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

Weight/100
Weight of Resin
Material: Solution
45 poise bodied Linseed Oil 35.8427
Low aromatic mineral spirits - D40 type 39.8034
Vinyl Toluene 23.8764
Triganox B 0.4775
Total 100.0000

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.

Final resin properties:

Solids 60%
Oil length 60%
Solvent D-40 White Spirits
Viscosity Y - Z1
Color 4 max
ii.) A PRE-VINYLATED VT RESIN

Weight/100
Weight Resin
Material: Solution
Linseed Oil 37.5297
Vinyl Toluene 23.0471
Triganox B 0.9238
Pentaerythritol 6.0144
LiOH 0.0075
Phthalic Anhydride 10.8259
Xylene reflux 2.4057
D-40 solvent 19.2460
D-40 solvent adjust 2.4057
Losses -2.4057
Total 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:
Weight/100
Weight Resin
Material: Solution
Linseed Oil 17.8625
Vinyl Toluene 17.8111
Triganox B 0.7119
Glycerol 5.1403
LiOH 0.0036
Phthalic Anhydride 9.9721
Xylene reflux 1.2851
Mineral Spirits (or SBP6) 46.9051
Solvent adjust 1.2851
Losses -0.9767
Total 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
Weight/100
Weight Resin
Material: Solution
Soya Oil 12.7200
1.5 poise Dehydrated
Castor Oil 12.7200
Vinyl Toluene 25.7894
Triganox B 0.5178
Glycerol 7.1741
LiOH 0.0051
Phthalic Anhydride 14.1798
Xylene reflux 1.4036
D-40 solvent 26.9248
Losses -1.4348
Total 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:
Weight/100
Weight Resin
Material: Solution
Soya Oil 21.1487
1.5 poise Dehydrated
Castor Oil 7.0496
Glycerol (1) 5.9060
LiOH 0.0056
Phthalic Anhydride 13.6292
Glycerol (2) 2.0365
Xylene reflux 1.4882
Vinyl Toluene 32.1931
Triganox C 0.6423
Xylene 17.3890
Losses -1.4882
Total 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 Volume
per 100 per 100
Units of Units of
Weight 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 Xylene
4.49 25.04 VM&P Naphtha
0.02 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 Volume
per 100 per 100
Units of Units of
Weight 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 Viscosity
4.92 7.24 VM&P Naphtha
Pebble Mill 20 24 hours
46.55 55.60 Med. Oil VT Alkyd 50% non volitile in VM&P V-Y Viscosity
0.65 0.60 Ltd Nuxtra 18%
0.26 0.30 6% Co Naphthanate
0.06 0.06 Anti-skinning Agent (2)
8.50 12.60 VM&P Naphtha
100.00 100.00 Total

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 Volume
per 100 per 100
Units of Units of
Weight 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 Spirits
0.11 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 Volume
per 100 per 100
Units of Units of
Weight 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
Disperse to 7+ N.S.
33.62 41.17 VT Alkyd 80% non volitile at Z6+ Viscosity in Xylene (2)
0.30 0.42 6% Cobalt
0.60 0.79 6% Calcium
0.60 0.85 6% Zirconium
17.85 24.96 Xylene
100.00 100.00 Total

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, ½ Hour
Weight
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

-3 o
Density, g cm @ 25 C 0.893 0.892 0.884 0.902
-1 o
Surface Tension, dynes-cm @ 25 C 31 34 29 32
o
Boiling Point, C @ 760 mm HG 168 170 219 145
o
Freezing Point, C -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
o o
80 C (176 F) 35 35 6 90
o o
120 C (248 F) 176 170 37 368
o o
160 C (320 F) 341 325 77 661
-1
Heat of Polymerization, Kcal mole 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
o
Heat of Vaporization, cal/g @25 C -- 98.2 -- 102.4
o o
Specific Heat, cal/g C @25 C -- 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]