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(Terminating Alkyl - commonly Me)
Homo-polymer :R
O
O
y
R
Common Capped PAGs -Air-conditioning (mainly Auto HFC)
“Symetrically” Capped PAGs:
R
O
O
R
y
O
y
(Terminating Alkyl - commonly Me)
Random Co-polymer :
y
(Most commonly terminating R = Initiating R,
as both ends simultaneously capped)
Common Capped PAGs -Refrigeration / Air-conditioning (HFC)
“Zerol RFL” capped PAGs ( novel asymetric type) :
Homo-polymer
(Terminating Group - hydroxyl)O
O
y
HO
(Terminating Alkyl - commonly Me)
y
O
O
y
RO
Terminating R ≠≠≠≠ Initiating R
Common Uncapped PAGs -Air-conditioning (mainly Auto HFC)
eg. Zerol PAG
Water Insoluble:
(Terminating Hydroxide)
Homo-polymer
R
O
O H
x
(R - most commonly Me, Bu)
Homo-polymer
Random Co-polymer
R
O
O
H
y
O
y
(R - most commonly Me, Bu)
(Terminating Hydroxide)
Water Soluble:
• Zerol PAG Grades : Uncapped PAGs for HFC
• Zerol RFL : Capped basefluids for HFC & R744
Product Grade SummaryProduct Grade Summary
• Zerol RFL-X : Additised capped PAGs for HFC
• Zerol RFL- EP : Additised capped PAGs for R744
Main Performance advantages of asymetrically capped PAGs
(compared with symetrically capped PAGs and uncapped PAGs)
Improved refrigerant miscibility
Enhanced Extreme Pressure / Antiwear properties
Reduced water Absorption
Asymetric capped PAG -CO2 miscibility property.
Miscibility with CO2 enhanced compared with uncapped andsymetrically capped PAGs.
Viscosity reduction associated with miscibility minimal compared with POE.compared with POE.
Lubricity property not disadvantaged by improved miscibility.
Asymetric capped PAG -lubricating property in CO2 systems.
Trans-critical CO2 systems - higher load-bearing requirements.
Falex Block-on-Ring procedure:
Load steps: 50lb steps, followed by 20lb stepsRotation: 600 rpmAtmosphere: CO2
Overpressure: 10 bar (150psi)Step duration: 5 minutesTemperature: 90ºC minimumRing / Block: Steel
Capped PAGs -lubricating property in CO2 systems.
Falex Block-on-Ring Summary:
300
350
400
450
500
Competitor
dicapped PAG
for CO2
Zerol RFL-X (for
Failure Load(20 load steps)
0
50
100
150
200
250
300
Test sample
Zerol RFL-X (for
HFC systems)
Zerol RFL-EP
(For R744
systems)
Capped PAGs -Lubrication in CO2 systems - Block wear.
Competitordicapped PAG
(Symetric capped)
Zerol RFL-X(for HFC)
Zerol RFL-EP(for R744)
50lb load steps50lb load steps
50lb load steps
20lb load steps 20lb load steps 20lb load steps
0.5
0.6
We
ar
Sc
ar
(mm
)
C ompet it o r d icapp ed
Capped PAGs - lubricating property in CO2 systems.
Wear Property of Capped PAGs by falex pin & V-block.CO2 (1 atmos), 100°C:
0
0.1
0.2
0.3
0.4
200 400 600 800
Load (N)
We
ar
Sc
ar
(mm
)
C ompet it o r d icapp ed
PA G
C ompet it o r d icapp ed
PA G - ISO 10 0
Z ero l R F L 4 6 EP
Z ero l R F L 10 0 EP
Capped PAGs - thermal stability property
High Pressure Differential Scanning Calorimetry:
CO2 environment: (1100 Kpa)Temperature: 0 - 350 ºC
Capped PAGs - thermal stability by PDSC in CO2 systems.
SAMPLE START POINT (˚c)
PEAK (˚c) END POINT (˚c)
Zerol RFL 4EP 199.9 215.2 273.8
Competitor ISO 193.9 207.3 270.1 Competitor ISO 46 dicapped
PAG
193.9 207.3 270.1
Zerol RFL 100EP
191.7 208.1 227.6
Competitor ISO 100 dicapped
PAG
182 201.9 285.1
Capped PAGs - chemical stability property
Non-reactivity of PAG with water, hygroscopicity non-problematic.
PAGs non-reactive with any carbonic acid formed by reactionof CO2 with water. Carbonic acid further to SGT typically non-detectable.
Tendancy of PAGs to absorb water is reduced as a result of end-capping.
ASHRAE 97 – 14days, CO2, 175ºC, 0.1wt% H2O.
TAN (unreacted) MgKOH/g
TAN reacted MgKOH/g
Sample
Zerol RFL-EP
0.12 0.01
Zerol RFL-EP + 0.1wt% H2O
0.12
0.01
PAGs as Condensing Compressor Lubricants
HYGROSCOPICITY
PAG water absorption problematic?
Corrosion?
Freezing within capillaries?
Chemical stability?
POE requires:
Low water spec
For chemical stability.
Not required for PAG.
R
O
O
O
O
R
HO
HH
O
H
HO
HH
O
H
Water ‘Chemically’ bound and therefore undesired effects of water not experienced.
Hygroscopicity Comparison –Competitor vs RFL 100EP
2000
2500
3000
Water Content (ppm)
0
500
1000
1500
0 30
120
360
1440
Zerol RFL 100EP
Competitor
Time (mins)
Zerol RFL-EP / Competitor Compatibility
• RFL-EP & competitor dicapped PAGs fully compatible
over the full temperature range tested (-20 to +110°C).
• Fully compatible in all proportions (0-100% either component).
• All samples remain clear and homogeneous.
Conclusions
• Novel capping technology:-enables the synthesis of PAG type refrigeration lubricants with application specific properties, eg. R134a and CO2 compressor applications.
• Flexible “capping” process:allow structure modification and hence performance optimisation for the future refrigerant technology developments.
Zerol Capped PAGsFreedom / Availability to Use
• Worldwide patented “Asymetric Capped PAG” technology
• Non-infringing of competitor patents for HFC systems
• Worldwide freedom to supply for both HFC and CO2 systems
• Manufactured UK, delivered worldwide.