CONTRAM ST-1
CONTRAM ST-1 industrial biocide is an extremely effective antibacterial compound for use in aqueous metalworking fluids.
CONTRAM ST-1 is a highly concentrated and purified industrial bactericide based on N,N-Methylenebismorpholine (CAS#: 5625-90-1).
CONTRAM ST-1 was developed specifically for use in metalworking fluids, unlike competitive products, which are designed for other uses and may require the addition of non-ionics and more expensive emulsifiers.
CONTRAM ST-1 inhibits the Growth of Bacteria in Metalworking, Cutting, Cooling and Lubricating Fluid Concentrates that will be used only in Closed or Semi-Enclosed Machines
ACTIVE INGREDIENT
N,N-Methylenebismorpholine……………………………..98.5%
OTHER INGREDIENT(S) …………………………………..1.5%
TOTAL:…………………………………………………………100.00%
CONTRAM ST-1 is an EPA approved product and it is exceptionally stable in metalworking fluid concentrates and does not disrupt the balance of the emulsifier system.
CONTRAM ST-1 also demonstrates long lasting efficacy in diluted emulsions; CONTRAM ST-1 lasts throughout the majority of the life of the metalworking fluid, which means longer drain intervals, reduced maintenance costs, and much less work tank side.
CONTRAM ST-1 is a Metalworking Biocide Concentrate which is exceptionally stable in metalworking fluids
Although CONTRAM ST-1 contains and releases formaldehyde, the amount released during use in the industrial machine shop environment is negligible and even below the amount exhaled in human breath.
Introduction of this chemistry to the US market represents a significant decrease in exposure to formaldehyde compared with other formaldehyde release chemistry currently on the market, and may even pose a lower overall risk than “formaldehyde free” products on the market today.
CONTRAM ST-1 is effective against both gram-negative and gram-positive bacteria.
Since CONTRAM ST-1 has limited efficacy against fungi, the product should be used in combination with a fungicide like Exocide OIT or Exocide IPBC 20 or IPBC 30
To inhibit the growth of bacteria in soluble oil and semi-synthetic metalworking fluids, the recommended addition level for CONTRAM ST-1 is 3% in concentrates designed for 20:1 dilution.
At a 3 % treat level, this results in a 3000ppm concentration in the diluted metalworking fluid.
CONTRAM ST-1 might be added to the oil phase prior to addition of water when preparing a semi-synthetic formulation in order to maximize product efficacy and ensure long lasting performance.
CONTRAM ST-1
More information about CONTRAM ST-1: info@atamankimya.com
Features
CONTRAM ST-1 is a very stable and purified bactericide for metalworking concentrates with balanced oil and water solubility.
In the EU this biocidal substance is already authorized under the Biocidal Products Regulation (BPR) for use in PT6 and PT13, and this Biocidal Product CONTRAM ST-1 is in the authorization process as a biocidal Product for use in PT13 for concentrate and tank side.
In Germany its use is limited to Export Only products
CONTRAM ST-1 is also registered in the United States under the Federal Insecticide, Fungicide and Rodenticide Act (FIFRA) for use in metalworking concentrates.
The Environmental Protection Agency (EPA) registration number is 52484-3.
Metal working fluid concentrates containing CONTRAM ST-1 are therefor allowed for Import into the US.
Metalworking fluids
CONTRAM ST-1
Biocide
Product Description
CONTRAM ST-1 is a highly concentrated industrial bactericide based on tetrahydrooxazines.
Owing to its good solubility this preserving agent is suitable for oily as well as aqueous systems.
CONTRAM ST-1 is effective against gram-negative and grampositive bacterias.
In order to get an additional effieciency against fungies we recommend using in combination withour Exocide OIT or Exocide IPBC range.
Typical Properties
Aspect(visual)Clear low viscous liquid
Colour(visual)Colour less to slightly yellowish
Odour Mild
Solubility Water soluble
Applications
CONTRAM ST-1 is successfully applied for the preservation, mineral oil containing, water miscible coolants.
Compared to hexahydrotriazines and oxazolidines, CONTRAM ST-1 is more stable in metalworking concentrates.
CONTRAM ST-1 should be used at an addition level of 1 – 3 % in a concentrate and at 0.3% in finished cutting fluid user dilutions,in order to have a concentration of 1,000 to 1,500 ppm of the active.
Other remarkable features:
Low odour
Low formaldehyde content
Helps in the corrosion protection
Very stable molecule
Good compatibility and solubility
Very good performance
It can be used in fluids with pH of 3 to12.
Formaldehyde release bactericides have been the predominant type of chemistry used to preserve metalworking fluids over the last 4 or more decades.
Concerns regarding exposure to formaldehyde in the metalworking and many other industries have arisen over the last 10 to 15 years.
In exploring the apparent dichotomy of the rapid hydrolysis of N,N’-Methylenebismorpholine (MBM) in water, which occurs at low concentration in water in under six seconds, and a half-life of several months in a metalworking fluid, Lubrizol discovered that the MBM has sufficient oil solubility to be incorporated into the oil micelles formed in metalworking fluid emulsions.
This not only provides stability in the metalworking fluid, but also provides slow release of formaldehyde and therefore a very low airborne concentration in metalworking production plants.
One study conducted in the UK(1) found 1.1 to 3.3 parts per billion formaldehyde, which is lower than the concentration found in human breath(2,3) and well below the EPA occupational level of concern of 100 ppb.
Although formaldehyde is a chemical of concern, EPA concluded that MBM is a reduced risk alternative to formaldehyde releasers currently on the market and a viable option for users to move away from products with higher formaldehyde release rates.
EPA further states that the metalworking fluid use pattern is expected to pose little to no environmental concern(4).
Since the product is very compatible with most metalworking fluid concentrates, the registration applied for was intentionally limited to use solely in concentrates in order to minimize exposure to US workers.
Many bactericides are added to the diluted fluids “tankside”, which results in many more workers being exposed to the highly concentrated antimicrobial.
CONTRAM ST-1 is a highly concentrated industrial bactericide based on N,N Methylenebismorpholine, an extremely effective anti-bacterial compound for use in aqueous metalworking fluids.
CONTRAM ST-1 provides a unique balance of oil and water solubility allowing for longer fluid stability and it is proven to be highly effective against a wide variety of bacteria.
biocidesmolecule3
Enhanced Performance
Long-lasting, persistent bacteria control for extended fluid life with minimal tankside supplements
Exceptional stability in metalworking fluid concentrates
Unique solubility properties in both oil and water
Safe and effective when applied and handled properly – not classified as a skin sensitizer
Extensive history of successful use – millions of liters of diluted metalworking fluid have been protected with CONTRAM ST-1
Typical Properties of CONTRAM ST-1
Appearance Clear, light yellow liquid
pH, dilute 9.0-11.0
Activity, % > 98
Activity, % Oil and Water Soluble
Total Bound Formaldehyde Content, % 14-16
Biocidal Efficacy
CONTRAM ST-1 demonstrates efficacy against a wide variety of bacteria and limited efficacy against fungi, including the following typical metalworking fluid spoilage organisms:
Acremonium spec.
Candida albicans
Escherichia coli
Fusarium spec.
Klebsiella aerogenes
Legionella pneumophila
Mycobacterium immunogenum
Pseudomonas aeruginosa
Pseudomonas fluorescens
Pseudomonas putida
Staphylococcus aureus
In metalworking fluid concentrates and emulsion systems, a balanced solubility between the oil and water phases is key to biocidal efficacy and long-term stability in use.
Unlike commonly used HHT biocide, CONTRAM ST-1 and MBO are engineered to provide greater oil phase solubility, as demonstrated by a controlled solubility study in heptane.
This property is one factor that makes CONTRAM technology the ideal choice for metalworking fluid protection.
Metalworking fluid concentrate compatibility is key to the performance of CONTRAM ST-1.
The above study monitored simple soluble oil concentrates protected with either CONTRAM ST-1, or the commonly-used HHT molecule.
Concentrates stored at elevated temperatures were checked for emulsion performance at seven day intervals.
When protected with CONTRAM ST-1, no loss of emulsion quality was observed throughout the storage period.
Concentrates using HHT demonstrated complete loss of emulsion quality, resulting in a product that would be unsuitable for use following extended storage.
Recommended Use Directions
CONTRAM ST-1 is primarily recommended for incorporation into metalworking fluid concentrates intended for water dilution at the final use site.
Metalworking fluid concentrates intended for 20:1 water dilution should utilize 2.0-3.0% CONTRAM ST-1 by weight. This will result in a final dilution concentration of 1,000-1,500 ppm. Treat rates in metalworking fluid concentrates intended for different water dilution rates should be adjusted to deliver 1,000-1,500 ppm CONTRAM ST-1 in the final working dilution.
In-Depth Industry Knowledge
Lubrizol’s comprehensive knowledge of the metalworking fluid industry helps us provide unequaled consultative support at all stages of the metalworking fluid application.
From product development in the laboratory to troubleshooting challenges in the end use environment, we work with customers on specific formulation strategies to improve products or to help incorporate additives in existing product lines.
When properly applied, CONTRAM ST-1 will safely and effectively control the hazards of microbial growth in metalworking fluids.
The Lubrizol Corporation:CONTRAM ST-1
Biocide
Dr. Uwe Falk
Globally Proven; Now Available in the United States
Lubrizol’s CONTRAM ST-1 industrial biocide, an extremely effective antibacterial compound for use in aqueous metalworking fluids, was recently approved by the Environmental Protection Agency (EPA) for use in the United States.
Regulating biocides
Biocides are needed to control microbes; a fact well recognized within the metalworking industry.
Without the use of biocides, bacterial counts in metalworking fluids rise rapidly, causing the fluid to spoil and resulting in an unhealthy work environment for machine shop employees.
In the US, all biocide materials are regulated by the Federal Insecticide, Fungicide and Rodenticide Act (FIFRA) under the auspices of the EPA.
FIFRA, which has been in effect for over 60 years, requires extensive data generation in consideration of a product’s health, safety and environmental impact as well as of its efficacy.
This is an expensive process. Coupled with the high cost of new molecule development, the expense of registration in the US can be a limiting factor to new product introduction.
Approvals and Re-registration
The recent EPA approval of Lubrizol’s CONTRAM ST-1 product will remain in effect for the standard 15 year period.
After that time, like all established chemistries, CONTRAM ST-1 will need to undergo Registration Review, which is replacing the Re-registration Eligibility Decision or RED program.
Suppliers may want to consider approval, Registration Review and RED dates carefully when choosing a biocide.
As re-registration dates draw close, biocide manufacturers will face the decision to generate additional data (if required by the EPA) or they may choose to drop out of the market due to the high cost of reregistration.
Newly approved or re-registered products offer a significant window of stability.
The formaldehyde question
Regulations are particularly pertinent to the discussion of biocides.
The most effective biocide type for metalworking, one that has been used globally for years, is formaldehyde release chemistry.
For many of those years, formaldehyde has been the regulatory focus of governmental and non-governmental agencies, with the current EPA threshold for exposure at 100 ppb over eight hours.
A recent RED conducted on hexahydrotriazine, also known as HHT, brought issues surrounding formaldehyde to the forefront.
HHT dominates metalworking fluid applications, and over the decades, it has been shown to be effective at a reasonable cost.
However, with the recent RED, the EPA is giving serious consideration to regulating HHT to reduce the maximum treat level from 1500 ppm to 500 ppm in metalworking applications.
The Canadian government is also discussing enacting similar regulations, although a final determination has not been made by either group.
The regulators are seeing pushback from some in the industry, however, because HHT is in – effective as a biocide at those low treat rates.
CONTRAM ST-1: A reduced risk alternative
With an extensive history of successful application, the CONTRAM ST-1 biocide offers an alternative to HHT.
The bound formaldehyde content of the CONTRAM ST-1 product is almost half of that of HHT, although the treat rate is also in the 1,000 to 1,500 ppm range.
Unlike HHT, CONTRAM ST-1 is soluble in oil, a valuable characteristic for a product used predominantly in soluble oils and semi-synthetic oil emulsions.
On November 2, 2011 CONTRAM ST-1 biocide, which has already successfully been used commercially in 36 countries over the past few decades, received FIFRA registration for use in closed (closed on all sides with mechanical exhaust) and enclosed (physical barriers controlling exposure to mist) machines.
The registration covered not just the product, but a new active ingredient, which requires an even more rigorous approval process.
It’s important to note that the EPA approved CONTRAM ST-1 biocide despite heightened concerns about formaldehyde.
In its risk assessment, the EPA noted that “the available formaldehyde is estimated to be 1.1 ppb with an upper-bound estimated concentration of 3.3 ppb.”
These levels are below the agency’s occupational level of concern of 100 ppb of formaldehyde.
The EPA further stated that “the proposed metalworking fluid use pattern is expected to pose little or no environmental exposure.
MBM (CONTRAM ST-1) is a reduced risk alternative to formaldehyde releasers currently on the market.”
Unlike competitive products, which are designed for other uses and may re quire the addition of non-ionics and more expensive emulsifiers, CONTRAMST-1 was built specifically for use in metal working fluids. (Lubrizol is the only supplier of biocides designed exclusively for metalworking.)
It is exceptionally stable in metalworking fluid concentrates and does not disrupt the balance of the emulsifier system.
The result is ease of formulation and reduced complexity for metalworking fluid producers.
The product also demonstrates long lasting efficacy in diluted emulsions; it is not a “one time fix” and it is not added tank side.
Instead, it is only registered for use in concentrate.
CONTRAM ST-1 lasts throughout the majority of the life of the metalworking fluid, which means longer drain intervals, reduced maintenance costs and much less work tank side.
Because operators don’t need to measure and pour biocides into the tank, the opportunity for error—and the dangers of over- or under-treatment— are significantly reduced and human exposure to active biocides is limited.
Proven performance
Developing a high-quality biocide is just the first step. Equally as important is its performance in the finished fluid where it is impacted by other factors including the fluid formulation itself; the use conditions and maintenance practices.
CONTRAM ST-1’s wide use globally is the strongest testimony to its performance, but controlled laboratory studies also support the product’s performance benefits.
In studies focused on long-term storage stability and concentrate compatibility, Lubrizol evaluated basic soluble oil formulations; one unprotected (no biocide); one treated with HHT and one treated with CONTRAM ST-1.
Stability of concentrate
There is no guarantee when metalworking concentrate will be used or what the storage conditions will be.
Metalworking fluids may be stored for months under extreme temperature s, and it’s critical that they perform as well after six months as they do on day one.
To test emulsion stability, formulations of HHT (adjusted to match clear, stable emulsions of CONTRAM ST-1 formulations), CONTRAM ST-1 formulations and a control were tested.
The formulations were:
• Stored at 40° C for extended periods
• Monitored for phase separation and instability
• Checked at regular intervals to confirm emulsions were suitable for use after storage inwarm conditions.
Results confirm that CONTRAM ST-1 offers exceptional long term concentrate stability.
Biocidal efficacy
Lubrizol used ASTM E 2275, a well-known bacterial challenge, to test the efficacy of its product compared to HHT.
Experience shows that all freshly prepared biocide containing products perform well in this method.
But again, fluids must provide optimum performance after being in storage for six months or longer.
In this test, concentrates were stored for six months at 40° C prior to emulsion preparation and testing. Testing began with 800 mL of fluid added to a quart jar:
• 715 mL metalworking fluid
• 85 mL inoculum
• 10g cast iron chips.
In the standard test, the mixture is aerated for five days on and two days off for a total of 12 days.
Test results indicate that CONTRAM ST-1 maintained its efficacy even in aged concentrates.
Results are expressed as bacteria colony forming units / mL as measured using a dip slide
In addition to the standard test, Lubrizol runs an extended test, stopping only when all emulsions have failed.
In the example below, bacterial testing was continued for 13 weeks.
Fresh concentrates with a 3% biocide treat rate were diluted to 5%, resulting in 1500 ppm active biocide.
The pH of each formulation was monitored through out the test period.
An indicator of bacteria growth, pH goes down as bacteria increase, the result of acidic by-products.
Since a high pH creates an unfriendly environment for bacteria, a stable pH of approximately 8 or 9 is critical in a metalworking fluid.
Anything lower may result in corrosion issues.
The right choice for metalworking
CONTRAM ST-1 is a new, safer alternative biocide for the US market with exceptional performance properties in metalworking fluids.
Backed by an extensive testing and a proven performance history, CONTRAM ST-1 is the right choice for today’s metalworking fluids.
The active substance N,N-Methylenebismorpholine (short: MBM) is attributed the CAS-No 5625-90-1 and the EC- No 227-062-3.
The molecular formula is C9H1aN202, and the molecular weight is 186.26 g/mol.
The minimum degree of purity is 92.10/ow/w.
Structural formula: The structure of N,N-Methylenebismorpholine is confirmed by all spectra (IR, NMR, UV/VI S and MS).
Physico-Chemical Properties of the Active substance: The physico- chemical properties are studied for the active substance of stated specification (min. 92. 1 %w/w N,N- Methylenebismorpholine [short: MBM]) according to the demands of the data requirements.
MBM is a pale yellow liquid, has a slightly amine like odour.
Its melt ing point range is 18 – 21°C, and the boiling point is 266.4°C.
The relative density is 1.05 at 20°C and the density is 1.0647 g/cm3 at 20°C.
The calculated vapour pressure of the active substance is 0.625 Pa at 25°C ( EpiSuite) and 0.443 at 20°C (conversion of the Episuite value to 20°C by EUSES).
The calculated Henry’s law constant is 2. 72×10-s Pa m3 mo1-1 at 25°C.
Water solubility cannot be determined as the active substance is hydrolysable.
MBM is miscible in water in all proportions (at 10 -30°C and at pH 5 -9).
The dissociation constant (pKa) is calculated to be 7.39 and 2.98 at 20°C.
(MBM cannot be isolated because of its hydrolysis properties and therefore determination of the single pKa values is not possible.)
The solubility of MBM is 2000 -2500 mg/L in Heptan and MBM is completely miscible in DMSO, Toluene, Ethanol, n-Octanol, Acetone and partially soluble in Cyclohexane at 2 1-23 °C. (Concentrations tested: 5000, 2500, 1000, and 500 mg/ml)
The active substance as manufactured does not contain any organic solvents.
The calculated partition coefficient Octanol-Water is -1.53, the measured log Pow ::; 0 .3 (hydrolysed test substance; pH: 5, 7, 9 at 30°C).
The surface tension cannot be determined due to hydrolysis in aqueous solution.
The viscosity is 16 m Pas at 20°C.
The active substance MBM displays neither explosive nor oxidizing properties based on its structure.
Its flash point is 115°C.
The substance can be safely handled up to its flash point ( 115°C). It is not considered to be reactive to container material ( LOPE.)
N,N-Methylenebismorpholine
Product-type 6, 13November 2014
Physico-Chemical Properties of the Hydrolysis product Morpholine:Morpholine is a hydrolysis product of the active substance N,N-Methylenebismorpholine
Selected literature data on physico–chemical properties were provided by the applicant: Morpholine is an oily ,hygroscopic, colourless liquid; has a characteristic amine smell.
Its melting point range is -3,1 to -5°C, and the boiling point is 128°C.
The relative density is 1.0001 at 20°C.
The vapour pressure of morpholine are 1.1 kPa at 20°C; 3.2 kPa at 40°C and 1.34 kPa at 25°C
The literature data of Henry’s law constant are 49 Pa m3 mol-1(20°C); 244 Pa*m3*mol-1and 0.012 Pa*m3*mol-1(25°C)
The structure of morpholine is confirmed by IR- spectra.
Morpholine is miscible with water and has a low soluble in alkaline aqueous solutions.
The dissociation constant (pKa) is to be 8.5 and 8.33 at 25°C. Morpholine is completely miscible with, for instance, methanol, ethanol, acetone, diethyl ether, benzene, toluene, xylol.
The partition coefficient Octanol-Water is -0.86 (pH no data), and -2.55 (pH 7).
Morpholine is not surface active and the viscosity is 2.021 mPas at 25°C.
The hydrolysis product morpholine displays neither explosive nor oxidizing properties based on its structure.
Its flash point is 38°C- Open cup and 33°C – Closed cup.
Morpholine is a flammable liquid Category 3.
It is not considered to be reactive to container material (LDPE.).
Analytical Methods:The active substance N,N-Methylenebismorpholine as manufactured is in equilibrium with the starting materials.
Because of the dynamic nature of the equilibrium analytical standard methods like HPLC/UV, LC/MS, GC/MS, photometry are difficult to use for characterisation of the composition and the determination of the active-ingredient-content or the impurities.
The content of the active substance N,N-Methylenebismorpholine and its organic impurities has been determined by NMR-analysis using 1H- and 13C- NMR techniques.
The remaining inorganic impurity has been determined by titration method.
The method has been validated and shown to be sufficiently specific, accurate and sensitive.
2.1.2.Intended Uses and Efficacy
N,N-Methylenebismorpholine containing biocidal products are used as bactericides for the preservation of fuels (PT6) and metal working fluids (PT13) which are prone to bacterial decay.
Two out of seven studies submitted were suitable for proof of preservation, whereas the remaining five studies, which also covered mycobacteria and fungi, were rather suitable for proof of disinfection properties.
The active substance is a formaldehyde-releaser.
The biocidal activity of the active substance is due to the interaction of the released formaldehyde with protein, DNA and RNA.
The interaction with protein results from a combination with the primary amide and the amino groups.
It reacts with carboxyl, sulfhydryl and hydroxyl groups.
As formaldehyde is not specific for one cellular target the development of resistances is not to be expected.6
N,N-Methylenebismorpholine
Product-type 6, 13November 2014
For applications in PT 6 the product is intended to be incorporated by industrial users into fuels during the formulation process, which is carried out automatically, to act as a preservative with bactericidal activity.
Formulation is performed in closed systems and high degree of automation resulting in a final concentration of the active substance of concentration of 0.01-0.1% in the fuel.
For applications in PT 13 (Metalworking fluid preservative) the product is intended to be incorporated by professional users into water based emulsifiable metalworking fluids (MWF) to act as a preservative with bactericidal activity.
The lubricant concentrate, intended for the preparation of water based emulsifiable metal working fluids, contains the active substance at a concentration of 3% w/w.
The use concentration of the active substance in metalworking fluids is typically 0.15% w/w.
The active substance has to be regularly or occasionally re-dosed if a.s. is below effective concentration of 0.15% w/w.
The assessment of the biocidal activity of the active substance demonstrates that it has a sufficient level of efficacy against gram negative bacteria such as Citrobacter freundii, Alcaligenes faecalis, Pseudomonas aeruginosa and Enterobacter aerogenes).
The active substance MBM is used for the preservation of fuels (PT 6).
Most sites apply MBM in closed systems using automatic dosage during formulation of fuels.
The lubricant concentrates and the metalworking fluids contain significant amounts of water and MBM hydrolyses quickly, therefore, total transformation of MBM to formaldehyde and morpholine seems to be an acceptable assumption.
As formaldehyde reveals a higher toxicity and volatility than morpholine, the calculations target only 13
N,N-Methylenebismorpholine
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