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Vinyl Toluene For Alkyd Resins For Coatings
Vinyl Toluene For Alkyd Resins
For Coatings
Contents
1. Overview 2. Applications Features and Benefits 3. Example Resin Formulations and
Manufacturing Features 4. Example Paint Formulations and
Manufacturing Procedures 5. Vinyl Toluene Technical Data 6. Contacts
Vinyl Toluene Modified Resins
1. Overview In the United States Vinyl Toluene has been used to modify alkyd resins for many years.
Unlike most fast dry systems, the addition of Vinyl Toluene provides compatibility with both
aliphatic and aromatic solvents giving the paint formulator a great deal of flexibility in
formulating paints. Typically the level of VT modification of alkyd resins is between 30% and
40% VT by weight on resin solid content.
The improved solubility of Vinyl Toluene Modified Resins provides the paint formulator with a resin, which has key advantages in several areas. Using VT modified alkyds a paint formulator can:
Formulate fast dry paints with aliphatic solvents making the paint suitable for indoor industrial and other production applications.
Formulate fast dry paints that can be brush, roll, dip, or spray applied and easily re-coated, which make them particularly useful in maintenance and refinish products.
Formulate fast dry paints with low cost and low odor solvents such as mineral spirits and VM&P.
Formulate higher solids coatings with excellent gloss, hardness and moisture resistance.
This brochure provides an overview of VT alkyd technology; including sections on Applications Features and Benefits, Example Resins and Paint Formulations, and Manufacturing Procedures.
2. Applications Features and Benefits
Typical applications for VT modified resins include:
Aerosols, Sanding sealers, Production line pre-finishing, Primers, Hardware and implement enamels, Toy and hobby finishes, Metal furniture, Machinery enamels, Hammer finishes, Multi color finishes, Industrial brushing enamels, General purpose fast dry maintenance enamels, Ink varnishes, and
VT oils for paper coatings.
Features and Benefits Aliphatic solubility
VM&P naphtha, Mineral spirits, Isobutane / propane for aerosols, Also soluble / compatible with most other paint solvents.
Fast drying – typically 5-10 minutes set to touch with approximately 30 minutes Zapon 500 dry,
VT alkyds also find use as blending resins in other alkyd systems to speed up drying times and develop early hardness.
Relative to other typical fast drying resin systems, VT alkyds exhibit:
Higher flash point, Lower vapor pressure, Lower HAP emissions, Lower odor, Good hardness, Acid, caustic, and moisture resistance.
They can be brush, roll, dip, or spray applied. Aliphatic versions exhibit extremely flexible recoat and touch up schedules (open time), and Their good substrate wetting allows excellent flow and leveling leading to high gloss.
3. Example Resin Formulations and Manufacturing Procedures VT modified oils and alkyds can be made using several routes:
a) VT modified oils are made by polymerising a vegetable oil (usually linseed or soya) with VT (usually about 50% VT) at a temperature of about 160 deg C in the presence of a peroxide catalyst such as Triganox B (Ditertiary Butyl Peroxide).
b) VT alkyds can be made by reacting an oil with VT as discussed above followed by
reaction with a polyol (such as pentaerythritol) and a diacid (such a phthalic anhydride). This process is known as pre-vinylation.
c) VT alkyds can also be made by making the base alkyd first followed by treatment of
the base alkyd with VT. This process is known as post-vinylation. More details follow concerning the manufacturing processes and formulations for:
i) A VT modified oil, ii) A pre-vinylated VT resin suitable for toy enamels, iii) A pre-vinylated VT resin for general purpose industrial applications, iv) A post-vinylated VT resin suitable for hammer finishes, and v) A high solids post-vinylated VT resin in xylene.
i.) A VT MODIFIED OIL
Material:
Weight/100 Weight of Resin
Solution45 poise bodied Linseed Oil 35.8427Low aromatic mineral spirits - D40 type 39.8034Vinyl Toluene 23.8764Triganox B 0.4775 Total 100.0000
Final resin properties: Solids 60% Oil length 60% Solvent D-40 White Spirits Viscosity Y - Z1 Color 4 max
Procedure: Heat the linseed oil mixed with the D40 solvent to 155 deg C under a flow of nitrogen. Add the mix of the VT and Trig B constantly over a period of three hours. For safety reasons it is preferable to add the VT and Trig B from separate vessels i.e. unmixed. When addition is complete hold for 1 hour at 155 deg C. Test for viscosity and solids. Adjust solids and viscosity to specification by adding a spike of 0.0079 wt parts of Triganox B per 100 parts of resin solution in 0.079 wt parts D40 per 100 parts of resin solution. Spike at 155 deg C and hold for one hour at 155deg C before retesting. Make further additions of Triganox B in D40 as necessary.
ii.) A PRE-VINYLATED VT RESIN
Material:
Weight/100 Weight Resin
SolutionLinseed Oil 37.5297Vinyl Toluene 23.0471Triganox B 0.9238Pentaerythritol 6.0144LiOH 0.0075Phthalic Anhydride 10.8259Xylene reflux 2.4057D-40 solvent 19.2460D-40 solvent adjust 2.4057Losses -2.4057Total 100.0000
Procedure: Add the linseed oil to the reactor, heat to 155-160 deg C. Nitrogen purge on from start. Add the Vinyl Toluene and Triganox B mixture over 3 hours; it is preferable to add the Vinyl Toluene and Triganox B at the same time unmixed for safety reasons. Hold for one hour at 160 deg C. Sample for solids and viscosity. Heat on to 240 deg C, hold for 30 minutes at 240 deg C, cool to 160 deg C (test for solids and viscosity). At 160 deg C, add the penta and lithium, heat to 240-245 deg C for mono, hold at 240 – 245 deg C for one hour then test using phthalic anhydride. Take 6.15 parts mono solution from reactor and add 1.00 parts phthalic anhydride in a beaker. Heat on a hot plate at approx 240 deg C for 15 mins. Mono is complete when the solution is clear hot and cold, and is a single phase. Hold reactor at 240-245 deg C until the mono passes. Retest hourly. When mono passed, cook for a further 30 minutes at 240 deg C, then cool to 180 deg C. Add the phthalic anhydride and the reflux xylene. If necessary add a small further quantity of reflux xylene – if required to give a good reflux. Heat to 240-245 deg C under reflux, test for viscosity and acid value using a 1.29 dilution factor (to give 75% in D40 solvent) Cook to a reduced viscosity of Z3 to Z4 (at 75% solids in D40), acid value 10 max; check every half hour towards end. Upon reaching spec, cool to 160 deg C, then add D40 solvent to kettle, adjusting as necessary.
Final resin properties: Solids 73-77% Oil length 50% VT Content 30% Solvent D-40 White Spirits Viscosity Z3 - Z4 Acid Value 10 max Color 8 max
iii.) A PRE-VINYLATED VT RESIN FOR GENERAL PURPOSE INDUSTRIAL APPLICATIONS:
Material:
Weight/100 Weight Resin
SolutionLinseed Oil 17.8625Vinyl Toluene 17.8111Triganox B 0.7119Glycerol 5.1403LiOH 0.0036Phthalic Anhydride 9.9721Xylene reflux 1.2851Mineral Spirits (or SBP6) 46.9051Solvent adjust 1.2851Losses -0.9767Total 100.0000
Procedure: Add the linseed oil to the reactor, heat to 155-160 deg C. Nitrogen purge on from start. Add the Vinyl Toluene and Triganox B mixture over 3 hours; it is preferable to add the Vinyl Toluene and Triganox B at the same time unmixed for safety reasons, hold for one hour at 160 deg C. Sample for solids and viscosity. Heat on to 240 deg C, hold for 30 minutes at 240 deg C, cool to 160 deg C (test for solids and viscosity). At 160 deg C, add the glycerol and lithium, heat to 240-245 deg C for mono, hold at 240 – 245 deg C for one hour then test using phthalic anhydride. Take 4.09 parts mono solution from reactor and add 1.00 parts phthalic anhydride in a beaker. Heat on a hot plate at approx 240 deg C for 15 mins. Mono is complete when the solution is clear hot and cold, and is a single phase. Hold reactor at 240-245 deg C until the mono passes. Retest hourly. When mono passed cook for a further 30 minutes at 240 deg C, then cool to 180 deg C. Add the phthalic anhydride and the reflux xylene. If necessary add a small further quantity of reflux xylene – if required to give a good reflux. Heat to 240-245 deg C under reflux, test for viscosity and acid value using a 1.29 dilution factor (to give 75% in D40 solvent). Cook to a reduced viscosity of Y - Z (at 50% solids in solvent), acid value 10 max, check every half hour towards end. Upon reaching spec, cool to 160 deg C, then add solvent to kettle, adjusting as necessary.
Final resin properties: Solids 48-52% Oil length 36% VT Content 36% Solvent SBP6 Naphtha Viscosity Y - Z Acid Value 10 max Color 8 max
iv.) A POST VINYLATED VT HAMMER FINISH RESIN
Material:
Weight/100 Weight Resin
SolutionSoya Oil 12.72001.5 poise Dehydrated Castor Oil 12.7200Vinyl Toluene 25.7894Triganox B 0.5178Glycerol 7.1741LiOH 0.0051Phthalic Anhydride 14.1798Xylene reflux 1.4036D-40 solvent 26.9248Losses -1.4348Total 100.0000
Procedure:
Add the soya oil, dehydrated castor oil, glycerol and lithium hydroxide, have nitrogen purge on, heat to 260/265 deg C for mono-glyceride. When mono-glyceride passed, cool to 180 deg C. Add the phthalic anhydride and the reflux xylene. If necessary add a small further quantity of reflux xylene to give a suitable reflux. Heat to 240-245 deg C under reflux, after one hour test for acid value and reduced viscosity (100.0 g resin with 38.6 g Xylene = 70% solids), then test hourly or more frequently as required. Near to the end of the cook, test every 30 minutes or as required, until a reduced viscosity of P-R is reached, acid value 15-18 max. Cool the batch to 155 deg C. Use the D40 addition to aid cooling as necessary. Do not carry out the VT treatment if a delay is possible. At 155 – 160 deg C add the Vinyl Toluene, Triganox B mixture over three hours; it is preferable to add the Vinyl Toluene and Triganox B at the same time unmixed for safety reasons. Hold for one hour at 155 deg C – 160 deg C. Sample for solids and viscosity. The reactor solids should be 71.5%.
Adjust solids and viscosity to specification by adding a spike of 0.023 wt parts of Triganox B per100 parts of resin solution in 0.12 wt parts D40 per 100 parts of resin solution. Spike at 155 deg C and hold for one hour at 155deg C before retesting. Make further spike additions of Triganox B in D40 as necessary.
Final resin properties: Solids 70-72% Oil length 36% VT Content 36% Solvent D-40 Mineral Spirits Viscosity 300-500 poise Acid Value 12 max Color 8 max
v.) A HIGH SOLIDS POST VINYLATED
VT RESIN IN XYLENE:
Material:
Weight/100 Weight Resin
SolutionSoya Oil 21.14871.5 poise Dehydrated Castor Oil 7.0496Glycerol (1) 5.9060LiOH 0.0056Phthalic Anhydride 13.6292Glycerol (2) 2.0365Xylene reflux 1.4882Vinyl Toluene 32.1931Triganox C 0.6423Xylene 17.3890Losses -1.4882Total 100.0000
Procedure:
Add the soya oil, dehydrated castor oil, glycerol (1) and lithium hydroxide, have nitrogen purge on, heat to 260/265 deg C for mono-glyceride. When mono-glyceride passed, cool to 180 deg C. Add the phthalic anhydride and glycerol (2) and the reflux xylene. If necessary, add a small further quantity of reflux xylene to give a suitable reflux. Heat to 240-245 deg C under reflux, after one hour, test for acid value and reduced viscosity (100.0 g resin with 38.6 g Xylene = 70% solids), then test hourly or more frequently as required. Near to the end of the cook test every 30 minutes or as required, until a reduced viscosity of H - J is reached, acid value 15-18 max. Cool the batch to 135 – 140 deg C. Use the xylene addition to aid cooling as necessary. Do not carry out the VT treatment if a delay is possible. At 135 – 140 deg C add the Vinyl Toluene, Triganox C mixture over three hours; it is preferable to add the Vinyl Toluene and Triganox C at the same time unmixed for safety reasons, hold for one hour at 135 deg C – 140 deg C. Sample for solids and viscosity. The reactor solids should be 81%.
Adjust solids and viscosity to specification by adding a spike of 0.042 wt parts of Triganox C per 100 parts of resin solution in 0.084 wt parts Xylene per 100 parts of resin solution. Spike at 135 deg C and hold for one hour at 135deg C before retesting. Make further spike additions of Triganox C in xylene as necessary
Final resin properties: Solids 78-82% Oil length 35% VT Content 40% Solvent Xylene Viscosity Z6 AV 12 max Color 8 max
4. Example Paint Formulations and Manufacturing Procedures This section gives guide formulations and methods to produce
i) Green Aerosol Enamel ii) Fast Dry White Enamel iii) Sanding Sealer iv) White High Solids Enamel
i.) GREEN AEROSOL ENAMEL
Weight per 100 Units of Weight
Volume per 100 Units of Volume Material
32.18 4.10 Chrome Oxide Green, G-6099 (1)0.92 0.35 Bentone 38 (2)0.46 0.38 Butyl Alcohol
57.00 42.48 VT Oil 60%-non volitile in VM&P Z-Z1 Viscosity (3)4.85 27.09 Xylene4.49 25.04 VM&P Naphtha0.02 0.12 6% Cobalt Naphthanate, 0.03%0.04 0.21 Skino No. 2, 0.2% or equivalent (4)0.04 0.24 Paint Additive #11 or equivalent (5)
100.00 100.00 Total
Analysis: 48 Viscosity at 25°C, Seconds, #4 Ford 15.4Percent Pigment Volume Concentration 28.6 Percent Vehicle Solids 39.0Percent Total Solids 8.60 Pounds per Gallon Suppliers: (1) Pfizer (4) OMG Chemicals (2) Elementis (5) Dow Corning (3) VT alkyd supplier KEY PROPERTIES - Fast dry; excellent aerosol stability and propellant compatibility; excellent spray characteristics: high gloss. FORMULATING NOTES - Normal grind equipment and procedures can be used. Sand mill equipment requires 0.1% of defoamer on solids. Use Chevron Phillips A-70 propellant (50/50 isobutane/propane). 27% Methylene Chloride, based on propellant, required when using 50/50 isobutane/propane. Suggested paint/propellant ratio 60/40 and 50/50. TYPICAL PERFORMANCE DATA Drying Data and Film Properties 3 Mils Wet Film Cast at 40% Non-Volatile 0.03% Co + 0.2% Antioxidant
Dry Time, 77°F/50% R.H. Tack-Free 10 Minutes Dry Hard 45 Minutes
Sward Hardness: 1 Hour 6
2 Hours 12 4 Hours 20
1 Day 28 1 Week 33
1 Month 41
ii.) FAST DRY WHITE ENAMEL BASED ON MEDIUM OIL VT ALKYD RESIN
Weight per 100 Units of Weight
Volume per 100 Units of Volume Material
24.40 6.20 Rutile Titanium Dioxide (1)14.66 17.40 Med. Oil VT Alkyd 50% non volitile in VM&P V-Y Viscosity4.92 7.24 VM&P Naphtha
46.55 55.60 Med. Oil VT Alkyd 50% non volitile in VM&P V-Y Viscosity0.65 0.60 Ltd Nuxtra 18%0.26 0.30 6% Co Naphthanate0.06 0.06 Anti-skinning Agent (2)8.50 12.60 VM&P Naphtha
100.00 100.00 Total
Pebble Mill 20 24 hours
Analysis: 8.94 Weight Units per Unit Volume 55.0 Percent total non-volatile 44.4 Percent Pigment (of total solids) 77 seconds Initial Viscosity (#4 Ford Cup) 97/90 60°/20° Gloss Suppliers: (1) TiPure R-902 Hi Gloss (DuPont) or equal (2) Exkin #2 (Huls) or equal TYPICAL PERFORMANCE DATA Drying Data:
Drying Time:
Zapon 500 10 minutes Foil Free 120 minutes
Sward Hardness:
24 Hrs. 26 48 Hrs. 34
iii.) SANDING SEALER
Weight per 100 Units of Weight
Volume per 100 Units of Volume Material
68.80 67.00 Med VT Alkyd 50% non volitile in Mineral Spirits at W - Z Viscosity (1)3.52 2.73 Zinc Stearate, DLG-20. Stir in Zinc Stearate (2)
27.57 30.18 Mineral Spirits0.11 0.09 6% Cobalt Naphthanate
100.00 100.00 Total Analysis: 7.11 Pounds/Gallon 35.7 Percent Vehicle Non-volatile 40-45 Sec. Viscosity, #4 Ford Cup E-F Viscosity, Gardner-Holdt 0.02 % Drier. Cobalt as Metal On Vehicle Solids Suppliers: (1) VT Alkyd Resin Supplier (2) Nuodex TYPICAL PERFORMANCE DATA Sanding Properties: 1 Hr. = Powders white without gumming 2 Hrs.= Powders white without gumming Drying Data: Air Dry
Drying Time: Set-To-Touch 16 Minutes
Zapon Dry, 500 grams, Weight 22 Minutes Sward Hardness:
2 Hours 36 48 Hours 42
iv.) WHITE HIGH SOLIDS AIR-DRY ENAMEL
Weight per 100 Units of Weight
Volume per 100 Units of Volume Material
28.92 8.57 Rutile Titanium Dioxide. Titanox 2150 or equivalent (1)11.57 14.17 VT Alkyd 80% non volitile at Z6+ Viscosity in Xylene (2)0.69 0.89 Dispersing Agent, Nuosperse 657 or equivalent (3)0.07 0.09 Anti-Skinning Agent, Exkin No. 2 (3)5.78 8.09 Xylene
33.62 41.17 VT Alkyd 80% non volitile at Z6+ Viscosity in Xylene (2)0.30 0.42 6% Cobalt0.60 0.79 6% Calcium0.60 0.85 6% Zirconium
17.85 24.96 Xylene100.00 100.00 Total
Disperse to 7+ N.S.
Analysis: 0.8/1.0 Pigment/Binder Ratio 66.05 Percent Solids, Weight 52.40 Percent Solids, Volume 35-40 Viscosity @ 25°C, #4 Ford Cup, Seconds VOC 413 Grams/Liter 3.44 Pounds/Gallon Drier Recommendations: Air Dry 0.05% Co 0.10% Zr 0.10% Ca Suppliers: (1) Kronos. Inc. (2) VT Alkyd Resin Supplier (3) Huls America
TYPICAL PERFORMANCE DATA Drying Data: White Enamel, 1.5 ml wet film application on glass
Drying Time:
Set-To-Touch 8 Minutes Dry-Thru ½ Hour Dry Hard 6 Hours
Zapon Dry-500 grams, Weight
½ Hour
Sward Hardness: 72 hrs 32
1 week 34
Film Properties: White Enamel, 1.5 mil wet film on Bonderite 1000, CRS After 1 Week Air-Dry Gloss, 50/20 88/84 “b” Value, Color +0.5 Pencil Hardness B Crosshatch Adhesion (0.5, 5=best) 4 Mandrel Flexibility Pass, 1/4 inch
5. Vinyl Toluene Technical Data
VT (monomer) Vinyltoluene
VT monomer produced by Deltech Corporation is a mixture of methylstyrene isomers with approximately 55% meta and 45% para isomer distribution. The monomer has chemical properties and polymerization behavior similar to styrene monomer but provides superior properties in many applications. Applications requiring a single methylstyrene isomer should consider Deltech's PMS monomer, which contains 99% para-methylstyrene.
Molecular Weight: 118.18 Typical Isomer Distribution: 45% Para 55% Meta
VT is a reactive monomer, which readily polymerizes to form a high clarity, colorless polymer with excellent electrical and physical properties. Like styrene monomer, VT monomer can be polymerized by any of the conventional methods of initiation and in the presence of inert materials such as fillers, dyes, solvents, resins, rubbers and plasticizers. Copolymerization of VT monomer with other monomers such as acrylate, acrylonitrile, butadiene, divinylbenzene or methacrylate and maleic anhydride yields products with wide variations of physical properties.
VT monomer is widely used in the coatings industry as a modifier for drying oils and oil modified alkyds. These monomer modified resins have good chemical resistance, fast drying, durability, excellent solution color and color retention properties. Another important advantage for VT modified oils and alkyd is their solubility in low cost solvents.
Typical precautions in handling VT monomer include wearing protective clothing, the use of impermeable gloves and use in a well-ventilated area. Do not store in direct sunlight. Maintain storage temperature below 75oF if extended storage is required. VT monomer contains the polymerization inhibitor tertiary butylcatechol (TBC) to reduce polymer formation during storage. For other product safety and toxicological information, please consult the Material Safety Data Sheets for VT monomer.
Typical Monomer Values Chemical Analysis Test Method VT PMS TBS Styrene
Purity, Weight % vinyl GC 99.2 99.7 >98.0 99.7 Isomer Distribution GC Para % 43.0 99.0 95.0 -- Meta % 56.0 1.0 5.0 -- Ortho % 1 -- -- -- Polymer, ppm ASTM D-2121-84 Neg. Neg. Neg. Neg. Inhibitor, ppm TBC ASTM D-2120-82 12 25 50 12
Physical Properties Refractive Index, n25D 1.54 1.54 1.52 1.54 Density, g cm-3 @ 25oC 0.893 0.892 0.884 0.902 Surface Tension, dynes-cm-1 @ 25oC 31 34 29 32 Boiling Point, oC @ 760 mm HG 168 170 219 145 Freezing Point, oC -77 -34 -38 -31 Volume Concentration on Polymerization % calculated @ 25oC 12 12 7 17 Vapor Pressure, mm HG at 40oC (104oF) 4 4 1 14 80oC (176oF) 35 35 6 90 120oC (248oF) 176 170 37 368 160oC (320oF) 341 325 77 661 Heat of Polymerization, Kcal mole-1 15-17 15-17 16-18 17 Copolymerization Q & e values Q 1.06 1.27 1.39 1.00 E -0.78 -0.98 -0.90 -0.80 Heat of Vaporization, cal/g @25oC -- 98.2 -- 102.4 Specific Heat, cal/goC @25oC -- 0.413 -- 0.408
6. Contacts Further resin details can be found on the European Resin Manufactures Website at www.erma.org.uk, and on the Deltech Corporation Website at www.deltechcorp.com Technical resin inquiries can be directed to Dr Chris Riley at [email protected] and Vinyl Toluene monomer inquiries to Melvin Duhon at [email protected]
