Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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NOVEL NON-AQUEOU5 DISPERSIONS
R~ Tomko
M. Rao
M. Shalati
J. Kraan
BACKGROUND OF THE INVl :NTION
Non-aqueous dispersions (NAD's) are well known in the art and
typically consist of disperaions of addition polymers in a
relatively non-polar non-aqueous liquid containing a steric
stabilizing agent having dual affinity to ~oth the dispersing and
the dispersed media. For example, U.S. Patent 3,198,759 teaches
dispersions of addition polymers in a hydrocarbon medium. The
hydrocarbon medium contains one or more;aliphatic hydrocarbons
containing dissolved therein an alkyd formed by either the direct
esterification of a drying oil fatty acid with a dicarboxylic acid
and a polyhydric alcohol or the indirect esteri~ication o~ a drying
oil by first alcoholization with a polyhydric alcohol and second
esterification with a polybasic acid. European Patent Application
a 310 331 A2 teaches a non-aqueous dispersion of a soluble low
molecular weiy~t non-alkyd polymer which is attached or adsorbed
onto a second non-soluble alkyd-free polymer. U.S. Patent
4,530,957 teaches non-aqueous dispersions based on crosslinked
acrylic poly~er partlcles dispersed in a non-aqueous medium having
a polymeric dispersion stabilizer. The polymeric dispersion
stabilizer can be an alkyd which is ~ormed by the sel~ condensation
o~ 12-hydroxystearic acid ~ollowed by a capping reaction with
glycidyl methacrylate. U.S. Patent 4,206,099 teaches non-aqueous
dispersions o~ crosslinked polymer particLes in a non-aqueous
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.ledium having an amphipathic steric stahilizing agent. Th ~
stabilizing agent can be a graft copolymer obtained by reacting a
low molecular weight carboxyl group terminated condensate of
linseed oil fatty acids and 12-hydroxystearic acid with acrylic
copolymers. U.S. Patent 3,779,977 teaches non-aqueous dispersions
of an acrylonitrile copolymer in a liquid butacliene homopolymer or
copolymer in a non-polar organic hydrocarbon liquid.
A review of those patents clearly shows that most NAD's have
solids contents in a range generally less than 60% ~y weight and
have relatively high volatile organic contents. Attempts to raise
the solids content and lower the volatile organic content of these
NAD's has led to compositions which either gell unacceptably,
exhibit extremaly high viscosities, are not stable fox any
appreciable length of time or exhibit extremely long and
unacceptable dxy times as air dry coatings.
In our attempts to decrease the VOC contents o~ NADIs, we have
~ound that many alkyds produced via the traditional "alcoholysis"
process (alcoholysis of a drying oil followed by reaction with a
polybasic acid) have extremely high viscosities. The use of such
alkyds in a non-aqueous dispersion can force the formulator to use
a large amount of solvent to lower viscosity. This in turn causes
the VOC of the NAD to increase unacceptably. Additionally, we have
found that whila many alkyds produced via the traditional "fatty
acid esterification" process can be used to produce stable NA~'s,
they typically are limited in their ability to produce NAD's or
coatings having NVM's greater than about 70% and VOC's less than
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about 350 g/l.
The present invention produces very high solids NAD's, greater
than about 75% NVM, with very low VOC's of less than 305 g/l, which
exhibit excellent stability, filterability, low grit, viscosity and
tack-free and dry times when formulated as air dry coating
compositions. Thase NAD's are the result of a selection process
wherein certain critical parameters, described fully below, must
be observed.
SUMMARY OF THE INVENTION
This invention relates to novel, high solids, low VoC non-
aqueous dispersions ~NADIs) and a process for producing these non-
aqueous dispersions. The N~D'~ of this invention comprise an alkyd
as the dispersing medium and steric stabilizer for the
polymeri7.ation product of one or more monomers whlch are
predominantly non-soluble in the alkyd medium. The N~DIs of this
invention are the product of a process which requires, in addition
to other factors, at least one alkyd stabilizer, which stabilizer
has a z-average molecular weight between about 10,000 and 250,000,
pre~erably between about 15,000 and 150,000; and which stabilizer
has a polydispersity between about 2.0 and 20, preferably between
about 2.0 and 6Ø The use of this alkyd as the dispersing medium
for the polymerization of free radical addition monomers, one of
which is hydroxy-functional, further in the presence of a chain
transfer agent~ yields N~D's having non-volatile materials (NVM)
contents greater than about 75% by weiyht, typically approaching
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100% NVM, having volatile organic contents (VOC) typically less
than about 305 g/l, preferably less than about 250 g/l, which NAD's
exhibit excellent dry times not heretofore associated with very
high solids alkyds or NAD's. The NAD's of this invention are
particularly suited for interior and exterior applications in the
architectural, industrial maintenance, and traffic paint and
coatings industries.
The process for producing the NAD's of this invention
comprises using an alkyd meeting the criteria established herein
as the dispersing medium, either alone or in combination with some
minor amount of hydrocarbon, aromatic, polar, ketone, ester, or
alcohol solvent, or in combination wlth other minor amounts of
other alkyd, modified-alkyd, or hydrocarbon dispersing media, for
the polymerization of monomers which are predominantly insoluble
in the alkyd medium. The particular means for the production of
the alkyd are not of import to this invention. Thus, the alkyd can
be produced accordin~ to any of the traditional processes ~or the
production of alkyds which are readily available from the art or
the alkyd can be produced according to the teachings ~f pending
patent application number 464,841 filed January 16, 1990,
incorporated by refPrence herein. Critical to the success of this
inven~ion i~ that the alkyds used must have z-average molecular
weights between about 10,000 and about 250lO00, preferably between
about 15,000 and 150,000; with a polydispersity between about 2.0
and 20, preferably between about 2.0 and about 6~0. Preferably,
the alkyd stabilizer has an NVM solids content of at least about
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5%, more preferably at least about 90%.
The alkyd serves as the dispersing medium and steric
stabilizer for the reaction of free radical addition monomers which
produce a polymer which is predominantly insoluble in the alkyd
medium. The monomers are polymerized in the presence of the alkyd
to produce the novel NAD's of this invention. Another critical
parameter which must be followed is that at least one monomer must
have hydroxy-functionality. A third critical parameter which must
be followed is that the polymerization must take place in the
presence of a chain transfer agent.
We have found that by following these key critical parameters,
one can formulate an NAD having an NVM greater than about 70%,
which is stable, non-gritty, filterable, and low in viscosity. ~e
have found that failure to follow these key critical parameters
results in NAD's which are not stable, have very poor yields, do
not filter properly and/or are unacceptably high in viscosity.
~ ccordingly, it is an object of this invention to teach novel
non~aqueous dispersions.
It is another object of this invention tv teach a high solids
low VOC, non-aqueous dispersion having acceptable air dry times.
It is a further object of this invention to teach a process
for producing high solids, low VOC non-agueous dispersions having
acceptable air dry times.
DETAILED DESCRIPTION OF THE INVENTION
As stated above, t~e process for producing the NAD's of this
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invention comprisas selecting an alkyd having a z-average molecular
weight between about lO,OOo and about 250,000, preferably between
about 15,000 and 150,000, with a polydispersity hetween about 2-.0
and about 20, preferably between about 2.0 and about 6.0; and using
this alXyd as the dispersing medium, either alone or in combination
with some minor amount of solvent or other dispersing med.ia, for
the polymeri ation of monomers which are predomînantly insoluble
in the alkyd medium. The alkyd used in these NADIs is formed by
any of the traditional processes such as fatty acid esteriEication
or alcoholysis of a drying oil with later reaction with a di- or
~ri- basic acid, or the alkyd can be formed according to the
teaching of U.S. patent application number 464,841 filed January
16, lg90.
The alkyds o~ this invention must have ~ z-average molecular
weight between about 10,000 and 250,000, preEerably between about
15,000 and 150,000; with a polydispersity between about 2.0 and
about 20, preferably between about 2.0 and about 6Ø Alkyds in
this range provide the basis for a high solids, low VOC
composition.
Typical raw materials for the formation of alkyds include
triglyceride oils or the fatty acids thereof. These can be
selected from the group consisting of linseed oil, soya oil,
coconut oil, cottonseed oil, peanut oil, canola oil, corn oil~
safflower oil, sunflower oil, dehydrated castor oil, fish oil,
perilla, lard, walnut oil, tung oil, tall oil, the fatty acids
thereof and mixtures thereof. Particularly preferred are those
oils and acids containing unsaturation in the glyceride chains.
Particularly preferred are soya oil, dehydrated castor oil and
lin~eed oil and the fatty acids thereof.
Multi-functional alcohols, and mixtures thereof, are also
common raw materials for the production of alkyds. One suitable
hexafunctional alcohol includes dipentaerythritol. One suitable
tetrafunctional alcohol includes pentaerythritol. Suitable
trifunctional alcohols include the group consisting of trimethylol
propane, trimethylol ethane, glycerine, tris hydroxyethyl
isocyanurate, and mixtures thereof, either alone or in com~ination
with a difunctional alcohol selected from the group consisting of
ethylene glycol, propylene glycol, cyclohexane dimethanoL, and
mixtures thereof. Additionally, dimethylol propionic acid can be
used in combination with the trifunctional alcohol. Multi-
functional alcohols, trifunctional alcohols, and mixtures thereof
are particularly preferred due ~o the degree of branching they
allow. Difunctional alcohols, if used, are preferably used as a
minor component in combination with trifunctional alcohols. A
portion of monofunctional alcohol, or monobasic acid ~uch as soya
~atty acid, linseed oil fatty acid or crotonic acid, up to about
20% by wei~ht of the total alkyd can be added with the
multifunctional alcohol to control molecular weight and act as a
chain stopper.
Another typical raw material used in the formation of alkyds
is multi-~unctional carboxylic acids or anhydrides. Suitable
trifunctional carboxylic acids include trimelletic acid, trimesic
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Icid, 1,3,5-pentane tricarboxylic acid, citric acid and others
whereas suitable trifunctional anhydrides include trimelletic
.anhydride, pyromellet.ic anhydride and others. Difunctional
carboxylic acids include phthalic acid, isophthalic acid,
terephthalic acid~ maleic acid and fumaric acid and mixtures
thereof. Mixtures of such acids and anhydrides are also
acceptable.
The amounts of oil, acid and alcohol used should be such that
the resulting alkyd has a high degree of branching~j a.z~.average
molecular weight, M~, between about lU,000 and 250,000, preferably
between about 15,000 and 150,000, a polydispersity between ahout
2.0 and about 20, preferably between about 2.0 and about ~.0, an
oil length of between about 65% and 85%, an acid value less than
about 20, and a hydroxyl number less than 100, preferably less than
60. The NVM should be above about 70%, preferably up ko about
100~6 .
If desired, a reaction catalyst such as lithium hydroxide
monohydrate, barium hydroxide, or di-butyl tin oxide can be added
in an amount of approximately 0.02% by weight of oil.
Alkyds having Mz between about 10,000 and about 250,000 are
especially suitable ~or use in the non-aqueous dispersions of this
invention as the dispersing medium and to disperse and stabilize
insoluble monomers and polymers. The NAD's made according to this
invention typically have NVM's of about 75% or more, preferably up
to about 100~ NVM, have Brookfield LVT #3 (6/12 rpm) viscosities
less than about 60,000 cps at 25 degrees C, preferably less than
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about 30,000 cps, more preferably less than about lo,ooo cps, have
volatile organic contents less than 305 g/l, preferably less than
250 g/l, and exhibi,t excellent air dry times usin~ conventional
drier compounds.
Two particularly suitable commercially available alkyds which
exhibit the requisite Mz values and thus are suitable for use in
this invention include the 98% solids, long oil alkyd marketed by
Cargill, Inc. under the designation 57-5843 (Mz of approximately
45,000 and polydi~persity of about S.63; and the 100% solids
i~ophthalic alkyd oil marketed by McCloskey under the designation
Varkydol~ 210-100 (Mz of approximately 18,000 and polydisparsity
of about 2.7~.
When preparing non-aqueous dispersions according to this
invention, the`monomers should be selected from monomers which
would produce a polymer via the free radical addition reaction
mechanism which is predominantly insoluble in the alkyd medium.
It is essential that at least one of the monomers contain hydroxy
functionality. More preferably, between about 5~ and 35% by weight
of the total reactor charge comprises hydroxy functional monomers.
Most preferably, between about 10% and about 30% by weight of the
total reactor charge comprises a hydroxy functional monomer such
as hydroxy ethyl acrylate. Suitable monomers can be selected from
the group consisting of acrylonitril~, methacrylonitrile, hydroxy
ethyl acrylate and methacrylate, hydroxy propyl acrylate and
~ethacrylate, methyl acrylate and methacrylate, ethyl acrylate and
methacrylate, butyl acrylate and methacrylate, lauryl acrylate and
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..~ethacrylate, and the like, trimethylol propane triacrylate and
trimethacrylate, hexanediol diacrylate, Tone M-100 (caprolactone
modified hydroxy ethyl acrylate), polyethylene oxide acrylate,and
methacrylate, polypropylene oxide acrylate and methacrylate, allyl
alcohol, acrylamide, methacrylamide, vinyl chloride, vinylidene
chloride, and mixtures thereof. In addition to pure monomers,
preformed polymers, polymeric intermediates, multifunctional
epoxides, melamines and isocyanates, can be included in the reactor
charge. Most preferred is a combination of methyl methacrylate and
hydroxy ethyl acrylate wherein the methyl methacrylate is present
in an amount of between about 20 and ~0~, and the hydroxy ethyl
acrylate is present in an amount of between about 10 and 30%, by
weight of total reactor charge.
Certain monomers should be included in the reactor charge in
relatively minor amounts, if at all, due to their affect on the
viscosity of the NAD or the grittiness of the NAD. These include
acrylic a~id, methacrylic acid, and itaconic acid as the inclusion
of such acids tends to create a gritty NAD. Also included is
styrene because of an unacceptable resultant increase in NAD
viscosity. Also included are divinyl benzene, vinyl napthalene,
and vinyl toluene because these are generally soluble in a].kyds.
These monomers have been found to contribute to a decrease in
yield, addltional grit, and/or a lessening of stability over time.
To prepare the NAD's o~ this invention, the alkyd dispersing
medium is used as the polymeriæation medium for the monomer charge.
The alkyd medium can be diluted with mineral spirits or other
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solvent if dasired, with the primary limitation being concern for
the VOC of the composition.
The total amount of alkyd contained in the reaction vessel,
including any alkyd which may be added with the monomer charge,
should comprise between about 25% to about 75%, preferably from
about 40% to about 60%, by weight of the total reactor charge. The
fxae radical addition monomer charge should, after completely added
to the reaction vessel, account for approximately 75% to about 25%,
preferably between about 60% to about 40%, by weight of-the total
reactor charge. A mercaptan-containing chain transfer agent such
as methyl mercaptopropionate, dodecyl mercaptan, thioglycolic acid,
or 2-mercapto ethanol must also be added to the vessel in an amount
from about 0.1% to about 6.0% by weight of total reactor charge.
Most preferred is 2 mercapto ethanol. An initiator selected from
the group consisting of organic peroxides such as benzoyl peroxide,
lauroyl peroxide, di-t-butyl peroxide, acetyl peroxide, t--butyl
peroctoate, t-amyl peroctoate, and t-butyl perbenzoate, and
selected from the group consisting of nitrile initiators such as
a,a'-azobisisobutyronitrile, and mixtures thersof are also added
in an amount up to about 3% by weight of the total monomer charge.
All frea radical addition reactants are preferably added via
dxopwise addition over a period of time to the alkyd dispersing
medium. The monomer charge can be added pure, or, in a preferred
embodiment, the monomers can be dispersed in an amount of the alkyd
of this invention prior to addition to the dispersing medium. The
amount of alkyd used for such a dispersion should be included in
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~he calculation of the overall amount of alkyd present in the
reaction vessel. Any additional ingredients such as acrylic
polymers and copolymers, macromonomers, silicones, XI-100~ from
Monsanto (poly allyl glycidyl ether), alkyds, uralkyds, urethane-
modified oils, polyesters, and epoxy esters can be included in the
reactor charge provided thay are solubilized in either the monomer
charge or the alkyd dispersing media.
The temperature of the contents o~ the reaction vessel should
be maintained between about 200~F and 250F for the-entire period
that monomer charge is being added. A nitrogen blanket is also
highly preferred. Upon completion of the monomer addition, an
activator selected from the group consisting of the iron, copper,
vanadium, cobalt and manganese naphthenates, octoates, hexanates
and isodecanoates is added to the reactor vesssl and a
hydroperoxide chaser composition selected from the group consisting
oP cumane hydroperoxide, t-butyl hydroperoxide, t-amyl
hydroperoxide, and the like is added dropwise over a period o~
about 90 minutes. Upon completion o~ the chase, the temperature
should be maintained between 200F and 250F for approximately one
hour. At the end of that hour, the heat is removed and the
contents of the vessel are filtered.
The non-aqueous dispersions of this invention can be used
alone as coating compositions. Or, they can be used in combination
with other high or low VOC alkyds to reduce the overall VOC of a
coating. They can be combined with other film-forming compositions
such as acrylic polymers and copolymers, polybutadiene, and
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polyallyl glycidyl ether. They can be formula~ed with other
readily available, standard paint ingredients and components such
as crosslinking agents, catalysts, rheology modifiers~ ~hixotropes,
extenders, colors and pigments, solvents, anti-skinning agents,
drying agents, dispersants and surfactants, fungicides,
mildewcides, preservatives, UV absorbers, anti-marring agents,
anti-cratering agents, flow and leveling agents, fragrances,
defoaming agen~s, chelating agents, flattening agents, and anti-
rusting agents.
Suitable rheology modifiers are well known in the art and can
comprise organoclays, fumed silicat dehydrated castor oil organic
derivatives (exemplary tradenames Thixatrol (R), NL Industries;
Flowtone ~R), English China Clay), polyamides, polyamide modified
alkyds, MPSA-60, Rheox, alkylbenzene sulphonate derivatives,
aluminum, calcium and zinc stearates, calcium soyate, and the like.
Suitable extenders are also well known in the art and can
comprise amorphous, diatomaceous, fumed, quartz and crystalline
~ilica, clays, aluminum silicates, magnesium aluminum silicates,
talc, mica, delaminated clays, calcium carbonates and silicates,
gypsum, barium sulfate, zinc, calcium zinc molybdates, zinc oxide,
phosphosiliaates and borosilicates of calcium, barium and
strontium, barium metaborate monohydrate, and the like.
Suitable colors and pigments are well known in the art and
can comprise for example, titanium dioxide, carbon black, graphite,
ceramic black, antimony sulfide, black iron oxide, aluminum pastes,
yellow iron oxide, red iron oxide, iron blue, phthalo blue, nickel
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~itaslate, dianisidine orange, dinitroaniline orange, imidazole
orange, quinacridone red, violet and magenta, toluidine red,
molybdate orange, and the like.
Suitable solvents can comprise propylene and ethylene glycol
ethers and acetates, alcohols, ketones, aliphatic and aromatic
hydrocarbons and naphthas, petroleum and wood distillates,
turpentine, pine oil, and the like. Solvent selection is limited
primarily by the desire to maintain the overall VOC level of the
coating composition below 305 g/l, preferably below~250 g~l.
Anti-skinning agents such as methyl ethyl ketoxime, o-cresol,
and hydroquinone can be included.
Drying agents can comprise standard metallic and rare earth
driers such as cobalt, calcium, potassium, barium, zinc, manganese,
tin, aluminuml zirconium and vanadium napthenates, octoatest
hexanates, and isodecanoates. A particularly preferred drier
composition is a combination of cobalt, calc.ium and ~irconium
driers present in an amount from about 0.1% to about 2.5% by weight
of the coating composition.
Suitable dispersants and surfactants can comprise any of the
rea~ily available dispersants and surfactants to the coatings
industry, including the anionic and nonionic surfactants, soya
lecithin, alkyl ammonium salts of fatty acids, amine salts of alkyl
aryl sulfonates, unsaturated organic acids, sulfonated castor oil,
mixtures of high boiling point aromatic and ester solvents, sodium
salts of aryl sulfonic acid, Solsperse~ from ICI, and the like.
The following examples will demonstrate various embodiments
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of this invention.
EXAMPLE ONE--PREPA~TION OF ALKYD WITII Mz OF ABCUT 13, 973
Charge 1819g of soya fatty acid, 496g of pentaerythritol,
0.36g of dibutyltin catalyst and 32g of xylene to a reactor
equipped with inert gas, mechanical stirrer, barrett tube and
Friedrich's condenser. Heat to 370 degrees F and hold for one
hour. Cool to 360 degrees F and add 283g of crotonic acid, 400g
isophthalic acid, 186g RJ-101 (a styrene-allyl alcohol copolymer
available from Monsanto) and 32g xylene. ~eat to 485..degre~s F and
hold for a viscosity of Z4 (maximum) and an acid value <20 at 97.5%
NVM. Cool. The resultant alkyd has an NVM of 98.2, a viscosity
of Z3, an acid value of about 16, Mz of about 13,g73, Mw of about
5582, Mn of about 2113 and a polydispersity of about 2.64.
EXAMPLE TWO--PREPARATION OF ALKYD WITH Mz OF ABOVT 47,400
Charge 1808g of soya ~atty acid, 493g of pentaerythritol and
0.36g of a dibutyltin catalyst to a 51, 4-necked round bottom Plask
equipped with inert gas, mechanical stirrer, barrett tube and
Friedricks condenser. Heat to 370 degrees F and hold for one hour.
Add 280.96g of crotonic acid, 433.92g of isophthalic acid and
115.2g of RJ-101. Heat to about 478 degrees F and hold for a
viscosity of Z-Z2 at 90% NVM in mineral spirits and an aci~ value
~14. Cool to room temperature~ and reduce to 90% NVM in ~I:ineral
spirits. The resultant alkyd has ~0% NVM, viscosity of about Zl,
acid value of about 13.5, color of 6-7, Mz of about 47,404, Mw of
about 13,869, Mn of about 3r044 and a polydispersity of about 4.56.
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~AMPLE THREE--PREPARATION OF ALKYD WITH Mz OF ABOUT 2 8, 2?0
Charge 1354.7 grams of soya oil and 243.3 grams of trimelletic
anhydride to a 3 liter, 4-necked, round bottom flask equippPd with
inert gas blanket and mechanical stirrer. Heat the contents to
about 480F and hold for about one-half hour. Cool to about 400F
and add 255.3 grams of trimethylol propane, 25.6 grams of
trimethylol ethane and 408.2 grams of linseed fatty acid. Heat to
480F and hold for an Acid Value less than or equal to 13 and a
viscosity of W.
The resulting alkyd has an NVM of about 100%, a Gardner-Holdt
viscosity of about W, an Acid Value of about 9.7, an M2 of about
28,200, an oil length of about 80 and a Hydroxyl No. of about 37.
EXAMPLE FOUR--PREPARATION OF ALKYD WITH Mz OF ABOUT 23,639
Charge 1996.3g of soya fatty acid, 760.5g of dipentaerythritol
and 0.41g of dibutyltin catalyst to a 51, 4-necked reactor equipped
~ith inert gas, mechanical stirrer, barrett tube and Friedrich's
condenser. Heat to 370 degrees F and hold for one hour. Add
335.6g of crotonic acid, 321.6g of isophthalic acid and 85.76g of
xylene. Heat to 480 degrees F and hold for a viscosity of Z4
(maximum) and an acid value <13 at 100% NVM. The resultant alkyd
has an NVM of about 99.0%, a viscosity of about Z4, an acid value
of about 11, Mz of about 23,639, Mw of about 8,432, Mn of about
2829 and a polydispersity of about 2.98.
COMPARATIVE EXAMPLE ONE--ALKYD WITH Mz OF ABOUT 9,700
Charge 1861.3g soya fatty a¢id, 507.lg pentaerythritol and
0.37g of dibutyltin catalyst to a 51, 4-necked reactor equipped
.~lth inert gas, mechanica} stirrer, barrett tube and Friedric~'3(~
condenser. Heat to 370 degrees F and hold for one hour~ Add
189.8g RJ-101, 289.1g crotonic acid, 294.7g isophthalic acid and
58g of xylene. Heat to 485 degrees F and hold for a viscosity of
Y-Zl and an acid value <14 at 97.5% NVM. The resultant alkyd has
an NVM of about 98.25%, a viscosity of Y-z, an acid ~alue of about
10.8, color of about 4, Mz of about 9,716, Mw of about 3,927, Mn
of about 1894, and a polydispersity of about 2.07.
PREPARATION OF NADS
Four cate~ories of NAD's were prepared from each of the above
alkyds as well as from the Cargill 57-5843 alkyd and the McCloskey
Varkydol~210-lO0 alkyd. The NAD categories had the following
approximate compositions by weight:
NAD "Ai' 50 parts alkyd
35 parts methyl methacrylate
15 parts hydroxy ethyl acrylate
0.2 parts chain trans~er agent
NAD "B" 50 parts alXyd
50 parts methyl methacrylate
0 parts OH-functional monomer
0.2 parts chain transfer agent
NAD ~'C~' 50 parts alkyd
35 parts methyl methacrylate
15 parts hydroxy ethyl acrylate
0 parts chain transfer agent
NAD "D" 50 parts alkyd
50 parts methyl methacrylate
0 parts OH-functional monomer
0 parts chain transfer agent
The following procedure was used to make each NAD:
Charge about 1/2 of the alkyd to a reactor equipped with a
mechanical stirrer. Heat to 100C. Disperse the monomer/chain
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cransfer agent solution in the remainder of the alkyd and begin a
three hour dropwise addition of the solution along with a initiator
solution comprising t-butyl peroctoate in mineral spirits to the
reactor. Upon completion of the addition of the solutions, hold
for approximately one hour and then add vanadium naphthenat~ to the
reactor. Begin a 90 minute addition of a "chase" comprisin~
mineral spirits and cumene hydroperoxide. Hold the temperature at
100C for approximately ~ to 1 hour after the chase has been
completely added. Shut off heat and filter the contents o~ the
reactar through a 15 micron polyester filter bag.
Table I demonstrates the properties of each NAD:
Alkyd~CTA NAD l'AI' NAD "Bl' NAD "CI' ND'~'
Ex. I NVM 83% NVM 82.2% SCRAP SCRAP
2-Me* 6/12 rpm FILTER CLOG
3750/3875cps Hegman:0
**Hegman:8
Ex. II NVM 85.4% SCRAP SCRAP SCRAP
DM* 6 rpm
57000 cps
Hegman:l
Ex. III NVM 86.8% SCRAP SCRAP SCRAP
2-Me 6/12 rpm
2100/2150cps
~egman:8
Ex. IV NVM 82.1% SCRAP SCRAP SCRAP
2-Me 6/12 rpm
8800/9000cps
Hegman:8
Ca~gill 5843 NVM 83% NVM 78.1% NVM 82.2% SCRAP
DM 6/12 rpm ~ILTER CLOG FILTER CLOG
5900/5200cps Hegman:1 Hegman:l
Hegman:5
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tf~ 3 ~ ~
Cargill 5843 NVM 82.4% NVM 81.4% SCRAP SCRAP
2-Me 6/12 rpm FILTER CLOG
1850/1~50cps
Hegman:5
McCloskey NVM 82.2~ NVM 86~3~ SCRAP SCRAP
2-Me 6/12 rpm FILTER CLOG
860/860cps
Hegman:8
McCloskey NVM 97.8% NVM 95.9% SCRAP SCRAP
2-~e 6/12 rpm FILTER CLOG
24,600cps
Hegman:8
Comp. ~x. I SCRAP SCRAP SCRAP SCRAP
2-Ma
* 2-Me refers to 2-mercapto ethanol and DM refers to dodecyl
mercaptan.
** The Hegman values were taken prior to filtration and measure
grittiness with a value of "O" representiny all grit and a value
of ~'8" representing no grit.
305 g/l VOC PAINT PREPARATION EXAMPLES
The following procedure was generally followed for each paint
composition below. Charge a vessel with the initial NAD and the
mineral spirits charges shown below. Start dispersing and add soya
lecithin and titanium dioxide under low speed. Increase to high
spee~ mixing. Run approximately 10 to 15 minutes. Decrea~e to low
speed mixing and add the remaining materials in the order shown
~elow.
EXAMPLE FIVE
~ he following formula was used to prepare a 3U5 g/l VOC gloss
paint:
:NAD l'A'I from Alkyd of Ex. I 302.33 lbs
Mineral Spirits 24.96
Soya Lecithin 3.00
Rutile Titanium Dioxide190.00
NAD "All from Alkyd of Ex. I 305.63
Mineral Spirits 21.59
19
~: :
: . -
12% Cobalt Catalyst 1.24
10~ Ca Synthetic Acid Drier 7.96
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 98.36
The paint had KU and ICI viscosities at 25 degrees C of 67 and
3.1, respectively.
EXAMPLE SIX
The following formula was used to prepare a 305 g/l VOC gloss
paint:
NAD "~" from Alkyd of Ex. II 302.33 lbs
Mineral Spirits 24.96
Soya Lecithin 3.00
Rutile Titanium Dioxide 190.00
NAD "A" from Alkyd of Ex. II 282.86
Mineral Spirits 21.59
12~ Cobalt Catalyst 1.24
10~ Ca Synthetic Acid Driar 7.96
Methyl Ethyl Ketoxime 2.Q0
Mineral Spirits 119.38
The paint had XU and ICI viscosities at 25 degrees C of 106
and 5+, respectively.
EXAMP~E SEVEN
The following formula was used to prepare a 305 g/l VOC gloss
paint:
NAD "A" from Alkyd of Ex~ III 305~66 lbs
Mineral Spirits 24.96
Soya Lecithin 3.00
Rutile Titanium Dioxide 190.00
NAD "A" from AlXyd of Ex. III 319.76
Mineral Spirits 21.59
12% Cobalt Catalyst 1.24
10% Ca Synthetic Acid Drier 7.96
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 93.85
The paint had KU and ICI viscosities at 25 degrees C of 62
and 1.3, respectively~
EXAMPLE EIGHT
The following formula was used to prepare a 305 g/l VOC gloss
paint:
NAD "A" from Alkyd of Ex. IV 302.33 lbs
~0
, : :
' ' ~ ' ' ' ~ " '' ' . ' '
3 .
2 ~
Mineral Spirits 24.96
Soya Lecithin 3.00
Rutile Titanium Dioxidel90.Q0
NAD l'A" from Alkyd of Ex. IV 310.71
Mineral Spirits 21.59
12% Cobalt Catalyst 1.24
10% Ca Synthetic Acid Drier 7.96
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 92.08
The paint had KU and ICI viscosities at 25 degrees C of 72
and 4.8, respectively.
EXAMPLE NINE
The following formula was used to prepare a 305 ~ OC ~loss
paint:
NAD "A" from Cargill 57-5843/DM 305.66 lbs
Mineral Spirits 24.96
Soya Lecithin 3.00
Rutile Titanium Dioxide190.00
NAD "A" 303.20
Minexal Spirits 21.59
12% Cobalt Catalyst 1.24
10% Ca Synthetic Acid Drier 7.96
~ethyl Ethyl Ketoxime 2.00
Mineral Spirits 98.23
The paint had KU and ICI visco5ities at 25 degrees C o~ 73
and 3.6, respectively.
EXAMPLE TEN
The following ~ormula was used to prepare a 305 g/l VOC gloss
paint:
NAD "A" ~rom Cargill 57-5843/2-Me 304.47 lbs
Mineral Spirits 24.96
Soya Lecithin 3.00
Rutile Titanium Dioxide190.00
NAD "A" 303.20
Mineral Spirits Z1.59
12% Cobalt Catalyst 1.24
10~ Ca Synthetic Acid Drier 7.96
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 95.00
The paint had KU and ICI viscosities at 25 degrees C of 61
and 1.6, respectively.
IF..~ ~; ,,
2~3~$
EXAMPLE ELEVEN
The following formula was used to prepare a 305 ~/1 VOC gloss
paint:
NAD "A" (NVM 82.2) McCloskey Alkyd 305.66 lbs
Mineral Spirits 25~08
Soya Lecithin 3.00
Rutile Titanium Dioxide 190.00
NAD "Al' 300.00
Mineral Spirits 21.5
12~ Cobalt Catalyst 1.24
10% Ca Synthetic Acid Drier 7.96
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 93.73
The paint had KU and ICI viscosities at 25 degrees C of 65
and 1.5, respectively. ~
EXAMPLE TWELVE
The following formula was used to prepare a 305 g/l VOC gloss
paint:
NAD "A" (NVM 97.~) McCloskey Alkyd 308.80 lbs
Mineral Spirlts 25.08
Soya Lecithin 3.00
Rutile Titanium Dioxide 190.00
NAD "A" 190 32
Mineral Spirits 21 59
12% Cobalt Catalyst 1.24
10% Ca Synthetic Acid Drier 7.96
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 190.56
The~ paint had KU and ICI viscosities at 25 degrees C of 61
and 1.2, respectively.
243 g/l VOC PAINT PREPARATION EXAMPLES
EXAMPLE THIRTEEN
The following formula was used to prepare a 243 g/l VOC gloss
paint ~ormula:
NAD l'A'' from Alkyd of Ex. I 302.33 lbs
Mineral Spirits 24~96
Soya Lecithin 3.00
Rutile Titaniu~ Dioxide 190.00
MAD "A" from Alkyd of Ex. I 397.24
Mineral Spirits 21.59
12% Cobalt Catalyst 1.44
22
'
.
.
- ~ :
2~.3~
10~ Ca Synthetic Acid Drier 9.18
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 30.42
The paint had KU and ICI viscosities at 25 degrees C of 95 and
5+, respectively.
EXAMPLE FOURTEEN
The following formula was used to prepare a 243 g/l VoC gloss
paint formula:
N~D "A" from Alkyd of Ex. III 305.66 lbs
Mineral Spirits 24.g6
Soya Lecithin 3.00
Rutile Titanium Dioxide 190.00
NAD "A" Erom Alkyd of Ex. III 414.03
Mineral Spirits 21.59
12% Cobalt Catalyst 1.44
10% Ca Synthetic Acid Drier 9.18
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 25.21
The paint had KU and ICI viscosities at 25 degrees C of 83 and
3.7, respectively.
EXAMPLE FIFTEEN
The following formula was used to prepare a 243 g/l VOC gloss
paint formula:
NAD 'IAl' from Cargill 57-5843/DM 305.66 lbs
Mineral Spirits 24.96
Soya Lecithin 3.00
~util~ Titanium Dioxide 190.00
NAD "A" 394.91
Mineral Spirits 21.59
12% Cobalt Catalyst 1.44
10% Ca Synthetic Acid Drier 9.18
Methyl Ethyl Ketoxime 2.00
~ineral Spirits 30.29
The paint had KU and ICI viscosities at 25 degrees C of 124
and 5+, respectively.
EXAMPLE SIXTEEN
The following formula was used to prepare a 243 g/l VOC gloss
paint formula:
NAD "A" from Cargill 57-5843/2-Me 304.47 lbs
Mineral Spirits 24.96
23
~, ' ' -
. ~ - -
:; :
2 ~
Soya Lecithin 3.00
Rutile Titanium Dioxide 190.00
NAD "A" 394-74
Mineral Spirits 21.59
12% Cobalt Catalyst 1.44
10% Ca Synthetic Acid Drier 9.18
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 26.54
The paint had KU and ICI viscosities at 25 degrees C of 86 and
5+, respectively.
EXAMPLE SEVENTEEN
The following formula was used to prepare a 243 ~/1 VOC gloss
paint formula:
NAD "A" (NVM 82.2~ McCloskey Alkyd 305.66 lbs
Mineral Spirits 24.13
Soya Lecithin 3.00
Rutile Titanium Dioxide 190.00
NAD "A" 391.33
Mineral Spirits 21.59
12% Cobalt Catalyst 1.44
10% Ca Synthetic Acid Drier 9.18
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 26.04
The paint had KU and ICI viscosities at 25 degrees C o ~6 and
4.8, respectively.
EXAMPLE EIGHTEEN
The following formula was used to prepare a 243 g/l VOC gloss
paint ~ormula:
NAD "A" (NVM 97.8) McCloskey Alkyd 308.80 lbs
Mineral Spirits Z5.08
Soya Lecithin 3.00
Rutile Titanium Dioxide ~90.00
NAD "A" 265.46
Mineral Spirits 21.59
12% Cobalt Catalyst 1.44
10% Ca Synthetic Acid Drier 9.18
Methyl Ethyl Ketoxime 2.00
Mineral Spirits 136.59
The paint had KU and ICI viscosities at 25 degrees C of 82 and
3.5, respectively.
24
., . , ~ , . .
-
. ' : ~ :' ~
- . ., : :
