1,4 DMN and Plastic Interaction

K. Amos, K. Waynant, E. Aston,

University of Idaho Chemistry, Chemical, and Material Science Engineering Department
Plastics purchased from Specialty Plastics Boise, Idaho

Introduction
1,4 DMN is a chemical (patented by 1,4 Group) that is used to treat potatoes for sprout
suppression in storages. In some of the locations world-wide, the company has been observing a
degradation in certain plastics around the storage facility. This is seen in the light fixtures, wire
coatings, electrical panels, and other plastic/polymer objects within the storage facility. While
this interaction in the US was treated by replacing the susceptible plastics with other plastics, the
company overall wanted a professional research group or team finding the answers to this issue.
Research of this interaction was designed to observe the parameters the polymer degradation this
occurs and see the interaction on the molecular scale. The interaction was tested in depth with
Polycarbonate, Poly Vinyl Chloride, High Density Polyethylene. The research also touched on
the interaction between Polypropylene, Teflon, Delrin, and Acrylic.

Experimentation and Analysis: Bath

In the first experiment, we observed the Chemical-Polymer interaction with room temperature
bath tests. Each plastic was roughly 1-2 grams bathing in 3 ml of 1,4 DMN. We observed the
interaction for roughly 1 hour and found immediate results. We observed the samples absorbing
into the polymeric matrix. After one hour, the largest increase in mass of the sample was 11%
after 1 hour (Polycarbonate) and the least (Acrylic) which had a constant volume.

Figure 1&2. Mass of Plastic over time of room temperature chemical bath (Left). In figure 2, we can see the affect
the chemical bath has on the PC before and after treatment (Right).

The qualitative results of the tests showed color changes, brittleness, swelling, and softness
depending on the sample. Liquid room temperature treatment affected the PVC, PC, and HDPE
while the rest of the samples showed resistance to the chemical. Also from the room temperature
baths after more time was given, we observed an absorption of the plastic in the solution. This
means that the 1,4 DMN solidified to a gelatin like substance. We believe that while the 1,4
DMN was being absorbed into the polymer, the polymer was also broken down and retained in
the solution.
The analysis of this experiment was to observe any chemical change in the bathed
specimen. We would use the University’s instruments to see if there was a chemical interacting
between the chemical and the different polymers.
Infrared Spectrum

Figure 3&4. Infrared Spectrum of PC before and after chemical baths.

The Infrared Spectrum shown above show there was no change in the chemical structure of the
PC. A similar spectrum for the PVC and HDPE was also shown where the chemical structure
stayed the same after the treatment.

Experimentation and Analysis: Coatings

One method we decided to test were coatings. The reasoning for this method was to find a cheap
and safe way to protect electrical wiring and light fixtures without completely replacing and
upgrading at every storage facility. This would protect the polymer regardless of the chemical
reaction or physical degradation caused by the 1,4 DMN. The coatings we decided to test were
Teflon, Teflon-Silicone, and Acrylic coatings. We specifically chose these chemical coatings due
Acrylic’s resistance to 1,4 DMN in the previous tests and Teflon’s ability to be resistant to
hydrophilic/phobic chemicals while already being used in the food industry (pots and pans).
Figure 5. Control (Left) and Acrylic coated (Right) PVC and PC (respectively) chemical bath tests after 1 day of
treatment.

The experiment resulted in a similar outcome, but an increase in resistance was observed in the
PC treatment with the acrylic coating. The Teflon and Teflon-Silicone coating were relatively
penetrable. While this application was somewhat promising, the experiment was abandoned due
to health concerns. The group did not want to risk cross contamination by any means.

Experimental and Analysis: 1,4 Group Fogged Plastics

Phase 2
While the chemical treatments mainly consisted of liquid tests, the importance of vapor tests was
also considered. 1,4 Group vapor treated PVC, PC, and PP at 3 different temperatures (350-50
F)400 F, 550-580 F, and +6) for 6 Treatments. We would receive care packages consisting of
each temperature treated plastic at a given treatment. The treatment dates took the majority of
November and the analysis of this phase took from November to March.
Analysis Method: Raman Spectroscopy

Figure 6&7. Raman spectra of PC between the first and third high temperature vapor treatment.

The Raman Spectra between treatment 1 and 3 of the PC shows little difference. Between 3000
and 3500, we observe a difference in height. This is due to the reflective nature of the plastic
itself rather than a change in chemical or physical character caused by the 1,4 DMN. In
conclusion of Raman, we observe no chemical changes in the interaction of the vapor treatments.
[Similar results were observed in the PVC and PP]
Scanning Electron Microscopy
SEM is a method used to observe the surface of materials on a microscopic scale. We use this to
observe and compare the surface of the PVC and PC.

Figure 8&9. SEM images of liquid treated (Right, 5000x Magnification) and untreated (Left, 4700x Magnification)
PVC.

Figure 10&11. SEM images of liquid treated (Right, 500x Magnification) and untreated (Left, 500x Magnification)
PC.

In the case of these plastics, we observed the cross-sectional area of the treated end. This allowed
us to observe how to material changed in physical structure and how it breached the matrix.
In the PVC, SEM observed strands/fibers of polymers (figure 8). Once treated, the surface was
very flat with little texture and fibers. This led the team to believe that the chemical was
absorbed into the matrix and physically changed the overall structure. Evidence of the 1,4 DMN
remaining in the polymer was the swelling of the material as well at the smell of the chemical
diffusing through the material. Over time, the material would decrease in mass as the 1,4 DMN
slowly diffused through the material.
The PC absorbed the 1,4 DMN but rather than only swelling, polymer degradation and
brittleness occurred. Under the SEM, we observed spherical surface roughness in the treated end.
This is unclear why this happens, but we are observing a physical change in the PVC and PC
rather than a chemical change. The 1,4 DMN diffuses from the PC in the same way, but over
time, the PC seems to dry and become more brittle when open to the atmosphere.
Overall, we can conclude the 1,4 DMN remains in the polymeric matrix for a long period of
time, due to its high boiling point, and physically changes the polymer’s macro-characteristics.
While the characteristics of PVC become soft, the PC becomes brittle and increases in brittleness
the longer the chemical remains in the material.
Bending Tests
Bending tests were conducted to stress the surface of the material to quantitate the maximum
stress in hopes to find a trend with the vapor treatments.

Figure 12, 13, & 14. Bend tests 1-5 for PVC Control, 1 Treatment, and 6 Treatments of 1,4
DMN.
Figure 15 & 16. Charts representing how the Average Max Force changed as a function of
treatments. (Control is fixed at 100% for both charts)
The bend tests where conducted by using an Instron instrument. Each sample was balanced on
two points and the instrument forcefully lowered a bolt downward, recording its force applied
and displacement, until failure or max displacement was reached. Each sample was rectangular
with desired dimension of (5*1*.25) (length*width*thickness). This test was conducted as
consistent as possible but the slight differences in width, length, or prior crack propagation in
samples skewed each result.
Figure 12, 13, and 14, are examples of the data of each treatment set. From these sets, maximum
force was recorded and averaged, then used to compare with each set in figures 15 and 16.
Analysis took place in Excel.
In PVC, we observe a decrease in max force with high temperature treatments while there was an
increase with low temperature treatments. We assume with the increase in maximum force, the
shear strength of the material was more ‘ductile’ compared to its control group. This is still an
undesired characteristic because PVC is still susceptible to 1,4 DMN. In conclusion, 1,4 DMN
is more destructive to PVC at higher temperature treatments.
In PC, we observe and increase in max force with all treatments. The high temperature
treatments accelerated the change in behavior, so we can also conclude: 1,4 DMN is more
destructive to PC at higher temperature treatments.
Conclusion
In conclusion, we observe no chemical changes in the polymer caused my the 1,4 DMN. The
only change is physical structure of the plastic which affects the macro structure and
characteristics. The elongate the life of plastics in the storage:
1) Replace damaged plastics with Polypropylene, Delrin, Acrylic, High Density
Polyethylene, or other high-density polymer
2) Coat wiring and covers with acrylic spray
3) Treat potatoes at lower temperatures to prevent the high kinetic energy in the chemical
interaction