Synthetic Esters:
Mother Nature’s Second Choice ™
Author: Tyler Housel, CLS
Member ACS, STLE, ILMA
Inolex 215 271 0800 office
2101 S. Swanson St. 215 271 2621 fax
[Link] Philadelphia, PA 19148 lubeinfo@[Link] email
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Synthetic Esters: Mother Nature’s Second Choice™
Organic esters are one of the basic building blocks of life on Earth. All living things
biochemically manipulate organic alcohols and fatty acids to form esters that suit the needs
of the organism. Esters have always been a part of the food chain, and humans have worked
with these natural and abundant esters for millennia to develop products such as wood
varnish, sealing wax, axle grease and lamp oil.
Naturally occurring lipids are widely available and have many undeniable advantages
including biodegradability, low cost, low flammability and they are non-toxic. Unfortunately,
animal and vegetable oils cannot be used in most modern industrial applications because
poor hydrolytic, oxidative and bio-stability leads to rancidity and degradation.
Industrial automation in the 20th century put additional stresses on process fluids and it
became clear that natural oils were not up to the task. Chemists learned to intelligently
design oils by rearranging and purifying natural lipids to suit their purpose.
Synthetic esters are manufactured by combining alcohols and carboxylic acids in an
esterification reaction. There are dozens of commercially available alcohols and acids to
choose from, and many feedstocks are derived from vegetable or animal sources. Ester
chemistry allows the user to formulate lubricant basestocks to meet virtually any lubrication
challenge. Although not quite natural, synthetic esters still retain the favorable health, toxicity
and environmental benefits of the natural oils. When compared to other lubrication base oils,
synthetic esters are clearly Mother Nature’s Second Choice™.
Why Synthetic Esters?
Esters are naturally polar molecules which gives them an affinity for each other in the liquid
state. This means they are less prone to evaporation than hydrocarbons, aromatics and
ethers. At a given temperature and viscosity, synthetic esters are much less volatile than
mineral oils, polyalphaolefins (PAO) and other less polar base oils.
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in existence. The Materials are intended to act as a guide for use at your discretion and risk. We assume no liability in connection with the use, or the utilization of the Materials or the
methods or products described therein. Information pertaining to availability, pricing and technical assistance for these products can be obtained from the marketing department, through
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Another benefit of polarity is that the ester groups are attracted esters to metal surfaces
where they form a molecular boundary layer which not only lubricates but also protects the
metal from oxidation and corrosion.
All esters are polar; the other properties are determined by the type and ratio of organic
alcohol and carboxylic acid ingredients. Therefore, the manufacturer designs a synthetic
ester to provide the appropriate viscosity, volatility, thermal stability, pour point, flash point,
biodegradability and even cost. To clarify this relationship, we divide synthetic esters into
four subgroups: fatty acid esters, diesters, polyol esters and complex esters
Fatty Acid Esters
Fatty acid esters are manufactured from naturally occurring fatty acids that are commercially
derived from animal or vegetable fats and oils. Based on renewable resources and also
biodegradable, these esters are widely used in skin creams and other cosmetics and have
an outstanding health and safety profile.
In industrial applications, synthetic fatty acid esters give a distinct performance advantage
over natural triglyceride oils because we fix two weak links that occur in nature. Specifically,
the triglyceride is deconstructed by separating the fatty acids from the glycerin. This fatty
acid mixture is then purified to improve the character of the acid component. Finally, the
acids are reconstituted with synthetic alcohols because glycerin is prone to oxidation and
rancidity at elevated temperature. The resulting synthetic fatty acid ester has superior
oxidative, hydrolytic and bio-stability and can be designed to meet the viscosity, volatility
and other characteristics required for the application.
Diesters
Diesters are historically made from synthetic diacids and synthetic alcohols. As such, they
are not based on renewable resources, but can still have an excellent health, safety and
toxicity profile if aromatic diacids (phthalates) are avoided. In recent years, bio-based diester
feedstocks have become available and it is likely that these will become more affordable in
coming years.
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Polyol Esters
Polyol esters have three or more ester groups so they give higher viscosity and lower in
volatility than diesters. The polyol center is extremely stable at high temperature so polyol
esters are preferred in hot operations where they give long life and resist varnish and deposit
formation.
The acid component can be renewable or fully synthetic. Synthetic feedstocks optimize
thermal stability and renewable acids are required if the oil must be readily biodegradable.
Complex Polyol Esters
Complex polyol esters are polymeric hybrids of polyol esters and diacids. By combining the
two technologies, it is possible to achieve excellent thermal stability at moderate to very high
viscosity. The polymeric character and multiple ester groups lead to a very high viscosity
index, outstanding tack and exceptional boundary lubrication. Complex polyol esters can
be manufactured with a large percentage of renewable carbons and many types are readily
biodegradable.
Representative Synthetic Esters
It is possible to synthesize thousands of ester combinations from existing feedstocks, so we
use simile to understand the toxicological and environmental properties. The ten compounds
described herein all have industrial applications, and cover a range of molecular weights,
volatilities and chemistries. It is reasonable to apply this information to similar synthetic
esters by analogy.
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Lexolube® Product Category Alcohol Acid Component
IPP Fatty acid ester Isopropyl Palmitic
IPO Fatty acid ester Isopropyl Oleic
NBS Fatty acid ester n-Butyl Stearic
EHP Fatty acid ester Ethyl hexyl Palmitic
B-109 Fatty acid ester Tridecyl Stearic
2X-109 Diester Tridecyl Adipic
3N-310 Polyol ester Trimethylol propane C8-10
3G-310 Fatty acid Trimethylol propane Oleic
polyol ester
POE series Polyol ester Dipentaerythritol C5-10
CPE series Complex Mixed polyol Mixed
polyol ester
Basic Physical Properties
The first step in understanding synthetic esters is to determine the effect of the molecular
size and structure. Esters used in the lubrication industry are not flammable under the DoT
definition and generally have at least 19 carbons. Smaller esters are better described as
solvents.
Viscosity and flash point increase quickly as the number of carbons in the ester increases.
As expected, the Volatile Organic Content (VOC) decreases with carbon count, and is
particularly sensitive to the number of carbons between 19 and 22. Air quality standards
require low VOC because organic volatiles play a role in creating photochemical smog.
Specific gravity is a measure of the ester density (number of ester groups divided by number
of carbons) which also tends to increase as the molecule grows.
Viscosity, flash point and specific gravity were tested according to ASTM D-445, D-92 and
D-1122 respectively. VOC was measured by ASTM E1868-10in accordance with SCAQMD
Rule 1144. This is the new VOC standard required for metalworking fluids in Southern
California.
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Lexolube® Number of Viscosity Flash Specific VOC -
Product Carbons @40°C Point Gravity Rule 1144
IPP 19 5 cSt 165°C 0.85 at 25°C 38 g/L
IPO 21 5 175 0.85 24
NBS 22 6 195 0.85 7
EHP 24 9 220 0.86 1
B-109 31 17 230 0.86 5
2X-109 32 27 240 0.91 2
3N-310 33 19 250 0.94 <1
3G-310 60 49 320 0.91 <1
POE-68HT 52 68 290 0.99 <1
CPE-70 ~70 68 290 0.98 <1
Toxicology, Health and Safety
Synthetic fatty acid esters such as IPP, NBS and EHP have been used in cosmetics for
over 50 years and have an excellent toxicological and environmental profile. Many synthetic
esters are approved by the FDA, CFIA, and other regulatory bodies for food processing
lubricants where incidental contact with food products is possible. In summary, synthetic
esters have an excellent health and safety profile.
The renewable content is the percentage of carbons in the final product that come from
renewable (generally plant based) feed stocks. In the near future, additional bio-based
feedstocks will be manufactured in commercial quantities and it is likely that fully renewable
synthetic esters will be available.
Biodegradability is tested by the OECD 301B protocol. Greater than 70% degradation in 28
days means the product is readily biodegradable. Some esters were not tested directly, but
were labeled readily biodegradable based on chemical analogs. Synthetic esters are designed
to be more stable than animal or vegetable oils. They are metabolized (biodegraded) slowly
and are non-toxic and increasingly bio-inert.
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LD 50 shows the dosage which causes death in 50% of a population of test animals
(normally rats). In almost all cases, the LD 50 values for esters are listed as “greater than”
meaning that most or all of the test population survived at the highest test concentration.
It is uncommon to continue testing beyond 5 grams per Kg of body weight because it is
unlikely that a person will accidentally ingest such a large amount of these compounds. The
United Nations“Globally Harmonized System of Classification and Labeling of Chemicals
(GHS), 2009” considers LD 50 values above 2 g/Kg to have a low acute toxicity hazard
(Category 5), and above 5 g/Kg they have no hazard classification. In Chapter 3.1, page
110, the UN document states: “Recognizing the need to protect animal welfare, animal
testing in Category 5 ranges is discouraged and should only be considered when there is
a strong likelihood that results of such a test would have a direct relevance for protecting
human health”.
The American Chemistry Council Synthetic Esters Panel has published over 1000 pages of
data on the toxicological, environmental and physical properties of synthetic esters over the
past 10 years. The Panel grouped the esters based on structural similarity and determined
that “read across” assessments were appropriate for expanding the data to cover analogous
chemistries. This decision limits the testing required and has been applauded by animal
rights activists.
The Environmental Working Group (EWG) maintains a safety database for cosmetic
ingredients called the Skin Deep Cosmetics Database. This data is available online and
contains entries for more than 79,000 products (as of early 2013). After considering
available health, safety and environmental data, the EWG provides a grade from zero
to ten. Higher numbers means the ingredient is more hazardous and consumers should
seek safer alternatives. Many synthetic esters appear in the database because they are also
used in cosmetics. With grades of 1 or lower, the synthetic esters are among the safest
chemicals on the list.
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Synthetic Renewable EWG Grade
Ester carbon Biodegradability LD50 (0-10 scale)
IPP 84% Readily (>70%) 64 g/kg (6.4%) 0
IPO 86 Readily Nd 0
NBS 82 Readily >32 0-1
EHP 67 Readily >5 0-1
B-109 58 Readily Nd 0-1
2X-109 0 58.5%- Inherently 16 1
3N-310 82 65.5%- Inherently >5 0
3G-310 90 Readily Nd -
POE-68HT 0 47.1%- Inherently >5 0
CPE-70 50 Readily >2 0
Performance Characteristics
Synthetic esters have been used in industrial lubricants for more than 50 years. They are
excellent boundary lubricants and have outstanding lubricity, thermal stability and service life.
Major markets for synthetic esters are metalworking fluids, textile lubricants, hydraulic fluids,
compressor oils, automotive lubricants, gear and chain lubricants and grease. Although this
paper focuses on the health and environmental benefits, it is important to remember that
synthetic esters do not require a sacrifice in performance.
Conclusions
Synthetic esters have an outstanding environmental profile and are worker friendly. In fact,
synthetic esters are widely used in cosmetics including skin care products. These products
have been used in the lubricants industry for most of the 20th century because they are
outstanding lubricants and perform well in many applications where other oils fail. There
is no need to sacrifice performance to find a superior lubricant basestock with a favorable
environmental and toxicological profile. If a vegetable oil doesn’t meet your performance
requirements, synthetic esters are Mother Nature’s Second Choice™.
Inolex 215 271 0800 office
2101 S. Swanson St. 215 271 2621 fax
[Link] Philadelphia, PA 19148 lubeinfo@[Link] email
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Author: Tyler Housel, CLS
Member ACS, STLE, ILMA
Inolex Chemical Company
2101 South Swanson Street
Philadelphia, PA 19148
215-847-6333
thousel@[Link]
Acknowledgements and References:
Inolex Chemical Company of Philadelphia, PA
• Funded this presentation and solely responsible for the content
• Funded analytical work on VOC
• Manufactured all synthetic esters tested
• Supplies Lexolube® synthetic esters
• [Link]
American Chemistry Council
• Sponsored High Production Volume (HPV) Chemical Challenge Program
• Primary source for biodegradability and LD 50 data
• [Link]
Environmental Working Group (EWG)
• Safety grade from SkinDeep Cosmetics Database
• [Link]
Inolex 215 271 0800 office
2101 S. Swanson St. 215 271 2621 fax
[Link] Philadelphia, PA 19148 lubeinfo@[Link] email