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Theory of Antistatic Agent Migration

Frank Lochel and Michael Watson – Chemax Polymer Additives

Abstract
A theory of antistatic agent migration is proposed based upon
specific additive and polymer properties. Two examples are
discussed. The first looks at the properties of a variety of
phosphate esters in low-density polyethylene. Their predicted
and actual performance is discussed. The second example
explores coco amine POE 2 incorporated into a range of
polymers looking at predicted versus actual results.

Polymer Properties

To begin developing our theory of chemical migration in polymeric


materials, we begin by first considering the gross structure of the
polymer itself. Polymers can be amorphous, crystalline or a blend
of both. This difference is analogous to a crystal of quartz versus
an amorphous quartz called an opal. One would never expect a
quartz crystal to be permeable to any chemical while opal is easily
permeable. The difference is in the molecular structure of these
materials. The crystal has very high intermolecular bonding
strength, the opal is composed of spheroids of SiO2 that are packed
in an ordered array but with large voids between the spheroids –
just like a box filled with uniformly sized balls.

Recognizing these differences, we theorized that migration in


polymers is most likely to occur in amorphous regions rather than
crystalline regions.

Given this theory there are three polymer properties that will impact
migration rate: Specific gravity, glass transition temperature and
polarity.

Specific gravity

Specific Gravity is the most easily measured indicator of


relative crystallinity within a chemical group. If one
compares the specific gravity of LDPE versus HDPE one
would expect that migration through LDPE would be faster
than through HDPE. This effect is even more pronounced

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when comparing more diverse polymers such as LDPE
versus Polystyrene.

LDPE HDPE PP PS ABS


Specific 0.91- 0.94 – 0.902 – 1.04 – 1.01 –
Gravity 0.93 0.96 0.906 1.10 1.07

Glass Transition Temperature Tg

Tg is a good indicator of the intermolecular bonding strength


in a polymer. It is expected that the lower the Tg the more
permeable the polymer If a very fast migrating additive is
present during processing of the polymer, it will have
maximum mobility while at a temperature > Tg.
LDPE HDPE PP PS ABS
Glass Transition -110 °C -90°C 0° 100°C 110°C
Temperature

Polarity

It is not the polarity of the molecules in the polymer that


determine additive migration speed, but the differences in
polarity between the polymer and the additive that is
important. One would expect a very polar additive to migrate
quickly through LDPE, itself non polar. We would expect a
non-polar additive to migrate quickly through very polar
polymer such as PVC.

PP LDPE HDPE PS ABS


Relative Polarity 1 2 2 4 5
Rank in order of increasing polarity

Additive Properties
There are a variety of additive properties that can impact migration. The
significance of some of these is in direct relationship to the polymer, such as
polarity. Others are independent of the polymer, such as molecular weight.
Outlined below are the suspected impact on migration for molecular weight,
solubility, viscosity, pH, HLB, thermal stability and terminal group chemistry. We
believe that these properties taken as a whole provide a predictive model for
migration.

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Molecular Weight

Some additives can be formulated to meet polarity and


functional group expectations as relatively small molecules
others are only possible as large molecules. Due to the
interstitial spaces in the polymer, the smaller the molecule
the faster the migration.

Solubility

If the additive is relatively insoluble in the polymer then the


polymer will be stressed by the presence of the additive and
in its effort to seek thermo dynamic stability will endeavor
to exclude the additive from its structure – this accelerates
migration. If additive solubility is extremely poor, the
polymer may suffer structural weakness. An example is if
excessive moisture is present in a polymer additive the
polymer, when processed, will lack integrity.

Conversely if the additive is very soluble in the polymer,


migration will be slow but dispersion of the additive in the
interstitial matrix will be greater.
pH

We have found that pH has a significant influence on antistat


performance. Additives having extreme pH’s have been
found to have excellent surface activity and fast migration
speeds.

HLB

The Hydrophilic-Lipophilic Balance (HLB) indicates whether


an additive is water or oil soluble. Due to the oil soluble
nature of most polymers one would expect that low HLB (oil
soluble) additives would be most useful in polymers. The
that HLB is a good representative for additive polarity. The
greater the HLB the more polar the additive. Surfactant
additives are ranked on a 1 to 20 scale where 1 to 6 are oil
soluble, 7-9 water dispersible and 10 and above water-
soluble.

Thermal Stability

The additive must be thermally stable at the processing


temperature of the polymer. While this is secondary to the
other properties discussed, not considering this important
parameter can be fatal to any model.

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Terminal Group Chemistry

For migrating antistats terminal group chemistry provides the


ability to hold moisture on the polymer’s surface. The
holding force is hydrogen bonding between the water
molecules and the antistat’s polar terminal groups.

Method
Summary:
We used surface resistivity measurements over time to
demonstrate migration speed. We conducted two studies. First we
evaluated a diverse range of phosphate ester chemistries (not
typically seen as antistatic agents in polymers) to determine if we
could predict their performance. We based the evaluation upon the
properties mentioned by looking at their performance in one
polymer, LPDE (Low Density Polyethylene).
Second we tested one known antistatic agent, coco amine POE2,
commonly know as CAM2, to determine if we could predict its
performance in a range of polymers.

For different additive types various properties will carry greater


weight in predicting performance. Major influences of antistat
migration are: additive solubility in the polymer, relative polarity of
the additive versus that of the polymer, molecular weight and
functional group concentration at the surface.

Procedure
Phosphate Esters
The phosphate esters synthesized for this worked have one of two
forms, either Mono-Ester or Di-Ester.
O O
|
R-O-P-OH R-O-P-OR
| |
OH OH
Mono-Ester Di-Ester

Phosphate esters can further be classified based on their R-groups.


For this study we used three main groups and modified them with-
in the group by adding various levels of polyoxyethylene (POE) to
vary solubility, molecular weight and HLB. These groups are:

Linear Chain:
These should have the least resistance to migration based on
spatial configuration. The following materials were selected:
• C4:(Butyl) mono-ester with 2 moles ethylene oxide
(C4 POE2)

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• C10: (Decyl) di-ester with 4 moles ethylene oxide
(C10 POE4)
• C10-12:(Decyl-Lauryl) mono-ester with 6 moles ethylene
oxide (C10-12 POE6)

Branched Chain:
These should be slower migrating versus the linear materials.
• C8: (2 Ethyl Hexyl) di-ester with 2 moles ethylene oxide
(C8 POE2)
• TDA-3:Tridecyl Alcohol di-ester with 3 moles ethylene oxide
(TDA POE3)
• TDA-6: Tridecyl Alcohol di-ester 6 moles ethylene oxide
(TDA POE6)
• TDA-9: Tridecyl Alcohol di-ester 9 moles ethylene oxide
(TDA POE9)

Aromatic:
These should be slowest migrating based on their larger spatial
configuration than either the linear or branched R-groups. Their
aromatic nature may make them more soluble in some polymers
such as PET or Styrene.
• Phenol di-ester with 6 moles ethylene oxide (Phenol POE6)
• Octyl Phenol monoester with 7 moles ethylene oxide
(OP POE7)
• Nonyl Phenol diester with 9 moles ethylene oxide
(NP POE9)
• Dinonyl Phenol diester with 8 moles ethylene oxide
(DNP POE8)

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Properties of Various Phosphate Esters
Linear Phosphate Esters Aromatic Phosphate Esters Branched Chain Phosphate Esters

Property C4 C10 C10-12 Phenol Octyl Nonyl Dinonyl Tridecyl Tridecyl Tridecyl C8
Phenol Phenol Alcohol Alcohol Alcohol
Moles EO 2 4 6 6 7 9 8 3 6 9 2
Mono or Di Mono Di Mono Di Mono Di Di Di Di Di Di
Ester
Molecular 242 730 516 778 594 1294 1458 726 990 1252 498
Wt
pH <3 <3 <3 <3 <3 <3 <3 <3 <3 <3 <3
Thermal >350 >350 >350 >350 >350 >350 >350 >350 >350 >350 >350
Stability °C

HLB 13.9 12.2 13.9 16 13.6 13.7 10.9 9.9 12.6 14.1 10.9
Terminal (OH)2 (OH) (OH)2 (OH) (OH)2 (OH) (OH) (OH) (OH) (OH) (OH)
Group

On a relative scale with other polymers we would expect additives


to migrate faster through LDPE due to its low specific gravity and
low Tg. Given that LDPE is a non-polar polymer we would expect
the additives with the greatest polarity to migrate fastest. Within
additives with similar polarity we would expect those with lower
molecular weight to migrate fastest. The fastest migrating additive
may not make the best antistatic agent. If it migrates too fast it may
be left on the barrel of the extruder, oil out on the surface of the
polymer or loose its effect over a short period of time.

We were able to keep the pH and thermal stability relatively


constant over the range of phosphate esters. The terminal groups
were the same within the mono-ester and di-ester subgroups.
Therefore the predictive factors are polarity (as described by HLB)
and molecular weight. Based on molecular weight we would expect
the C4 POE(2) mono-ester to be the fastest and the dinonyl phenol
POE(8) to be the slowest. Looking at polarity we would expect the
phenol POE(6) di-ester to be the fastest and the tridecyl alcohol
POE(3) di-ester to be the slowest.

The relative predictive effect of polarity versus molecular weight will


be seen by observing two sets of three phosphate esters:

In the first set they all have a similar molecular weight (near 730).
• C10: (Decyl) Di Ester with 4 moles ethylene oxide
• TDA-3:Tridecyl Alcohol diester with 3 moles ethylene oxide
• Phenol diester with 6 moles ethylene oxide

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In the second set they all have a similar HLB (polarity) value (10 –11):
• C8: (2 Ethyl Hexyl) Di Ester with 2 moles ethylene oxide
• TDA-3:Tridecyl Alcohol diester with 3 moles ethylene oxide
• Phenol diester with 6 moles ethylene oxide

Predicted Antistatic Performance of Various Phosphate Esters in LDPE


Property C4 C8 C10 C10- Phenol Octyl Nonyl Dinonyl Tridecyl Tridecyl Tridecyl
12 Phenol Phenol phenol Alcohol Alcohol Alcohol
Moles EO 2 2 4 6 6 7 9 8 3 6 9
Mono or Di Mono Di Di Mono Di Mono Di Di Di Di Di
Natural LDPE 13 13 13 13 13 13 13 13 13 13 13
Immediate SR 11 12 12 12 12 12 12 12 12 12 12
30 DaysSR 12 12 <11 11 <11 12 <11 <11 <11 <11 <11

Actual Antistatic Performance of Various Phosphate Esters in LDPE


Property C4 C8 C10 C10- Phenol Octyl Nonyl Dinonyl Tridecyl Tridecyl Tridecyl
12 Phenol Phenol phenol Alcohol Alcohol Alcohol
Moles EO 2 2 4 6 6 7 9 8 3 6 9
Mono or Di Mono Di Di Mono Di Mono Di Di Di Di Di
Natural LDPE 13 13 13 13 13 13 13 13 13 13 13
Immediate SR 11 13 11 12 12 13 12 12 11 12 12
10 Days SR 12 13 11 11 11 13 11 11 11 10 11
30 Days SR 12 13 11 11 12 13 11 10 11 11 -

Conclusion:
First we will consider the impact of molecular weight. Since we expected
differences between the mono-ester (OH)2 and di-esters (OH), we will address
each separately. Below are the results sorted by terminal group and by
molecular weight.

Performance Sorted by Terminal Group and Molecular Weight


Property C8 Tridecyl C10 Phenol Tridecyl Tridecyl Nonyl Dinonyl C4 C10-12 Octyl
Alcohol Alcohol Alcohol Phenol Phenol
Moles EO 2 3 4 6 6 9 9 8 2 6 7
Molecular 498 726 730 778 990 1252 1294 1458 242 516 594
Wt
HLB 10.9 9.9 12.2 16 12.6 14.1 13.7 10.9 13.9 13.9 13.6
Terminal (OH) (OH) (OH) (OH) (OH) (OH) (OH) (OH) (OH)2 (OH)2 (OH)2
Group
Initial SR 13 11 11 12 11 12 12 12 11 12 13
10 Day SR 13 11 11 11 10 11 11 11 12 11 13
30 day SR 13 11 11 12 11 11 11 10 12 11 13

Within the mono-esters the lowest molecular weight material acted as expected.
The C4 POE2 migrated fast but lost performance overtime. The midsize mono-
ester also reacted as predicted. C10-12 POE6 migrating slower with improved

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performance over time. Only the aromatic compound failed to meet the predicted
performance. This could be due to the aromatic nature of the molecule.

Within the di-esters, we observed either loss in extrusion or no effect, for the
lowest molecular weight material (C8 POE2). There is a general trend towards
slower initial migration as the molecular weight rises. It can also be seen that the
larger molecular weight items improve overtime.

Of those materials with very similar molecular weights but different HLB values
there were some interesting observations. The linear (C10) and the branched
(TDA POE3) had identical properties even though there was almost 2.5 points
difference in their HLB. Given this performance the aromatic material (Nonyl
Phenol POE9) would be expected to migrate faster due to the significantly
different HLB value (3.8 units higher than TDA POE3). Instead it migrates slowly
initially and looses performance quickly.

Performance Sorted by Terminal Group and HLB


Property Tridecyl C8 Dinonyl C10 Tridecyl Nonyl Tridecyl Phenol Octyl C4 C10-12
Alcohol Alcohol Phenol Alcohol Phenol
Moles EO 3 2 8 4 6 9 9 6 7 2 6
Molecular 726 498 1458 730 990 1294 1252 778 594 242 516
Wt
HLB 9.9 10.9 10.9 12.2 12.6 13.7 14.1 16 13.6 13.9 13.9
Terminal (OH) (OH) (OH) (OH) (OH) (OH) (OH) (OH) (OH)2 (OH)2 (OH)2
Group
Initial SR 11 13 12 11 11 12 12 12 13 11 12
10 Day 11 13 11 11 10 11 11 11 13 12 11
SR
30 Day 11 13 10 11 11 11 11 12 13 12 11
SR

Secondly we will consider the importance of HLB. Within the mono-esters there
is very little difference in the HLB values, although significant performance
differences resulted. This would imply that molecular weight and R-group spatial
configuration play a more significant role in their migration.

Within the di-esters, some interesting observations can be seen. We had


expected that the higher HLB (more polar material) would migrate fastest. The
ones with the highest HLB: Phenol POE6, TDA POE9 and Nonyl Phenol POE9
actually had slow initial migration with improvement overtime.

Within the materials with similar HLB values molecular weight was very
predictive. C8POE2 didn’t function at all, TDA POE3 was fast and steady and
Dinonyl Phenol POE8 improved overtime.

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Coco amine POE2 in Various Polymers

CH2CH2—OH
C12H25—N
CH2CH2—OH

Properties of Cocoamine POE 2


Molecular Viscosity PH Thermal HLB Terminal
Weight Stability Group
275 150mPa/s 10 >500°F 6.1 (OH)2

Coco amine POE2 has a relatively low molecular weight implying fast migration
in any polymer, especially an amphorous polymers. Its linear R-Group also
indicates fast migration is expected. The relatively low HLB indicates it would
move slower through non-polar polymers versus polar polymers. The terminal
group indicates sufficient hydrogen bonding to form a water layer at the surface
of the polymer.

Properties of Various Polymers


Polymer Property LDPE HDPE PP PS ABS
Specific Gravity 0.91- 0.94 – 0.902 – 1.04 – 1.01 –
0.93 0.96 0.906 1.10 1.07
Glass Transition -110°C -90°C 0°C 100°C 110°C
Temperature
Relative Polarity 2 2 1 4 5
Ranked in order of
increasing polarity

All of these polymers are processed above their Tg’s so we would not expect this
to have an impact on initial antistatic performance. The specific gravity would
indicate that PP is the least crystalline polymer and presents the lowest
resistance to migration. The polarity of the polymers would indicate that coco
amine POE2 would move faster through the PE polymers than through PP, PS or
ABS.

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Predicted Performance

Polymer Property LDPE HDPE PP PS ABS


Natural Polymer SR 13 13 13 12 13
Initial SR 11 12 12 11 12
60 Day SR 10 10 10 9 11

Actual Performance

Polymer Property LDPE HDPE PP PS ABS


Natural Polymer SR 13 13 13 12 13
Initial SR 10 12 11 11 11
3 Day SR 10 11 10 11 10
21 Day SR 10 11 10 10 10
60 Day SR 10 10 10 9 10
Use concentration 0.4% 0.4% 0.8% 2% 0.9%

Conclusion:
The expectation that coco amine POE2 would migrate faster in LDPE versus
HDPE was accurate given that HDPE is more crystalline than LDPE. HDPE did
show improvement overtime as would be expected with an additive that is slower
migrating. While PS, with the highest specific gravity, did show the slowest
migration there was no differentiation between PP and ABS even though there is
0.10 unit difference in their specific gravities. This would need to be studied
further to determine other causal factors.

Final Conclusion:
Given these results it can be seen that additive properties can predict
performance in different polymers. The various properties carry different weight
in predicting performance. In this study they can be ranked as molecular weight
first, functional group second and HLB third. While HLB is a good objective
measurement of additive polarity more work needs to be done to better
understand each polymers relative HLB. For example, coco amine POE2 has an
HLB of 6.1, which is the least polar of all additives in this study. It still migrated
quickly through LDPE. Possibly LDPE’s relative HLB is well below 6 allowing
materials like coco amine POE2 to migrate quickly.

Further Work:

In addition to further determining the relative HLB of the base polymers there are
a number of other additive properties we would like to explore to determine their
predictive effect:

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Refractive Index (RI)

Clarity is a major concern in many polymers and a number of


additives tend to haze polymers. Matching the RI of the
additive to that of the polymer is expected to have a
predictive effect on final clarity.

.
Functional Group Orientation

The molecular structure of an effective antistat must be


designed so that the lipophyllic portion of the molecule is
soluble in the polymer while its hydrophilic portion must
orient toward the polymer surface. Additionally the spacing
of the functional groups at the polymer surface must be of
the appropriate distance to maximize hydrogen bonding with
water to form a continuous water layer. While we did see
there was a difference in performance between mono-esters
with two hydroxyl groups and di-esters with one hydroxyl
group the result was actually the inverse of what would be
expected. The two-hydroxyl groups of the mono-ester
should increase hydrogen bonding, but this did not take
place. It is not a function of just having two hydroxyl groups
present because coco amine POE2, with the same groups,
has excellent performance. The way these groups orient
themselves on the surface may be the answer.

pH

While we briefly addressed pH we need a more systematic


study of its effect on migration using a broader range of
pH’s.

Viscosity

Viscosity is related to both molecular size and polarity. At


post extrusion storage temperature viscosity becomes an
important factor in additive migration speed. The lower
viscosity materials will be expected to migrate faster.

Acknowledgements:
We would like to acknowledge the hard work and dedication
of Mr. Sam Habib and Mr. Chris Sculthorpe, researchers at
Chemax Polymer Additives, for their contributions to this
paper.

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