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New Additive Solutions for the PVC Industry

CONFERENCE PAPER SEPTEMBER 2002

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New Additive Solutions for the PVC Industry

Alex Wegmann, Alfred G. Oertli, Wolfgang Voigt
Ciba Specialty Chemicals Inc.
Plastic Additives Segment
CH-4002 Basel / Switzerland
Abstract
Phenolic products, especially sterically hindered phenols, are widely used throughout the PVC industry.
For instance, as chain-stoppers and antioxidants in PVC polymerization, to terminate the reaction and
prevent degradation of the virgin resin in the stripper and dryer. Methylmethacrylate-butadiene-styrene
(MBS), a frequently used impact modifier for rigid PVC, needs highly efficient protection against
oxidative degradation of its rubber phase by a synergistic blend of a phenolic antioxidant with a
thiosynergist. Plasticizers for flexible PVC in thermally demanding applications are also stabilized with
phenolic antioxidants.
In the above mentioned applications, traditionally used solid antioxidants are increasingly replaced by
more efficient, liquid products which give additional invaluable advantages in handling, dosing, and ease
of emulsification, very important for introduction into aqueous processes, as well as a good toxicological
profile, enabling broad registration and food approval status, thereby enhancing PVC's environmental
acceptance. Alternatively to stabilizing plasticizers, or to further boost the thermal stability of PVC, solid
hindered phenol antioxidants can be added to heat stabilizers, or directly to the compound.
Newly developed high performance light stabilizers and other effect additives (biocides, antistats,
antifogging and fluorescent whitening agents, etc.) enhance the quality of finished PVC articles, thereby
further strengthening the position of PVC applications in the marketplace.
1) Introduction:
PVC is one the most important thermoplastic polymers, approximately 25 million tons are produced and
processed each year. PVC is very versatile, and can be mixed with a variety of other polymers or
substances, to modify its mechanical and physical properties, very important among them are impact
modifiers for rigid PVC (e.g., MBS, acrylates), plasticizers for flexible PVC (e.g., phthalates, adipates,
trimellitates), pigments, fillers, thermal stabilizers (salts based on Pb, Ca/Zn, Sn, etc.), effect additives
(UV light stabilizers, biocides, antistats, antifogging and fluorescent whitening agents, etc.). Hindered
phenols are used in the polymerization of PVC, of MBS resins, and also for the stabilization of
plasticizers, thermal stabilizers, and PVC compounds (figure 1).
2) Chain-stopper / antioxidant for the PVC polymerization process [1]:

A good chain-terminator has to stop the polymerization reaction completely, and quench any remaining
catalyst residues (radicals), to avoid post-polymerization during the work-up of the resin. This will
guarantee less cleaning operations and, thus, a better plant productivity. IRGANOX 1141 (AO1) is a
synergistic liquid blend of two hindered phenols (figure 2). It is an excellent chain-stopper and catalyst
quencher, and its antioxidant properties give good thermal stability to PVC resins and compounds.
Moreover, the liquid supply form ensures easy handling, storing, and dosing. There are no dust
problems, nor organic solvents or carriers needed. This greatly reduces potential health, fire and
environmental hazards. The product can be added to the aqueous PVC suspension, either as straight
liquid, or, alternatively, as emulsion. The low viscosity makes it easy to emulsify. There is no significant
weight loss of AO1 in the temperature range relevant to the PVC polymerization, stripping, and drying,
i.e. up to 150C. AO1 is increasingly replacing traditionally used products such as BPA (Bisphenol A)
or BHT (di-t-Butyl-Hydroxy-Toluene).
3) Polymerization of MBS:
MBS is produced, similarly to ABS, by emulsion copolymerisation of a rubber (polybutadiene or
styrene-butadiene-rubber) together with styrene and methylmethacrylate. The MBS copolymer is
separated from water by coagulation, centrifugation and drying. MBS has a large internal surface area
(because its particles are very small) and contains a high amount of unsaturated rubber (up to
approximately 80%). Therefore, it is very prone to oxidation in the drying step in presence of oxygen,
and needs extremely efficient thermal protection. Market requirements for antioxidants for MBS: give
very good thermal stability to the MBS powder, as well as better heat stability to PVC compounds
modified with MBS, improved handling of the additive, better cost/performance, easier preparation and
better storage stability of antioxidant emulsions.
State of the art have been solid, fully or partially hindered phenols, like IRGANOX 1076 (OBP) or
IRGANOX 245 (AO2) in emulsified form, together with thiosynergists, like DLTDP (dilaurylthiodipropionate) or DSTDP (distearyl-thiodipropionate). Here also, the liquid supply form of AO1 is a
big advantage. It can be emulsified easily, and the emulsion can be stored at room temperature. Figure 3
shows that AO1 is even better in thermal stabilization than other hindered phenols, and it also improves
the performance of PVC in the milling test (figure 4).
4) Antioxidants for plasticizers:
Only for thermally very demanding applications, like flexible PVC for wire & cable or automotive
interior, plasticizers need to be stabilized with antioxidants. The main purpose of the antioxidant is to
protect the plasticizer in the PVC formulation against thermal oxidation during the processing, as well as
during the manufacturing and the life time of the finished article. In presence of oxygen, tertiary carbon
atoms in the plasticizer can undergo autoxidation to form, ultimately, low molecular weight acids that
have no more plastifying effect (figure 5). The antioxidant, in combination with traditional heat stabilizers
(e.g. salts containing Sn, Pb, Ca/Zn), also helps to protect the PVC to a certain extent against
dehydrochlorination. This is also important because hydrogen chloride released during the thermal
dehydrochlorination of PVC can further accelerate the decomposition of the plasticizer.

Up to now, BPA has clearly dominated the market for the stabilization of plasticizers. For practical
reasons, and to ensure a homogeneous distribution, the antioxidant is usually added to the plasticizer.
Important requirements the antioxidant has to fulfill: Miscibility, compatibility, and good solubility in the
plasticizer; low volatility (little weight loss during thermal aging), and no fogging tendency; retention of
mechanical properties (tensile strength, elongation), no discoloration, and low hydrogen chloride release
under thermo-oxidative conditions.
In the so-called Congo-Red-Test (DIN VDE 0207 part 614), a good measure for the efficiency of an
antioxidant, IRGASTAB PVC 11 (AO PL-L), based on very similar chemistry as AO1, shows a
similar performance as BPA or OBP, whereas BHT is clearly inferior (figure 6). The clear advantage of
AO PL-L is the liquid supply form that renders it well soluble in plasticizers, compared to solid products,
and makes its handling and dosing very easy. The weight loss in a PVC compound (14 days/ 140C) is
approximately 5%, comparable to BPA. Alternatively, the antioxidant can be added by the PVC
compounder to the PVC formulation, in this case a solid supply form is preferred. IRGASTAB PVC
86 (AO CO-S) fulfills this requirement, and is also very effective in the Congo-Red-Test.
5) Regulatory issues:
Lately, BPA has come under pressure because of its alleged endocrine modulating properties (estrogen
mimic). Therefore, the PVC industry in Western Europe has made the decision to phase-out BPA in
PVC polymerization by the end of 2001. Depending on the actual recipes, the amount of BPA in PVC
compound formulations, needed for the stabilization of plasticizers, is about 10x higher than the amount
from the polymerization step. Therefore, the phase-out of BPA in PVC resins will remain of limited
practical value, as far as the concentration of BPA in the final PVC article is concerned, as long as BPA
is still used in plasticizers. Nevertheless, it is a first step and clear signal that the PVC industry is
determined to use additives which strengthen the image of PVC from an environmental point of view,
and foster its sustainable future.
Investigations have shown that AO1, and also AO PL-L and AO CO-S, do not show endocrine
modulating properties. Besides, the products have very favorable toxicological profiles, and are
registered globally. They have FDA approval for rigid PVC (0.04%), as well as for flexible PVC
(0.03%), in PVC films thinner than 1 mil (= 2.5mm), for aqueous and acidic food. In Europe, the
components of AO1 are approved in all plastics up to a SML (specific migration limit) of 1mg/kg food
(CGX AO 145), respectively 6 mg/kg food (OBP).
6) Effect additives:
High Performance UV Light Stabilizers
PVC compounds have traditionally been stabilized by hydroxyphenyl-benzophenone or hydroxyphenylbenzotriazole UV-absorbers (UVA). Although in certain formulations Hindered Amine Light Stabilizers
(HALS) showed an improvement of the light stability, HALS have so far not found broad acceptance in
PVC light stabilization. The reason is, most likely, that hydrogen chloride released during degradation of
PVC can protonate the HALS, thereby reducing their efficacy. Now, new high performance UV light
stabilizer systems (TINUVIN XT) have been developed, that can be effectively tailored towards the

type of PVC compound and its application. They do not react easily with hydrogen chloride, showing a
considerably improved light stability after artificial weathering, in retention of color (figure 7) and
mechanical properties (table 1).
Biocides
IRGAGUARD A 2000 (white powder, melting range 128 - 133C) prevents the growth of algae, moss,
etc., on the surface of PVC articles (inliners, sidings, roofings, tents, etc.), thereby retaining the original
appearance and transparency. Due to the good compatibility with PVC, it is highly efficient. Controlled
release of the molecule ensures an excellent long-term activity. It is highly specific and effective, by
inhibiting the photosynthesis in the algae (figure 8). The product has favorable toxicity and ecotoxicity
profiles: low acute toxicity, not irritant, not mutagenic, only weakly skin sensitizing, and inherently
biodegradable. Despite the intended high toxicity against algae, the product is not toxic against
invertebrates, birds, fish, and sediment living organisms.
IRGAGUARD B 1000, a bacteriostatic antimicrobial, can be incorporated into polymers, often via a
masterbatch. It migrates to the surface of the finished articles, thus inhibiting the growth of many
microorganisms (bacteria, mold, yeast, etc.) and, thereby, considerably increasing safety, hygiene, and
health standards. This antimicrobial is supplied as a fine, thermally stable (>300C) powder, with a
melting point of 57C. It is highly effective, has a broad spectrum of activity, and does not cause
resistance in microorganisms. Whereas PVC itself is relatively resistant to microbial attack, plasticizers,
fillers, pigments, and additives in the plastic can serve microorganisms as nutrients. Figure 9
demonstrates visually the efficacy of the antimicrobial in a rigid PVC formulation: there is a large zone
free of microbes around the treated article.
Antistatic Additives
Static electricity is commonly generated in polymers by friction. High electrical charges can have a
negative impact on polymer production and processing (risk of electrical shocks to employees, risk of
spontaneous electrical discharges causing fires or explosions, etc.), as well as on the use and appearance
of finished plastic materials (e.g., dust contamination). The magnitude of the charge depends on the
degree of contact, the plastics frictional and intrinsical electrical properties (dielectric constant and
resistivity), as well as the surrounding medium (relative humidity).
Antistatic additives are amphiphilic molecules, capable of reducing electrical charges on plastic surfaces
by rendering them slightly conductive, i.e. lowering their surface resistivity. Surface resistivity is defined
as the intensity of current flowing over the surface of a plastic when a given potential is applied between
two electrodes (ASTM D257). Internal antistats are added to polymers during the processing. In the
finished article they continuously migrate to the surface, where they adsorb water in order to develop a
mid to long term effect of reduced resistivity (figure 10). The rate of migration is influenced by the
concentration of the antistat, the temperature, the relative compatibility of the antistat with the polymer,
the polymer crystallinity (migration proceeds through the amorphous phase), and potential co-additives.
Fillers and pigments tend to adsorb and retard migration, whereas HALS and slip additives tend to
promote it. For good antistatic properties, the surface resistivity should be lower than 10-12 Ohm/Square.

ATMER 190 (AS-1, based on alkyl sulphonate) provides the best performance in terms of lowering
surface resistivity in rigid PVC. It is very suitable for high temperature processing, but leads to opacity in
clear articles. ATMER 129 (AS-2, based on GMS = glycerolmonostearate), on the other hand, is less
efficient, but has no adverse effect on transparency (figure 11). In flexible PVC, ATMER 154 (AS-3,
based on ethoxylated coconut acid) performs better than AS-2 (figure 12). An additional advantage of
AS-3 is its liquid product form, which enables an easy miscibility with other components in the PVC
formulation. In general, AS-2 is a suitable short term antistat with a quick performance build-up, but
provides less long-term effect compared to AS-3.
Antifogging Additives
The term fogging is typically used to describe the condensation of water vapor upon a plastic films
surface in form of small discrete droplets. Fogging may be observed when an enclosed mass of humid air
cools to a temperature below its dew point. This effect is especially undesired in food packages, stored
in refrigerated cabinets, where condensed water droplets reduce the attractiveness of the packed good,
and in agricultural applications, such as greenhouses, where the droplets and the resulting loss of
transparency reduces the light transmission and, therefore, the crop growth behind the film. Antifogging
Agents reduce the surface tension of the film, are soluble in water and, thus, lead to an improved spreadout of the water on the surface. The desired lifetime of the antifog effect necessitates a clear distinction
between the two major applications: food packaging and agricultural films:
In food packaging, the antifog effect should typically last for a few days, as the packed good will
normally not exceed a shelf life longer than one week in the cold cabinet. An excellent reduction of fog
formation in PVC with classical plasticizers is achieved by a combination of an ethoxylated sorbitan ester
such as ATMER 116 (AF-1) with a glycerol ester such as ATMER 1010 (AF-2) in a ratio of 1:2 or
1: 3 (table 2). If polymeric plasticizers are used, the migration of the antifogging agent is often reduced.
In these cases, the use of a sorbitan ester, e.g. ATMER 100 (AF-3) should be taken into
consideration. The choice of a suitable greenhouse antifogging agent is governed by different
requirements: long term performance for several months or years and continuous wash-off of the
antifogging agent by the condensed water necessitate a different approach: PVC films for greenhouse
application with antifogging effect typically contain sorbitan esters such as ATMER 103 (AF-4) with
a modified chemical structure in order to maximize the duration of the effect and to minimize the
extractability of the surfactant.
Fluorescent Whitening Agents (FWA):
Many thermoplastics absorb light in the blue spectral range of natural daylight (blue defect), hence
causing a more or less pronounced yellowish appearance. Fluorescent whitening agents, or optical
brighteners, are capable of absorbing invisible UV radiation, converting it to longer wavelength and reemitting it as a visible blue or violet light (fluorescence). Thereby, the unwanted yellowish appearance of
the substrate is compensated and, in addition, more visible light in the range of 400 to 600 nm is
reflected than was originally incident; hence the article appears whiter, brighter and more brilliant (figure
13). In practice, concentrations of 50 - 500 ppm of fluorescent whitening agents are used in
thermoplastics. Benefits for the end use articles include masking of the initial color of plastics, increase of

the brilliancy of white, black, or colored articles (fashion goods of imitation leather, packaging materials,
etc.).
For PVC, the following products are used: UVITEX OB (FWA-1), UVITEX FP (FWA-2);
UVITEX OB-ONE (FWA-3). They achieve a substantial whitening effect in rigid (figure 14), and
flexible PVC (figure 15), relatively good light fastness, excellent compatibility and thermal stability, which
makes them suitable for melt processing.
7) Conclusions:
Hindered phenol antioxidants are widely used in the PVC industry as chain-stoppers and antioxidants in
PVC polymerization, thermal stabilizers for MBS impact modifiers, antioxidants for PVC plasticizers and
heat stabilizers, as well as PVC compounds. Benefits are the excellent technical performance, easy
handling (liquid supply forms), good toxicological profile, and broad food approvals. New high performance
additives for PVC compounds feature UV light stabilizers, biocides, antistats, antifogging and fluorescent
whitening agents. These additives help considerably to strengthen the performance and acceptance of
PVC in the market.
8) Bibliography:
[1]

A. Wegmann, P. Xanthopoulos, Proceedings of the Current Trends in PVC Technology

Conference; 2000, Loughborough University, Loughborough, UK.

PVC Resin

Heat stabilizers
Ba / CaZn / Sn salts

AO

AO
Additives:
- Biocides
- Fluorescent Whitening
- Light stabilizers
- Antistats, Antifog

PVC Compound

AO
pigments

fillers

Figure 1: Use of phenolic antioxidants (AO) in PVC Applications

Plasticizer for
flexible PVC:
- phthalates,
- trimellitates,
- adipates, ...

AO

Impact modifier
for rigid PVC
- acrylic resin
- MBS
AO

OH

OH
OH

HO

O
BPA

C18 H 3 7
O
IRGANOX 1076 (OBP)

BHT

OH

OH

OH

C1 4 H 2 9
O

O
O

O
IRGANOX 245 (AO 2)

C G X-A O 1 4 5 ( 8 0 % )

C18 H 3 7

IRGANOX 1076 (20%)

IRGANOX 1141 (AO 1)

Figure 2: Chemical structures of chain stoppers / antioxidants

minutes to the
max of the exotherm

100
80
60
40
20
0
0.15% AO 1 / 0.45%
DLTDP

0.15% AO 2 / 0.45%
DLTDP

0.15% OBP / 0.45%

DLTDP

Figure 3: Thermal stability of MBS (DSC isothermal method, at 180C, oxygen)

Yellowness
Index

PVC stability
M i l l i n g t e s t o f R -P V C c o n t a i n i n g 1 5 % M B S

35

MBS Stabilization :
30

OBP

0.2 % AO +

25

1.0 % DLTDP

AO 2
20
15
10

P V C s t a b i l i z a t i o n:
octyltin stabilized

AO 1
5
0
0

10

20

30

Milling time in min

Figure 4: Thermal stability of PVC, evaluated by milling test at 180C

R-C-(CH2)x-CH3

O2

OOH
-C-(CH2)x-CH3

-scission

-C-(CH2)x-CH3

O
-C + CH2-(CH2)x-1-CH3

CH2

CH2

CH2

CH2

CH3

CH3

CH3

CH3
O

O2 / H
HOO-CH2-(CH2)x-1-CH3

C -(CH2)x-1-CH3
H

Figure 5: Autoxidation mechanism of branched plasticizers

ACIDS

Congo-Red-Value (minutes)

160

136

120

PVC Sheathing
Formulation: parts

130

132

125

PVC
100.0
DIDP
52.0
Filler
50.0
Heat stabilizer 4.5
AO
0.3

95.5
74

80

40

Lab Test: Congored

DIN VDE 0207 part 614)
AO

CO
-S

PL
-L
AO

OB
P

BP
A

co
ntr
ol

BH
T

Figure 6: Performance of antioxidants in plasticized cable formulations

6
0.5 parts Benzophenone UVA
0.5 parts High Performance UV LS

3.0 parts Ba/Zn

Thermal stabilizer

Delta YI

4
3

0.5 mm plaques;

WOM (xenon)
ASTM G 26

1
0
-1
0

2000

4000

6000
8000
Hours

10000

12000

Figure 7: Color retention of flexible PVC after artificial weathering

Table 1: Retention of mechanical properties of flexible PVC after artificial weathering

% Retention of elongation
after artificial weathering

2000 Hrs

4000 Hrs

6000 Hrs

8000 Hrs

0.5% Benzophenone UVA

100

100

100

71

0.5% High Performance

UV Light Stabilizer

100

100

100

91

Control

0.1% Algae growth inhibitor

Figure 8: Biocides for algae growth inhibition in flexible PVC

Pseudokirchneriella subcapitata SAG No. 61.81 (= Selenastrum capricornutum ATCC 22662)
Incubation period 7 days at 25C, continuous light 100 Microeinstein / m2 x sec (400-700 nm)
(1 Einstein = 1 Mol Photons = 6 x 1023 photons)].

No Microbial
Growth Inhibitor

0.1% Microbial
Growth Inhibitor

0.5% Microbial
Growth Inhibitor

Figure 9: Microbial Growth Inhibitors in rigid PVC formulations

(Staphylococcus aureus ATCC 9144)

H2O

H 2 O H 2O

Amphiphilic
Antistatic
Agent

H2 O

Plastic part

H 2O

H2O
H2 O

Figure 10: Mode of action of antistatic agents

LOG OF SURFACE RESISTIVITY

16

Rigid PVC formulation:

parts

14

PVC Resin:

12

100

ESBO:

Heat stabilizer:

Stearic acid:

0.5

Antistat:

10
1 day

1 week

control

Figure 11:

2 weeks

4 weeks 2 months

TIME

AS-1 (based on alkyl sulphonate; opacity)

AS-2

Antistatic agents in rigid PVC applications

AtmerTM is a trademark of UNIQEMA
All AtmerT M products are exclusively distributed by Ciba Specialty Chemicals

LOG OF SURFACE RESISTIVITY

Flexible PVC
formulation: parts

14
13

PVC Resin
12
11

100

DOP:

40

Rheofos 65:

12

Cereclor S45: 10
10

Heat stabilizer

Antistat:

1 day
control

1 week

2 weeks
AS-2

4 weeks 2 months

TIME

AS-3 (based on coconut acid ester)

Figure 12: Antistatic agents in flexible PVC applications

Table 2: Antifogging agents in flexible PVC food wrap films

refrigerator 4C
film

water

cold fog test

time

5
M

30
M

1
HR

3
HR

6
HR

1
D

4
D

1
W

control

AB

AB

AB

AB

AB

3 parts
AF-2

DE

DE

Description
Performance Rating
Opaque layer of small fog droplets
Very poor
A
Opaque or transparent layer of large droplets Poor
B
Complete layer of large transparent drops
Poor
C
Randomly scattered or large transparent drops Good
D
Transparent film displaying no visible water
Excellent
E

incident
radiation
reflection

visible light
absorption
UV light
absorption

Untreated material:
absorbs only visible, mainly blue
light yellow cast

Material + FWA: UV also absorbed,

converted to blue light reflectance
+ fluorescence. Compensates yellow cast
and increases brilliance

Figure 13: Mode of action of fluorescent whitening agents

Rigid PVC
Formulation:

170

Whiteness Index
(GANZ)

150

parts
100.0 PVC
2.5 S/Sn stabilizer
2.0 ESBO
0.2 Lubricants
5.0 Titanium dioxide

130
110
90
70

Control

FWA- 1

FWA- 2

FWA- 3

compression molded
plaques (1mm)

50
0

200

400

600

800

1000

concentration [ppm]

Figure 14: Whiteness index of a rigid PVC formulation as function of FWA concentration

210

Flexible PVC
Formulation:

190
Whiteness
Index (GANZ)

170

parts
100.0 PVC
35.0 DOP
2.0 Thermalstabilizer
5.0 Titanium
dioxide

150
130
110
90

Control

FWA- 1

70

FWA- 2

FWA- 3

50
0

200

400

600

800

1000

concentration [ppm]

Figure 15: Whiteness index of a flexible PVC formulation as function of

FWA concentration

compression molded
sheets (1mm)