through Solid Po l yethylene

IS® Xeasurements and Results

J. Polyra. Scl«« Polya* Phys* Sect* , VoU 15* 2665—74 { 1 97 7 i

90* Knibbe> D.E®

Theory of Estraction of Additives from Plastics by Swelling

S o l v em t s PI ssticat Vo l * 24* No. 8 * pp* 25 8— 63 ( 19 71)

91® Koch* J© « and Flgge* K®

Migration of Tin Stabilizers from PVC Bottles into Beer

Z * lebensBi*-Unters« Forsch** Vol© 147* No. 1® pp. 8— 10 (1971)

92® Koch* J® » and Flgge* K®

Decreasing the Fat Siaulant Quantity in Migration Investigations on

Plastics

Dtsch* Lebensm*-Rundsch» » Voi* 70* No® 6* pp© 2 5 7 — 8 £1974)

93® Koch® J * and Flgge* K»

Alteration of the Composition of Fats by Contact with Plastics

and Its Effect on the Accuracy of the Total Migration

Oetensination Methods

Dtsch© Lebenm.—Rundsch®* Vo l* 71* No. 5* pp® 170-7 (19

7

6 )

94® Koch® J©® Robinson* L®« and Flgge® K®

Deferilnation of Fat Release by Foods® I® Methods

Fette* Seifen* Anstrichm.® VoU 78* No® 9* pp* 371—7 (1976)

95* Kosnat su* Y®» Naeiiki. T®»amd Mori* F © On the Estractabi l ity of C£— Alkyl Tin Compounds from Rigid

Poly {vinyl Chloride) Containers

Jo Food Hyg® Soc® Jpn© (Shokuhin Elseigaku Z a s s h I ) * Vol® 11*

No© 1 * pp. 17-22 ( 19? J »

9 6® Komarova* E © N ® ® and Maksimova* N « S ® Hygenic Properties of PVC/AES compositions

Plast. Massy® No. 12* pp* 29 £1976) Inti® Polym* Sci « Tech not®

Vol© 4® No© 5® pp© 5 (1977)

97® Kotova® V • N © • Koval'chuks V . M © * Platonova* T . V ® * Tsivinskaya® L©K©, and El # tsefon e 6©$©

Toxicity Investigation of Polyformaldehyde Plastics

Soviet Plastics* Vol© 1972® No© 1® pp® 7 4— 6 ( 19 7 2)

90© Kovgan* N ® A ® Hygienic Evaluation of Met a l i t Utensils for Food Products

Vopr© PIten©® Vol® 28® No® 4* pp® 75—76 (1969)

99® Kwe i • T © K © » and Zupko® H » M © Diffusion In Glassy Polymers

J® Polym© Sc i * A • • Vol. 2* No 7 * p p © e 6 7 ( 16 6 9)

100© Kwei, ToK®

Diffusion In Glassy Polymers VI©

J « Polym. Sci® A®. Vol© 2* No. IQ, pp. 1849-1651 ( 1972)

- 23-
101 o

102 ,

103®

104®

i 05

10 6®

1 07 e

i oa®

109 a

110®

lila

112 ®

K. w e 4 ® T«Kt t and Wang® s © * © Diffusion in Glassy Polymers

Polymo Set© Technola, Vole 6® Permeability Plaste F i 1ms Coate Gases®

Vap©« Liq®« p p ® 63—71 (1974)

Kweit T © K ® ® Wang® 7 ® T ® » and Z u p k o ® H ® M © Diffusion in Glassy Polymers V® Combination of Fickian

and Case 11 Mechanisms

Macromole® Vol« 5® pp© 645 (1972)

a

a

Lefaus® R ® Migration of Monomers in Foods

E ra e hr

n

g

s f o r sc h u

g » Vo i« 16® No® 4® pp® 617-25 (1972)

Lehmann® H»0«

Migration of Antistats in Plastics

Chem«® Phys® Chem® Anwendungsteche G r en z f l a e c he n a k t i v e n Stoffe®

Inte Kongr, ( Vol, 6 » No® 3® po® 661 — 9 ( 1972)

Per*

Leimgruber® R © A © ® and Figge ( K ® Substances Migration from Plastics Food Packaging to

Contents as a Function of the Solvent Volume to Sample

Surface Area

Soc® Plast® Eng® NATEC® Nov® 1977® pp© 4 0—43

Lewis® TsJ®

Diffusion of Isopropyl Nitrate® Acetone® ana Water into Nitrocellulose

Polymer® Vol® 19® PP® 285—290 (1978)

Machin® D® and Rogers® C»£«

C o n c e n t r a t i o n Dependence of Diffusion Constants tn Polymers

CRC crit® Rev® Macromol® Sci ® « Vol® 1® pp®24 5— 2 13 ( 1972)

Maksimova® N®S©« Sukhareva® L«V*« Guricheva® Z®G«» Demidova®

V © M « ® Lazareva® N © P © ® and Sokolova® T®G®

Migration of Stabilizers from Polymers Used in Medicine

Plast. Massy. No. 10® pp. 61-2 (1972)

Markelov® M®A©» and Semenenko® E«I«

Oetermination of Vicroconcentraiions

Polymer Materials to Water

•Plast® Massy® No® 1® pp® 57-? ( 1976 )

° f Substances Migrating

Matveeva® E®N®

Determination of

Material

Plast® Massy® No

the Migration of Antioxidant on the Surface

8 , pp. 68-9 ( 1975

)

Mazur® H«» and Lewandowska® I®

Study of the Migration of Benzophenone Derivative U V (Light)

Stabilizers

Rocz® Panstw® 2akl® H i g « , Vol® 27® No® 6. pp «, 61 1—19 ( 1976)

from

o f Polymer

I Meier® L • Results of Studies on the Migration of the Plasticizer from PVC

into Tharisoplast ics

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(Hastwerarbe 5 ter Vat 2 8 » No 4 » p p © 165-98 Cl 9 7 7 5

113 .

114 .

1 1 5 .

11b.

117.

1 1 8 .

119.

120 •

12 1 .

122 .

123 .

124 .

Ml Uen* W « » and H a w k e s * S ® Diffusion of n — Alkanes in Polyidimathylsilonanes!

Macro is o l « « Vote 1 0 • No® t • p p » 1 2 5 J —

2

(1977)

Ministro per la Sanita> II

Modification of the Regulation 15 th April* 19 6 6 * Health

Regulation for wrappings

Industria Conserve* Vot. 43* No. 2* pp. 1 58-9 (19695

Moranot J.

Sorption of Vinyl Chloride In Various Poly(vinyt chloride 5 Food Simulating Solvent Systems

Ph.D. Thesis* Rutgers Univ©* 1975

Morano J • R ® » Giacin* J « k . « and Gilbert* S © G © SorptSon-Desorpt i on of Vinyl Chloride in Selected PVC-T cod S

Solvent Systems

J. Food Sci * * Vol. 42* pp. 23C i 1 9 7 7 j Morita* Z®» Abut hossain* T ® M . * and li jina* T . Diffusion and Adsorption of a Model Cationic Dye*

M— N i t r o b e nz y l

a

m i n e * in Polyacrylonitrile

Bull. Chem« Soc. Jpn.« Vol. 48* No. 4* pp® 1196—9 (1975)

Morsiers A. De

Migration of Plastic Adjuvant Agents with Regard to To* icoto

Aspects

Ernaehrungsforschung* Vol® 16* No© 4, pp ® 637—41 (1972)

Narkisi N ® * and Narkis* M ® Slow Release of Watei—Soluble Salts from Polymers

J. Appl® Polym© Sci.» Vol* 20* No© 12* pot 3431— c (1976)

Novitskaya* L®P®e Kazarinova* N®F® 9 and Kuznetsova* V»N«

Determination of Certain Stabilizers— Antioxidants during San

and Chemical St u dies of Polymeric Materials

Gig© Sanit., No® 7, pp. 74-7 (197 7)

Gsiromow* F©

Detection of Traces of Additives In Migration from Finished

Polymer Products by Determining the Functional Groups o Additives

Ann® 1st® Super. Sanita®* Vcl® 8* No® 2* pp. 474—89 (1972)

Pestova* A ® G © » Oavidan* R ® G ® » and Vladimiskaya* F * E © Toxicity Characterization of Polymeric Materials Used in

the Food Industry

Soviet Plastics* Vol® 1972* No® 3* pp® 84-6 (1972)

Peterlin* A©

Dependence of Diffusive Transport on Morphology of Crystalli

J. Macromol® Sci® 6* Vol. 11* No® 1* pp© 57—87 (1973)

Petrova* l « I

Migration of Low-Molecular— weight Substances

from Polystyrene Plastics into Liquid Media

- 25-

i m u l t a n t

g i c a l

I tar y

H { gh

f Su c h

ne Polymer
P 1 a s t © f^assy » No® 12 e ppe 34—5 S 1 9 7 fc ) T echnol# «

*, I n t U Poiym© Sc i « Vol© 4 « No« 5 g p p < 72 (1977)

125© Petrova* L®I©® and Eoikova? 2®K®

Study of the Health Aspects of U P M— 7 0 3 H« I » Polystyrene

Plasi® Massy® No® 5* p p © 62 (1976)1 Inti® Poiym* Sc i « Techno U t Vo l • 4® No. 1. pp® 24 ( 197 7

)

126© Petrova® L«2©« and Boikovas Z®K©

Possibility of the Use of ABS Plastics in Contact with Food

Piast* Massy® No© 12® pp® 31 (1976) Inti® Poiym# Sc i © TechnoU,

VoU 4® No. 5® pp© 99 ( 19 7 7)

127® Petrova® L ® £ a a Boikova® Z » X « « and Guricheva® 2©G©

Migration of Styrene from Polystyrene Plastics into Food Products

and a Method for Determining the Mo noraer In them

Plast. Massy® No® 11* pp® 57—60 (1970)

123® Petrova® L © 1 © ® Cu richevss Z®G®» Bailova* GaD«® Egorova® E© 1 «

®

Maksimova * K®S« 5 and Rudakowa® M « N

Toxicity Properties of High Impact Polystyrenes Based on

Various Rubbers

Soviet Plastics® No© 5® p p* 67—9 (1972)

129® Pfab® *a® Methods for Determining Total Migration into Fatty Foods

Ann* 1st© Super* Sanita»« Vcl® 8® No. 2® pp t 385—94 (1972)

150® P fab ® M*

Diffusion in a Plastic—Fat System

D + sch* Lebensist-Rundsch® i Vol® 69® No* 4® pp. 151 — 62 ( 1973)

131® Pfab® ® and Muecke* G*

Migration of Selected Monomers In Foods and Food Simulants

Dtsch® L e ben ssn ® — Ru nd s c h * © Vcl. 73® No. 1* pp. 1—5 ( 1977)

132® Piafert h* « and Figge® K«

Migration of Additives of Plastic Manufacturing from Films into

Gils and Fats® and Model Systems® Comparison of Gravimetrically

Determined Residues from Extraction Solvents with Actual

Extracted Additives

Dtsch. Lebenscia-Rundsch** Vcl© 67® No® 8* p p * 26 5— 9 ( 1971 )

133© PS ekaezi E©

Public Health Evaluation of Polyethylene Terephthalaie

Roe.z® Panst® Zakl© Hig®« Vol© 25® No* 3® pp® 281-265 (1974)

134. PUr\er» S.Kh.® and Govorukhina® V « 1 • Diffusion Properties of Plastics Films In Brine

Rybn® Khoz»* Vol. 45® No. 1® pp® 70—71 (1969)

135®

136.

Poorten* R® Van Cer

Migration from Plastics

Revue De L'Agricu Iture.

Pugina* M • 1 . * Zaikovai Go

Daumant i ene • V © ® Ja

Effect of Stabilizers an

Packagi ng Ma t eri a l s into Da C r y Pr o du c t s Vol® 27 9 No® 6® p p © 1501 -15 2 0 ( 1974)

E ® « Mo i s e e v ® Yu» V © ® T o r n a u » E© ® Kviklys® A

ske levi c i us® B ® ® and Mac i u l i s ® A*

d S t a b i l 5 z a t I o n Methods on the Pr op«rti e s

«

- 26 -
of Polymer ter » a ls» 7 ® Kinetic Laws of Diffusion

Stabilization of Polyamides

L let « Tsr Mokstu Akad* Darb*» Ser® D » No® 2® pp» 69—7 ‘3 (1974)

137® Quankenbos« H ® M © Plasticizers of Vinyl Chloride Resins Migration of Plasticizer

Ind« Eng® Chein®® Vol® 46® pp® 1235 (19541

138® Reed® M*C®» Kleimir® F ®F • « and Schulz® EoF®

Plasticizers of Vinyl Chloride Resins* Removal by Oil® Soapy Water and

Dry Powders

Ind® Eng® Chemc® Vol® 46® pp® 1244 (1954)

139® R he e » C • K * * and Ferry® J®D®

Diffusion of Radioactively Tagged Penetrants through Random and Block

S t y

r

en e — 6 u t a d i e n e Copolymers and Filled c i s —Po i y bu tadiene

j® Appl® Polym* Scia® Vol® 21® pp® 467—476 (1977)

140® R'nee* C © & ® ® and Ferry® J®C®

Diffusion of Radioactively Tagged Penetrants through Rubbery Polymers®

1® Penetrants with Very Low Solubility

Jo Appl# Polys. Sc i . ® Vol* 21® pp® 7 7 3-7 8 1 ( 19 7 7)

141® Rhee* C®— K®» Ferry® J®Do® and Fetters® L*J®

Diffusion of Radioactively Tagged Penetrants through Rubbery

Polymers® II® Dependence on Molecular Length of Penetrant

J® Appl® Poiym* Sci®» Vol® 21® No® 3® pp® 783—90 (1977)

142® Rienzi® R®

Determination of Migration of Vinyl Chloride Monomer out of PVC

Containers for Beverages

Ind® Celle Qevande® Vole 4® No® 5® pp® 11 o— 118 (1975)

143# Robinson® L a Anal® Sys® for the Admission of New Additives and the Control of

Migration

Ann* 1st* Super® Sanita*® Vol® 6® No* 2® f • p » 542 — 9 (1972)

144® Rozaci* C « • Burda® J®« Hlavnicka® J®» Krizek® V®® and Svoboda® ^ ® Migration og Additives from Rubber

Plast. Kaucki Vol® 11® No® 12® pp® 360 (1974)

145® Roe® ft®- J#

Physical Factors Controlling Retention of Additives in

Polyolefins

ACS® D I v # Crg# Coat® Plast® Chem# 9 Prcpt®, Vol® 34* No® 2* pp» 132—7

(1974)

146® Rohleder® K • « and Bruchhaussni B® Von

Direct Determination of Plasticizer Migration from Plastics into

Fat and Fat-Containing Foods

Dtsch® Lebensm® — Fundsch*® Vol* 68® No* 6® p p * 180—184 (1972)

147® Rombusch® K © » and Maahs® G®

On the Distribution and Migration of Antistatic Agents in Specimens

fronrs Polyolefins and Polystyrene

Angewo Makroroot® Chem® (Switza.De Vol® 34 ,, No® 5 31® pp® 55—

7

j (1973)1

NASA-TT-F- 1 4794

- 27 -
148 • Rost* S- »E e Contamination of Fats with Phthalaies from Plastics

Fette® Se i fen « Anstrich®** VoU 72® Not 7, pp. 5 52—3 { 1 97 y

)

149© Rubin® R « 0 . Biomedical Implications of the Migration of Phthalate Ester

Plasticizers from PVC Plastic

Tech® Pap®® Reg® Tech® Conf » « Sac® Piast«« Engs , Palisades Sect®

pp® 81-3 { M arch 20-22, 19731

150. Rudto U«

Effect of Plastics or. Foods

Gordian, Vole 71, No® 4® pp® 102 — 95? No® 5, pp®I4l — 45 (1971)

1 5 1 o Rysavyi L © Water Extraction of Stabilizing Additives and its Effect on

Atmospheric Aging of Polypropylene Films

Plasty Ka uc ® , Vole 1.3* No® 10* pp® 29 7 — 9 ( 1976)

152® Salamet M.

The Prediction of Liquid Permeation in Polyethylene and Related

Polymers

SPE Trans®, VoU 1« No, 4, pp® 1 — 11 Cl 96 1 )

153® S a l am e • M © , and Pinsky® J«

Permeability Prediction

Mod® Packag®, No® * pp® (1962)

154® Salvatore, G®

Method of Determination of the Global Migration of Plastics and Rubbe

in Fatty Foods®

Rass© Chira®, Vol® 27, No® 2, pp® 57—69 (1975)

155® Seidler® F © ® Haeftigs M » » Woggon, H® « and Jhde, m ® J © Examinations on the Migration of (1— 1 4 C ) — 2— Ethyl— Hexyl Ester of

D i — N— Cc tyl Tin Dithioglycolic Acid (Stabilizer Gt s 15) f r om Hard

PVC into Edible Cil

Nahrung, Vol© 15, No. 2® pp. 167-90 (1971)

156® Seidler® H ® « Waggon, H © « haerf ig* M® « and Uhde, w ® J ® Testing of Plastic Commodities? the Migration of

Hi s( 2— Ethyl hexyl) ((Di (Cetyl— 1— 1 4 C ) Stannylene)D5th£o)Diacetatc

from Rigid Poly(Vinyl Chloride) into Edible Oil

Nahrung* Vol. 13® No. 3, pp. 25 7— 64 { 1 9 b 9 )

157. Seidler, F e , Woggon® H® » and Haerti g« M®

Testing Plastics® Study of the Migration of Di — n-Dctyl ( l — ( 1 4 ) C ) Tin

2— E t b y l h e x y l — D i t h i o g l y c o l a t e from Rigid Poly (vinyl chloride) ini

Ecible Cils

Nahrung, Vol. 13® No. 3, pp. 15/— 64 (19b9)

158® Semenenko, E®I®» and Markelov, M«A.

Physicochemical Basis of Sanitary Chemistry of Polymer Materials

Kh im* Farm. Zh® Vol® 10, No* 9, pp® 129—136 (1976)

Phar®« Chem® J* (Engl® Trans U j »

159® Sluzewska, L®
160 •

161.

162 •

163 •

164 •

165.

166 •

167.

168.

169.

170.

Preliminary Hygienic Evaluation of Silicones Intended for Contact with

Foods

R o c z ® Panst« Zakl® Hi 9 . « Vol® 21* No® 2» pp« 16 9- 75 (197 3)

SoKolowsKa ® R

Phenol Detenaination Methods and their A 0 p l i cation to Hygienic

Evaluation of u lastics Utility Products. IV® Migration of Phenols

from Products Made from Phenol-Formaldehyde and Epok y—Pheno l Pesi ns Rocz© Panst* Zakl© Hi g.« Vol® 20* No. 4* pp* 382—89 (1969)

Soholowska * R

&

Identification of Antioxidants Use .d in Polyethylene* II® Identification

in Plastics Items and Migration Study

Rocz® Panst. Zakl. Hi g, , Vol® 23* No® 6 * pp. 661—72 (1969)

Svoboca* P®» Krali cek# J®» Vo ndruskova » Rozaci < G®» Vanek® P © * and Cockali J © Migration of Paraffin Waxes* I • Behavior of Paraffin 58/60 in

SBR and in Natural Rubber

Plast® Kaucuk* Vol. 13* No. 8 * pp. 241 (197o)

Tarasova* N © A ® ® Feofanov* V ® C ® » and G u l

e V © 2 © Benzene Content in Medium-Pressure Polyethylene

Gig. Sani t. • Vol. 36. No. 11 * pp. 114-16 (1971)

T roparewskys A.® Pi sarel lo De T r®, MeL.® and M i t t a » A« E« A*

Determination of Migration of Plasticizer by 14C Labeled Compounds

Report C N E A « No® 391* pp. 11* Avail. INIS Atominde*, Vol© 7, No® 5.

Abstr. 22760 (1976)

Tsam* Z « M ® Hygenic Evaluatio n of New P 0 Lymer Materials Used In Dr inking

Water System

Hy g» San S t® » Vela 36, No® 7 - 9 ® p p « 453-5 ( 197 1 ) Uhde » ( d • « and fc o g go n » H ® Testing Plastics® 3® Migration Rate of Hy droxyphenylbenzotr i azole

Plastics into Edible Cil

Nihrung* Vol. 12. No® 8 * pp® ft 2 5— 3 4 ( 196 8 ) Uhde® W.J.. and Woggan® H.

Analysis of Plastics Utensils. Migration of Antioxidants from Food

Wrappings

Dtsch. Lebensm®— Rundsch.* Vol. 67, No® 8 * pp® 25 7—262 (1971)

Uhde* W ® J ® « and Waggon* H®

Recent Results Concerning the Migration Behavior of Benzophenone Based

Ultraviolet Absorbents from Polyolefins in Foods

Nahrung* Vol® 20* No# 2* pp® 165—94 ( 1976)

Uhde® W.J.® tooggon* H© « and Koehler*

Testing from Plastics® 2® Migration

Plastics into Edible Oil

Nahrung® Vol® 12® No® 8 ® pp® 812— z4

U a of 4 ® 4 * — Thao — b i s( 6 ~ t — Rut y t— m — Crcso l )

(1968)

Uhde® w © J . * Woggon® H®« Zydek® 6 a * and Koehler© U © Testing Plastics® Migration of UV— Absorbents from Food Packaging

Materi als

- 29 -
Dtsch® L e ben s ro « — Run d s c

h

«

9

Vole 65 # No » 9® PP 2?l-78 (196 r')

17 1 ®

172®

173®

174®

175.

176.

177®

178.

179®

180.

18 1 ®

182.

Varsanoo J®L©. and Gilbert. S«G®

bva luat i o n of Interactions Retween Polymers and Low — Molecular Weight

Compounds by GLC (Gas- Liquid Chromatography). I. Methodology and

Interact Evaluation

J. Pharm, Set.® Vo L 6 2® No. 1® pp. 87—9 1 ( 1973)

V I e t h » W ® R ® ® ana Am ini. Mary A®

Generalized Dual Sorption Theory

Polyrn® Sci® Techmola 6 » Permeability Plast • Films Coat.

Gases® Vap®» L i q « ® p p » 46—61 11974)

Vieth* W ® R ® ® Howell® J.M**

Dual Sorption Theory

J® Membrane Sci.* Vol* 1*

and Hsieh J.H

pp. 17 (197 ) Vorob'evs V ® P ® » GurCcheva* Z«G«« Petrova* L ® 1 ® « and Sazhin. Bel®

Description of the Migration cf Low-Motecular-Weighi Components

from Polystyrene Plastics by Diffusion Equations

Plast. Massy* No® 7* pp® 57—60 (1972)

Wang* T.T.* and Kwei* T®K®

Diffusion in Polymers

Permeability of Plastic Films and Coatings

and Liquids. Hopfenberg* H. 8 .* Ed.

Plenum Press* N*Y®» pp. 62 (1974)

to Gases* Vapors*

Westerdahl* C«A»L»

Diffusion and Persistence of Silicone Gil in Rubbers and Low Density

Polyethylene

Picatinny Arsenal Technical Report* No. 2185® March 197c

Westlake® J a F ® « and Johnson® M®

Diffusion of Stabilizers in Polymers® 1®

2 » 4— D i h y d r o x y b en z o p h en o n e in Polyolefins

J. Appl. Polyro® Sci®» Vol® 19. No® 2® pp® 319—34 (1975)

Wewerka* D®» Fruwirth* Co* and Hummel* K®

Reactions in Crosslinked Polymers® 2® Purification of

Polytutadiene by Extraction with Liquefied Butane

Kaut, Gumrni* Kunstst.* Vol. 27, No. 3* pp® 92—3 (1974)

Wharton* F«D« * Jr* < and Levin skas* G® J®

Toxicological Studies on Nitrile Barrier Polymers

Chew. Ind. (London)® Vol. 11® pp. 47 0— 4 ( 197 6)

WIeczorek* H©

Isolation and Quantitative Determination of Qrganot in Compounds in

Edible Oil and Vinegar after Contact with Stabilized Rigid PVC

Fi l nr. s Dtsch® Le ben sm .-Rundsc h . • Vol. 66® No. 3* pp* 92 — 95 (1970)

Wilobrett® G ® The Extracting Effect of Detergent

Ml Ichwi ss«nscbaf ti Vol. 28* No® 7.

Solutions on PVf Milk tubes

pp. 443-446 (1973)

Wildbrett® G®
Diffusion of Phthaiic Acid Esters from PVC Milk Tubing

Environ® health Per spectu Vol# 3* pp# 2 9 — 35 ( 1 9735

183® W ( Icbrett* G © * Evers® K • w ® « and Kiermeier* F®

Investigations and Observations on the Application of Plastics

for Foods# XII® Migration of Monomeric Plasticizers from PVC Milk

Tubes into Cleaning Solutions

Fette* Seifen* Anstri chra» * Vol® 71* No* 4® pp« 3 3 J — 335 ( 1 5o5 5

184® Wildbrett® G ® ® Evers* K . — W « . and Kiermeier, F » Investigations and Observations on the Application of Plastics

for Foods® XIII® Interaction of Plastics with Milk

Z* Lebensm.-Untsrs. Forsch.* Vol® 142* No® 3* pp» 205—15 (197^5

18b® Witdbrett* G®» Evers* K ® — W ® * and Kiermeier® Fa

Investigations and Observations on the Application of Plastics

for Foods® XVI® Diffusion Process in PVC Tubing for Foods

Werkst® Kcrros®* Vol® 22# No® 9* pp® 753— 7 59 { 19715

186® Wilks* R ® A ® * Jr © * and Gilbert* S®G»

Sensory and Instrumental Evaluation in Model Systems of Residues

Migrating from Can Coatings

J. Food Set®. Vol. 37* No® 1. pp. 72-76 (1972)

187* Woggon* H®« Jehle® D® * and Uhde® «« j#

Testing of Plastic Commodities® Migration of PVC. (Pol y( V i ny i Chloride!! Stabilizers into Edible Cil

Nahrung* Vol® 13* No. 4* pp® 342-50 (1569!

18Q® Woggon® H»* and Koehler* U©

Testing of Plastic Utensils Polarographic Determination of D t - (2 — Ethyl

He«y l l-Phtha late and Investigation of the Tendency to Migration

Kunststoffe* Vol® 57* No® 7* pp® 583—586 (1967)* NA SA— TT— F— 1 38R9

189® Woggon* H # * and Koehler* U#

Testing Plastics* 4* Migration of Plasticizers from

Po lyeiethacr y lates into Food

Ernaehrungsforschung® Vol® 13* No® 4* pp® 651—55 (19685

190® Woggon* H • » Koehler* U * * and Uhde » nt#-J*

Testing Plastics® Migration of Cadmium Pigments from

Materials

Dtsch® L e b e n s m

. — F u n d sc h * « Vol® 64* No® 8* pp® 243—47

191® Woggon® H®» and Uhde* W«J®

Antistatic Finishing of Plastics from the Food— Tosicoiogical Point of

View

Nahrung* Vol® 21* No# 3* pp® 235—45 (19775

192® Woggon® h®« Uhde* W®J©« and Saeuberlich® H®

New Results on the Migration of Qrganotin Stabilizers in Food

Ernueihrungsforsehuny* Vol® 16* No® 4® pp® €45 — 55 (1572 5

193® Woggon® Ho® Uhde® W®J®« and Zydek® G®

Testing of plastics® Migration of 2* 6— Di-tert-Oui yl-p-Cresol (BUT) in

Edible Gils

Z® Lebensra® — (Inters* Porsche* Vol® 138® No® 2* p p » 16 9— 77 ( 19 6 8 5

Food Packaging

( 19685

- 31 -
1 94 « Yen® WsCoHs

Quantitative and Qualitative

Stabiliser from PolyCvin

Jiss« Abstr, Ints 0« 5c i © Enj

70- 1 1<36 2 l l <370 »

s t u i y o f the M i yra t ion o f Or y a n o t i n y i chl o r » de ) t o L » quid Poo d s

& V Vol © 3 1 » No <# d » po» 134 -j * —> 9 Order « No 3

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- 32 -
REVIEW AND EVALUATION OF AVAILABLE MIGRATION MODELS

Introduction

Migration of minor constituents from a polymeric film to a food or

simulating solvent is controlled by both transport and thermodynamic

factors. Neither can be ignored if a complete description of migration

is desired. For example, the diffusion of a species (hereafter referred

to as the "migrant") from a polymer film of thickness 2% and volume V

to a stirred solvent of volume V is given by

oo

FT

1 1 '2^ 2a(1 +

2

}

2 exp (1)

00 _ -j 1 + a + a q ^ n= i n

where the q

n

‘ s are the non-zero positive roots of

tan n + aq„ = o

n

n n

( 2 )

and

D= migrant diffusion constant in polymer

K = C / C = equilibrium distribution coefficient

S Cp= equilibrium concentrat ion of migrant in film

C c = equilibrium concentration of migrant in solvent

M

t

= amount of migrant transfered to solvent at time t

M = amount of migrant transfered to solvent at infinite time

If the initial concentration of migrant in the polymer film was C ,

M = VC and

o p o

i C

p

_ M

] _ e

°° = a

C 1+a

0 0

- 33-

( 4 )

then
Notice that Eq. (1) is a function of both D (a transport property) and K

(a thermodynamic property). Equation (4) determins the maxi mum amount

of migration that can occur and is strictly an equilibrium or thermodynamic

property of the system.

Equation (1) is the complete solution for a certain class of migration

problems; viz., those systems which obey Fick's two laws of diffusion

and for which D and K are known. Therefore, modeling migration behavior

for this type of system can be reduced to estimating, either theoretically

or by semi -emperi cal methods, K and D.

If the polymer film is appreciably penetrated by solvent, the

diffusion constant is not constant and Eq. (1) will no longer hold. But

even in these systems Eq. (4), which is only a function of K, is valuable

in the sense that it yields an upper limit for migration. Of course,

this upper limit equals (complete extraction of the migrant) if the

solvent mass is mtich larger than the film mass; i.e., if the film

is placed in an infinite solvent reservoir, migration continues to

completion at infinite time. However, in many food packaging applications

(e.g. plastic bottles) a will be finite and a residual amount of migrant

will be retained by the film.

In the next section, methods of theoretically estimating distribution

coefficients will be discussed which will then be followed by a discussion

of theoretical methods for estimating diffusion constants. A general and

practical migration model will ultimately depend on how well K and D (and

their temperature dependences) can be calculated from the physical

properties of the polymer, solvent, and migrant.

Distribution Coefficients

In principle, a relatively good estimate of K should be possible for

some polymer/solvent/migrant systems by using either the Flory equation

2-4

of state theory of solutions or the lattice fluid (LF) theory of

5 Sanchez and Lacombe . An important prerequisite for the application

- 34-
of either theory is that the thermodynamic behavior of the

migrant + polymer can be treated as an equilibrium mixture

of two fluids. The amorphous component of a semi -crystal 1 ine

polymer, such as polyethylene, can be treated as an equilibrium

liquid if the temperature is above the polymer glass transition

temperature. Under these conditions, the chemical potential

of any organic migrant species (liquid or gas) within the

amorphous regions can be calculated.

According to the well-known Flory-Huggins (F-H)

theory of solutions^, the chemical potential of component 1 in

a binary mixture is given by

(p

1 -w1 °)/RT = In*, + (1-V

1 /V2

)* 2

* xo

2

2

(5)

where is the molar Gibbs free energy of pure liquid

component 1 at temperature T, ^

= 1-<|> 9 is the volume

fraction of component 1, V-j and V

? are the respective molar

volumes of the two components and x is the reduced residual

4

chemical potential . In the original formulation of

F-H theory, x was strictly an energetic parameter that was

proportional to the energy required to form a 1-2 bond

from a 1-1 and 2-2 bond. It also had a simple 1/T temperature

dependence and was independent of solution composition. Now

it is known that x is in general concentration dependent

and possesses a more complicated temperature dependence than

1/T. Experimental ly , x is treated as an empirical parameter

which is adjusted as a function of concentration and

temperature to fit experimental ly determined chemical potentials.

- 35 -
Even in solutions containing polar components, positive x 4

values are usually required . Large positive x's are,

of course, thermodynamically unfavorable and will limit

miscibility.

This positive character of x has highlighted the

failure of F-H theory because the sign of x should be the

same as that of the heat of mixing, AiiL Exothermic mixing

requires a negative x> yet there exist many examples

where AHm

is negative and positive x's are required for

the chemical potentials. Even more puzzling within the

context of F-H theory is that large negative heats of

mixing often occur with mixtures of non-polar components

which require relatively large positive x values (see Table I

for some examples). However, both the new Flory and LF

theories have resolved this apparent paradox. Experimentally*

x often has a large positive entropic component which arises,

according to the Flory and LF theories, from differences

in the equation of state properties of the pure components.

Formally, the concentration dependence of x can be

expressed as

X

s

X-j +

x

2

(J) 2 + ( 6 )

There are two important limiting values of x- xrxUfD oo (7)

x°° = xU-j = o) = ? xi (8)

In almost all polymer solutions that have been studied,

x°° > x-j for the solvent chemical potential.

- 36 -
At equilibrium, the chemical potential (or activity) of

the migrant u

p in the amorphous regions of a semi-crystal 1 ine

polymer will equal the chemical potential of the migrant

in the solvent phase:

Pp - P

S (9)

Let the migrant be component 1 and present in small

quantities compared to the polymer film or simulating solvent;

thus 4

> 2+ 1 and the migrant chemical potentials approach

the following limiting forms:

(y

p -u°)/RT = lntj>p + 1 + Xp 0°)

(p

s -p°)/RT = 1 n<(> s + 0-V

m

/V

s

) + X

s " (11)

where V_ and V_ are the molar volumes of migrant and solvent

m s respectively (Vm/V

p - o and is ignored), <j> s is the migrant

volume fraction in the solvent phase, <(> is the migrant

volume fraction in the polymer phase and x~ anc* x"T ^re the

P ^

x°° values of the migrant in polymer and solvent phases,

respectively. At equilibrium, Eq. (9) holds and thus the

distribution coefficient is given by

K = 0 /<*> = exp ( V /V + x “

- x°° ) C12 ) S p m S p s

Equation (12) offers an alternative to extraction

experiments for experimentally determining distribution

coefficients. Recent advances in gas chromatographic

techniques have made it possible to determine x°° in low molecular weight

systems such as n-hexane/squalene 7 and in polymer/sol vent

g systems such as polyethyl ene/n-decane. The necessary

equations required to obtain chemical potentials from

equilibrium chromatograms are discussed in references 7 and 8

-37-
9

10

and in more recent papers by Purnell and Bonner and Brookmeier . 10

For polymers, measurements are normally carried out above the

polymer melting point or glass transition temperature. These

temperatures will usually be well above the anticipated use

temperatures of the polymeric food packaging material. However,

co with the aid of theory, experimental x values can be

extrapolated accurately to lower temperatures.

The Flory and lattice fluid (LP) theories incorporate

the "equation of state" properties of the pure component

fluids. Both theories require 3 equation of state parameters

for each pure component which are determined from PVT data.

5 For the LF, about 60 low molecular weight fluids and 10

1

1

different polymers have already been so characterized.

For a binary mixture, LF theory requires 7 parameters: 3 for

each pure component, which are already known or are calculable

from PVT data, and a seventh parameter that characterizes

the interaction between the two components. The Flory theory

requires an eighth parameter that is related to the surface/vol ume

properties of the pure components. A relatively concise

review and comparison of these two theories has been given

by Sanchez‘S.

oo For the LF, x for component 1, the migrant, is given by

where

v

oo M

* *

(13)

M-j= molecular weight of component 1 (migrant)

T-j , v- , p.j= characteristic temperature, volume, and mass

density, respectively, of the migrant

- 38-
r

\j * 'Xj p-,= p-j/p-j = 1/v-j reduced migrant density

P 2

= p 2 /p

2

= reducecl polymer density or reduced

simulating solvent density

^ * T^= T/T-j reduced migrant temperature

X

1 = aP*v*/RT (14)

and aP represents the net change in cohesive energy

density upon mixing components 1 and 2 at the aosolute

zero of temperature. X, is_ the only unknown parameter in

Eg. (13) . All others are known or derivable from pure

component PVT data. An experimental value of x°° would

establish the value of X-j , of course, but other kinds of

solution data (often more accessible experimentally) such

as heats of mixing, critical temperatures , solution densities,

etc. can be used to determine X5

. Thus, LF theory offers a

method of calculating x°° values without actually measuring

chemical potentials directly. To illustrate this possibility,

x°° values have been calculated for some polyisobutylene

solutions using AHm data to fix X-j. As a polymer solution

becomes dilute in polymer (component 2), the heat of mixing

approaches a limiting value, AH (»), defined by:

AHm

(oo) = lim AHm

/4> 2

(15)

In Table I AHm

(°°) values at 298 K for polyisobutylene in

n-pentane, n-octane, cyclohexane, and benzene are tabulated.

A striking feature of the data is that 3 out of 4 of these

non-polar solutions are exothermic. Notice, however, that all

- 39 -
* of the calculated aP and X-j values are positive as one

might expect for these non-polar components. The calculated

. oo X- values have then been used in Eq. (13) to calculate x ;

oo the experimental x values are also tabulated in Table I

for comparison. Also listed are the experimental and theoretical

values of x-| ax ( 4>=1 ) which shows how x can vary with concentration.

Although the agreement is not spectacular, it is encouraging.

Similar results can be obtained with the Flory theory whereas

the Flory-Huggins theory would fail miserably.

- 40 -
TABLE I

1/1 aso LO U3 r-» sc r— lT“ 6— r—

<V3 as

s_

A

a) CO CO oo oo

<o is- r— p— r— IT— -o os

s-a ID co ^3“ CO

Jx *3- oo VD

«3 • « • * O O O o o , X

cn vo o

Cl ^r «=sD X • • • • O) o o o o o 00 VD CO ID CO CO

<tS • • • ® a o o o o X

4-> CO <o

m

a. cr> ID %r> IF” X • • • •

(X) o o o c—

6— sx oo_ o O • • • o VO o

cx2

CM

<3 ^

SIo o CO CM o

CO CM CO

X cr> l~ r—

(— • • • • X CM CM COo 8 o r— Oi CO CTi ""e E oCM

ID CO o <

“D 8 I D 4-

<Dc

as ft! c as X

05 c as 05

4-> <o -C S= C +-> o as

as o r— N1 CL o o C 1 ! X 0J C E o jd - 41 -

Table IA

comparison

of

experimental

and

theoretical

reduced

residual

chemical

potentials

for

polyisobutylene

solutions

at

298K*
Diffusion Constants

1. General Properties

Typically, the self-diffusion constant D of an

-9 2 organic liquid is about 10 m /sec. At low concentrations

in a polymer, the same organic species diffuses at a drastically

-13 2

reduced rate; D can vary from about 10 m /sec at T + 100 K -20 2 to about 10 m /sec near T^.

Most diffusion studies have taken the form of

permeation or sorption experiments performed on amorphous

polymers (lightly crossl inked) above their glass transition

temperatures. Whereas diffusion behavior is relatively

simple at temperatures above T , it is exceedingly complex at

temperatures near or below T^.

In the usual absorption experiment a polymer film,

initially free of diffusant molecules, is suddenly exposed

to an organic vapor at a fixed pressure and the gain in weight

of the film is monitored as a function of time. Desorption

of the diffusant can also be studied by reducing the pressure

to a new fixed value and following the film weight loss.

Data from a sorption experiment (either absorption or desorption)

are generally represented by plotting the amount of vapor

M

t absorbed or desorbed against the square root of time. At

long times equilibrium is approached and M^-^M^.

Crank^ discusses at length the method of data

analysis required to obtain diffusion constants from sorption

data. It is assumed that D(c) is a function of concentration

c, but not of time, and that the diffusant concentrations at
the film surface increase or decrease instantaneously

with pressure to their equilibrium values. Under these

conditions the sorption is called Fickian and sorption

curves are expected to possess the following properties:

1 /2

a) Sorption curves are initially linear in t

'

. For

absorption, the linear region extends to over 60%

of M . For desorption, linearity is obtained almost

up to equilibrium if, as would normally be expected,

dD/dc > 0.

b) Above the linear portions, both absorption and desorption

1 /2 are concave to the t axis, irrespective of the

form of D(c)

.

c) Sorption curves are superimposable. A series of

absorption curves for films of different thicknesses (i)

1/2 are superposable if M

t is plotted against t /i. The

same applies to a corresponding series of desorption curves.

These properties are independent of the form of D(c) and

provide an experimental means of determining whether a given

system exhibits Fickian sorption. One of the most important

findings of sorption studies is that at temperatures well above

T

g

, the sorption kinetics of organic vapors are invariably Fickian .

Temperature dependent sorption studies have also

revealed another characteristic property of small molecule

diffusion in polymers: the temperature dependence is

strong and non-Arrhenius. A plot of log D vs 1/T will usually

18

be non-linear. For example, Hayes and Park studied

sorption of benzene in natural rubber and found that the

* apparent activation energy, aE e-R dlnD/d(l/T), is about

29kJ/mole at 373 K but increases to 96kJ/mol at 273 K.

- 43-
Another feature of the temperature dependence, which is

especially relevant for migration studies, is the finding that

aE often appears to be independent of the diffusant's chain length or

branching. Such has been the case for isomeric hydrocarbons

•; g 20

in natural rubber and polyisobutylene and n-alkyl acetates

21 22

in polymethyl acrylate 5

. In the case of natural rubber,

* the constancy of aE has been shown to hold up to as 23 large a molecule as octadecane . T hese findings tend to

support the thesis that the temperature dependence of

diffusion is largely determined by the properties of the

polymer and is relatively independent of the size and shape

of the diffusant.

2. Diffusion above

Theories of the diffusion constant fall into two broad

classes: In one, which is especially relevant for migration

studies, attention is directed at how the magnitude of D and

its temperature dependence are affected by such factors as

the size and shape of the diffusant, the nature of the polymer,

and the intermolecular interaction between diffusant and

polymer. In the second class, interest is focused on

interpreting the concentration and temperature dependence of D

and not its magnitude. A 1973 review of the latter class

24 of theories is available while the former and more important

25 class was reviewed in 1968 by Kumins and Kwei

Of the theories reviewed in 1968, two stand out. These

26 27 are the free volume theories of Cohen and Turnbull ’ and

28 * Bueche . Both theories require the probability P(v )

that the local volume v associated with the molecule or a

"segment" of the molecule be greater than some critical

ic volume v . The theories are different in that different

- 44 -
methods are used for calculating P(v ). Cohen and Turnbull

assumed that a multinomial distribution of free volumes

exist in a liquid to derive:

it P(v ) = exp (yV /V f)

D ^ u P(v )

( 16 ) 07 ) where f is the fractional free volume, v

& is the molecular or segment volume when f=o, yis a dimensionless constant (1/2 <y<l).

where <v> is the average segment volume, B is the isothermal

compressibility of the polymer and erfc is the complementary

error function.

Although both of these theories in their original

formulations did not consider the diffusion a small molecule

in a polymer, they have been successfully applied to such

29

systems. Fujita has demonstrated that the Cohen- l urnbul

1

theory adequately describes the temperature dependence of

diffusion in polymers in several systems. (Acutally Fujita

used an empirical equation for D due to Doolittle‘S which

29

is equivalent to the Cohen-Turnbul 1 equation for D). Fujita

31 -33

and others have shown that the Cohen-Turnbul 1 theory,

properly modified, adequately accounts for the concentration

34 dependence of D up to 10% of diffusant. Kumins and Roteman

have used Bueche's theory successfully to correlate the diffusion

behavior of small gas molecules with their van der Waal volumes.

and u is the average molecular or segment velocity [u=(kT/M) ‘^ 2

].

Beuche used the thermodynamic theory of fluctuations,

orginally derived by Einstein, to obtain

v - <v> 07 ) 08 )

- 45-
However, the success of both theories must be viewed as being

primarily correlative rather than truly predictive.

Recently Sanchez 35 obtained the following expression

for the diffusion of a small molecule in a polymer:

D = D(c=o)

o (19)

— oo where v is the partial molar voi ume of the diffusant in the

limit of zero concentration, 3 is the compressibility of the

polymer, and ail other symbols have the same meaning as before.

Equation (19) can also be suitably modified to treat the

diffusion of a large molecule composed of N segments, each

of which is able to execute independent diffusive motions.

Although Eq. (19) has yet to be tested quantitatively,

it has the potential of being a predictive theory of diffusion.

It is predictive in the sense that all of the requisite

parameters and variables can be determined independently

from other physical data; v can be determined from

viscosity or self-diffusion data on the pure liquid diffusant;

• oo v can be semi-quantitatively calculated using either the

2-4 5 Flory or lattice fluid theory of solutions; and 3 can

be determined either experimental ly or theoretically.

The attractive property of Eq. (19) is that it embodies

all of the physical factors judged important for diffusion in

* -00 * polymers through v , v , and 3; v is a unique property of

the shape and size of the diffusant; v°° is a property which

depends sensitively on the polymer-diffusant intermolecular

- 46 -
interaction; and b, of course, is a cha racteri Stic property

of the polymer.

Qualitatively, Eq. (19) also explains why the diffusion

of a small molecule decreases by 4 or 5 orders of magnitude

in a polymer. This can best be illustrated by expanding

36

erfc X in an asymptotic series so that Eq. (19) becomes

(val id for large X)

;

The equation for the self-diffusion constant of the

diffusant will be the same as Eq. (19) or (20) except

— oo that v is replaced by the molar volume v , of the diffusant

and b is replaced by the compressibility 3^ of the diffusant.

Compressibilities of polymer liquids are just about one

order of magnitude smaller than those of similar low molecular

weight liquids. Thus, the big difference between and D

Q

is the compressibility of the medium in which the diffusant

molecule finds itself. (Volume fluctuations are directly

proportional to 3 ). Decreasing s by an order of magnitude

can diminish D by a substantially larger

amount since 3 appears in the exponential.

Analysis of migration or diffusion in polymers is

often based on ideal conditions. That is, the diffusion

constant is assumed to be constant independent of the

concentration of the diffusing material in the polymer and

the concentration in the polymer is assumed to be given by

Henry's Law

( 20 )

C=kp

- 47 -

( 21 )
at equilibrium, where p is the pressure of the diffusant

in the gas surrounding the polymer or the concentration of the diffusant

in a solution surrounding the polymer. However for some

polymeric systems, especially glassy polymers, these

conditions do not hold, so that a more complicated analysis

is required.

37 Vieth and others have studied diffusion and sorption

in systems in which Eq. 21 is not obeyed. An example of

such a system is methane in orientated polystyrene. The slope

of the solubility versus pressure is not constant as in Eq. 21, but

decreases with pressure and becomes constant at high pressures. Vieth

and coworkers postulated that two modes of sorption are

operative in such systems. The first mode of sorption,

Cq, is proportional to the pressure, while the second mode of

sorption, C^, obeys Langmir sorption. Thus at equilibrium.

c = C n + c

u

= k n p

= C' H bp

1 + bp ( 22 )

The second mode of sorption, C^, is considered to be

due to holes or voids in the polymer. Methods have been

37 1 given to determine the constants k n , b and C_ in Eq. 22

from sorption curves. It was demonstrated that the

equilibrium gas solubilities in glassy polymers may

be characterized by the dual sorption model mathematically

expressed by Eq. 22.

- 48-
38

Vieth and Sladek developed a theory of diffusion in

systems that have dual sorption. They assumed the concentration

in the Langmuir isotherm, C

H

, of the adsorption did not

contribute to diffusion and that the diffusion constant D

of Cg, the Henry's law isotherm , is independent of concentration.

They obtained the diffusion equation

D

=

2

C

' H

b/k

D (l+bC

D

/k

d

) 2

(23 )

and applied Eq.23 to transient sorption of CO 2 in

Mylar. Eq. 23 could not be analytically solved for the

boundary conditions of transient sorption because it

is not linear in C^. Therefore, numerical solutions of Eq. 23

were obtained for assumed values of b, C^' and kp. A

method was given for matching these theoretical curves to

the experimental sorption curves to obtain the diffusion

constant D. Good agreement with the observed absorption was obtained.

The method has since been applied to other systems exhibiting dual

sorpti on

.

39

Paul and Kemp have investigated time lag experiments

for systems exhibiting dual sorption. While Eq. 23 cannot

be solved analytically for the boundary conditions (Barrer

conditions) used for time lag experiments, analytic expressions

40

for the permeability and time lags were derived. Kemp made

time lag experiments on a membrane of a silicone rubber

impregnated with molecular sieve particles. Becasue the

molecular sieve particles exhibited large Langmuir adsorption

of the gases used, the membrane exhibited dual sorption.

- 49 -
He was able to determine the constants b, C^, k, and D

from measurements of the silicone rubber and molecular

sieves and predict the results of the time lag experiments.

Good agreement was obtained.

The time lag experiment may be used to determine if

a material obeys ideal diffusion. Fig. 1 shows the amount of

CO^ (AQ

t

) diffused through a membrane versus the time. At

times greater than 100 minutes, the amount increases linearly

with time with a slope, transmission coefficient, of

P = 0.1564 cc/min. Extrapolating this linear relationship

(dashed curve) to AQ

t

= 0 gives a time lag of 81 minutes.

The amount of C0£ versus time that would diffuse through the

membrane for ideal diffusion with these values of the transmission

coefficient and time lag has been computed and is shown by

the crosses. This curve is far from the experimental curve

indicating that diffusion of CO^ in this membrane is not

ideal. In fact, the membrane is one made by Kemp to have strong

dual sorption. Thus, examination of the time lag curve

of a membrane may be used to determine if the system shows

ideal diffusion.

A simple test of ideal diffusion from a time lag

experiment may be made as follows. Determine the transmission

coefficient T and time lag 0 for the system. Then for

ideal diffusion, the amount of gas that has diffused through

the membrane at a time equal to the time lag 0 is given

by 0.33439T.

If the amount of gas at the time lag differs from this

value, the system does not exhibit ideal diffusion. For

the case discussed, we obtain 0.3343 x 81 x 0.1564 = 3 cc.

Since the experiment gives 1 cc, the system aoes not obey ideal diffusion.
- 51 -
G . A IS CL L LANE 0 IS

N,N' -Diphenyl thiourea (thiocarbanilide) 0 . 5 / P VC (c)

Cy an o gu an i d i n e ( Di cy an di ami de ) 1/POl

N-n-Alkyl-N' - c a rb o xy me thy 1- N , N ’ -trinethy lenedigiy cine

R = C 14- C 18

1 . 35 /NR

p~t~ Amy lphenol- formaldehyde Resins 2 . 1/PA

Nylon 60 / 6 IO /6 terpolymer 1 . 5 / P 0A

Po ly

(

1 , 4-cy clohexylenedi methylene-3 , 3 ' - thiodi propionate) partially terminated with

stearyl alcohol, I4W 1800-2 200 0. 5 / P P / .005

- 52 -
D. PHENOLS (continued)

Tetra-

Tetrakisf methylene(3, 5-di-£-butyl-4-hydroxybydrocinnamate) ] methane

Irganox 1010

. 5/PO

. 05/E-MA, E-AA/

. 005

. 5 /PS , E- AA, E- \Ac

,

S-B , IB

1/POM

. 5 / P OM

E . PHOSPHITES

Hydrogenated 4 ,

4

1 - z - p r o p y 1 i de n e diphenolp ho s p h i t e e s t e r resins 2400-3000 0 . 5 5 / P VC ( c ) 4,4'-'5-Propylidenediphenol alkyl (C.

£ ~ C ) - phosphites 1 / P VC ( c ) Tri (mixed mono- and dinonyl phenol) phosphite

2-t-Butyl- a- (3 - £-Butyl-4-hydroxyphenyl)- 1.35/NR,B-A,A-B-S,

p-cumenyl b is (p-n ony lpheny 1 ) phosph i t e B-S/.004

Cyclic ne op en t ane t e

t

r ay 1 b i s (

o

c t ade cy 1 phosphite) 0 . 25/PO

0 . 15/PO

0 . 20/PS , PS

I. THIO CARBOXYLIC ACIDS AND ESTERS

Thiodipropionic Acid

Dimyristyl thiodipropionate

Dicetyl thiodipropionate

Distearyl thiodipropionate

Antioxydans As

Advastab PS 802

- 53 -
References

); J. Crank, "Mathematics of Diffusion", 2nd Ed. Clarendon Press, Oxford (1975).

2) P. J. Flory, 0. Amer. Chern. Soc. , 87 , 1873 (1965).

3) B. E. Eichinger and P. J. Flory, Trans. Faraday Soc. , 64 , 2035 (1968).

4) P. J. Flory, Discuss. Faraday Soc. , 49 , 7 (1970).

5) I. C. Sanchez and R. H. Locombe, J. Phys. Chem , 80 , 2352, 2568 (1976).

6) P. J. Flory, "Principles of Polymer Chemistry", Cornell Univ. Press, Ithaca, NY (1953).

7) J. R. Conder and J. H. Purnell, Trans. Faraday Soc. , 65 , 839 (1969).

8) N. F. Brockmeier, R. W. McCoy and 0. A. Meyer, Macromol ecu I es . 5_, 130 (1972).

9) H. Purnell, "Advances in Analytical Chemistry and Instrumentation", Vol . 2, John Wiley

& Sons, New York (1973).

10) D. C. Bonner and N. F. Brookmeier, Ind. Eng. Chem. , Process Des. Dev. 16 , 180 (1977).

11) I. C. Sanchez and R. H. Lacombe, J. Poly. Sci. Polym. Letters Ed. , 15 , 71 (1977)

12) i. C. Sanchez, "Polymer Blends", edited by D. R. Paul and S. Neuman, Vol. 1, Academic

Press, New York (1978).

13) G. Delmar, D. Patterson, and T. Somcynsky, J. Polym. Sci , 57 , 79 (1962).

14) B. E. Eichinger and P. J. Flory, Trans. Faraday Soc., 64, 2061 (1968).

15) P. J. Flory, J. L. Ellenson and B. E. Eichinger, Macromolecules , 1_, 279 (1968).

16) B. E. Eichinger and P. J. Flory, Trans. Faraday Soc. , 64 , 2061 (1968).

17) B. E. Eichinger and P. J. Flory, Ibid . , 64 , 2053 (1968).

18) M. J. Hayes and G. S. Park, Ibid , 51 , 1134 (1955).

19) A. Aitken and R. M. Barrer, Ibid , 51 , 116 (1955).

20) S. Prager, E. Bagley and F. A. Long, J. Amer. Chern. Soc. , 75 , 1255 (1953).

21) H. Fujita, A. Kishimoto, and K. Matsumoto, Trans. Faraday Soc. 56 , 424 (1960).

22) H. Fujita, "Diffusion in Polymers", ed. by J. Crank and G. S. Park, Academic Press, NY

23) I. Auerback, et. al., J. Polym. Sci. , 28 129 (1958).

24) R. K. Ghai, H. Ertl , and F. A. L. Dullien, AICHE Journal , 19 , 881, 1215 (1973).

25) Chapter 4 in reference 22

26) M. H. Cohen and D. Turnbull, J. Chem. Phys. , 31 , 1164 (1959).

-54-
27) D. Turnbull and M. H. Cohen, ibid , 52 , 3038 (1970).

28) F. Bueche, Ibid , 21 , 1850 (1953).

29) H. Fujita, Fortschi. Hochpolym. - Forsch. , 3, 1 (1961).

30) A. K. Doolittle, J. Appl . Ph.ys. , 22, 1471 (1951 ), 23 236 (1952).

31) A. Kishimoto and Y. Endu, J. Polym. Sci. A . 1799 (1963).

32) A. Kishimoto, Ibid , 2: , 1421 (1964).

33) A. C. Newns, Trans. Faraday Soc. 59 , 2150 (1963).

34) C. A. Kumins and J. Poteman, J. Polym. Sci. , 55 , 699 (1961).

35) Unpublished calculations of I. C. Sanchez.

36) “Handbook of Mathematical Functions", M. Abramowitz and I. A. Stegur. editors,

Dover Publications, New York (1965) p. 298.

37) W. R. Vieth, J. M. Howell and J. H. Hsieh J. Membrane Sci. , X, 177 (1976)

and references given therin.

38) W. R. Vieth and K. J. Slakek, J . Col 1 . Sci » 20 , 1014 (1965).

39) D. R. Kemp and D. R. Paul J. Polm. Sci ., Part A-2, J_2 S 485 (1974).

D. R. Paul and D. R. Kemp J. Polm. Sci , Part C, 41_, 79 (1973).

40) D. R. Kemp, "The Diffusion Time Lag in Heterogeneous Polymer Membranes"

Dissentation, the University of Texas, (1972).

University Microfilms Ann Arbor, Mich. No. 73-466.

- 55-
PRELIMINARY CLASSIFICATION OF ADDITIVE TYPES

Introduction

A J 1. h L of FDA approved additives (Section 178) for plastics

lo be used in contact with food are classified as to their

chemical characteristics, along with their maximum allowable

amounts (%)/ in particular types of plastics/and the maximum

thickness of the plastics in inches.

i Classification

A. ALCOHOLS AND ESTERS

1,3 - B ut anedio

1

P an t ae ry t h r i t o 1 0.4/PVC

P an t e a ry th r i t o 1 stearate 0.4/PVC

B. BENZOPHENONES

2- Hy d r o xy- 4-n- o c t o xy- b en z op he none 0.5/PO

Ad vas tab 4 6 Cyasorb UV5 3

1

2-Hydro xy-4-i-octoxy-benzophenone 0.5/P0(c)

Me th anone

[2-Hydro xy- 4- (i- o c t oxy ) pheny 1 ] pheny

1

C. METALLIC SALTS

1. CALCIUM:

2. COPPER:

3. LITHIUM:

4. MAGNESIUM:

5. POTASSIUM:

benzoate

my ris t ate

stearate

cupric acetate

cupric carbonate

cuprous bromide

cup rous iodide

iodide

salicylate

bromide

1 / POM ( c )

.025/ NY 66/ .0012

.005/ NY 66/ .0015

.0175/ NY 66/. 0015

.0025/ NY 66/ .0015

.065/ NY 66/. 0012

0. 3/RPVC(c)

0.18/ NY 66/. 0015

- 56-
6 . TIN : Di-n- o c ty 1- t in maleate polymer PVC

Di-n-octy 1-tin-bis (i-Octylmercap toacetate) PVC

Poly [ (1, 3-di-butyl-di-Stannthianediylidene)l,3-dithio] 0.2/PVC

7. ZINC: dibuty ldithiocarbamate 0.2/lB-IP(c)

salicylate 0.3/RPVC

palmitate

stearate

D. PHENOLS

Mono- :

2.6-

Di-t-butyl-p-cresol

I on o 1 BHT

Advastab 401

2.

6-

Di-t-butyl-4 -ethyl-phenol 0.1/E-P(c)/‘^^

Antioxidant 724 ,uZ " 2,6-Bis(i-me thy lheptadecyl )-p- ere sol .3/PO/.004

4-Hydroxy nethvl-2, 6-di -t-buty 1 phenol

Antioxidant 754

n-0ctadecyl-3 - (4' -hydroxy-3' 5 ' -di-t-butyl phenyl)

propionate

. 25 /PO/ . 0025

.05/P0/no limit

Octadecyl-3 , 5-di-£-butyl-4-hydroxy-hydrocinn am a t e Irganox 10 76

. 25 /PS , PS

. 5 / A-B-S

2 (2 ' -Hydroxy -5 '-methyl pheny l)benzotriazole

Tinuvin P

. 25/PVC(c) ,PS

2 (3' -b-Butyl-2 1 -hydroxy-5 ' -methylphenyl)-5-

ch lo r ob en zo t r i a zo 1 e .5/PO

Tinuvin 326

Butyrated styrenated cresols . 5/PS S P0

- 57 -
D. PHENOLS (continued)

fe

Di- :

4, 4 '-Methylene-bis (2, 6-di-b-butylphenoi) . 25/PHC resins,

Antioxidant 702 turpene resins

. 5 / P E , P B

2 , 2 ' -Methylene-bis (6- t-butyl-4-ethylphenol) . 6/ A-B-S

. IP A

2, 2 '-Methylene-bis (4- me thyl-6-t-butylphenol) . 1/PO

i / P OM ( c

)

. 5 /POM

4 , 4 ' -Butylidene-bis (4-t-buty 1-m-cresol) . 5/PP

. 3/PE

4 , 4

* -Thio-bis (6-t-buty

1

-m- c r e s o 1

)

Santonox

Advastab 415

Antioxydans KS

. 25/PE

2, 2* -Methylene-bis [6-(l-methylcyclohexyl)-p-cresol] . 2/PE/ .0005

4,4'-Cyclohexylidene-bis(2-cyclohexylphenol) . 1/PO

2,2'- Me thylene-bis(4-methyl-6-nonylphenol) A-B-S

Tri- :

2 , 6-Bis (2-hydroxy- 3-nonyl-5-methy l-benzyl)-p-cresol A-B-S

T r i s ( 2 - m e t h y 1 - 4 - h y d r o xy - 5 - t

b u t y 1 p h e n y 1 ) b u t a n e . 25 /A-B-S

. 1/ A-B-S

. 2/PS

1, 3,5-Trimethyl-2,4,6-tris-

(3,5-di-t-butyl-4-hydroxybenzyl)benzene

lonox 330 , Antioxidant 330

. 5 1/NY

1, 3, 5-Tris (3, 5-di-t-butyl- 4 -hydroxy-hydrocinnamoyl) hexanydro-s-triazine. 25/PP

. 1/PE

. 5 /E-P-EN/

. 005/ .005

l,3,5-Tris(3,5-di-£-butyl-4-hydrobenzyl)-

5-triazine-2 , 4 , 6 (1H, 3H, 5H) t rione

- 58 -

. 25/PP

.1/PE

. 5 /PE

. 5 /E-P-EN/

. 005

M

i

M

a

a

a

a

a

a

a

a

a

a

a

a

a

i
ABBREVIATIONS FOR POLYMERS

AA

A

B

(C)

E

Acrylic Acid

B utadiene

Copolyme r Ethylene

en S-Ethylidine-2-norbornene

IB Isobutylene

IP Isop rene

1 A Methacrylic Acid

NR Natural rubber

NY Nylon

P Propylene

PA P o ly ami de

PBD P o 1 y b u t adi ene

PE Polyetiiy lene

PHC Petroleum hydrocarbon

PO Polyolefin

POM Polyoxymethylene

PP Polypropylene

p Poly(vinyl chloride)

S Styrene

VAc Vinyl acetate
Molecular Models of Some of the Additives

o (O.lnm or 1A is represented by 1.2 cm of the model)

-AO-
-Di-^-butyl-p-cresol

rHowa) u01CuI rH

>1

-pI +iI •HQi

(N t

CD P

n3£

fdcc

•HUop

TS

x:

t>i X0u

TD

k“i ,C1 TI P

£3I -wI •HI inm

£0o

CD V

<d •PO01c

-6 2-

-Thio-bis (

6-

t-butyl-m-cresol)

- 63 -

Tetrakis

[methylene

(3,

5-di-t-buty

1-4-hydroxyhydrocinnamate)

]

methane

- 64-

Distearvl

thiopropionate
aaaaaaaaaaa
N6S-1 14A ihev /- / o

U.S. DEPT. OF COMM.

§ ]. HI J Js 1 K Al'ION OR REPORT NO. I 2. Gov’t Accession

BIBLIOGRAPHIC DATA MDC TD .... No. SHEET 1 NBS-IR - 78-1499

3. Recipient’s Accession No.

4. m i l: AND SUBTITLE

AN EVALUATION OF EXISTING MODELS DESCRIBING THE

MIGRATION OF ADDITIVES IN POLYMERS

5. Publication Date

6. Performing Organization Code

?'. A bT

M ^anchez ; S. S. Chang; F. L. McCrackin; & L. E. Smith

S. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No. 5630446

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

same as Item 9

13. Type of Report & Period

Covered

r inal 9-1-77 to 3-30-78

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSTRAC T (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.)

The objective of this work is the development of mathematical models

that describe the migration of a variety of small molecules in polymers

that have applications in food contact uses. In the most general cases,

these models will be able to predict the amount of additive migration

given any particular time and temperature history. These models can serve as the technical basis for more efficient regulatory methods under

existing frameworks or in the design and implementation of new indirect

additive regulations or policy.

The first steps in the development and assessment of such models

are given in this report. The first section presents a preliminary survey

of migration data applicable to food contact situations that are available

in the current literature. The second section surveys available models

describing migration and evaluates their present and potential utility.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons

)

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

regulati on

18. AVAILABILITY [TCj Unlimited

[j

' For Official Distribution. Do Not Release to NTIS

[ 1 Order From Sup. of Doc., U.S. Government Printing Office Washington, D.C.. 20402, SP Gat. No. G ) * Lj Order From National Technical Information Service (NTIS)

Springfield, Virginia 22151 USCOMM-DC 29042-P74

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