Note: Descriptions are shown in the official language in which they were submitted.
2~
IMPROVED NON-AQUEOUS DISPERSIONS
R~ Tomko
M. Rao
D. Sayre
BACKGROUND OF THE INVENTION
Non~aqueous dispersions (NAD's) are well known in the art and
typically consist of dispersions of addition polymers in a
relatively non-polar non-aqueous liquid containing a steric
stabilizing agent having dual a~finity to both 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 ~y either the direct
esterification of a drying oil *atty acid with a diaarboxylic acid
and a polyhydric alcohol or the indirect esterification of a drying
oil by first alcoholization with a polyhydric alcohol and second
esterification with a polybasic acid. European Patent Application
0 310 331 A2 teaches a non-a~ueous di~persion of a soluble low
molecular weight non-alkyd polymer which i8 attached or adsor~ed
onto a second non-soluble alkyd-~ree polymer. U.S. Patent
4,530,957 teaches non-aqueous dispersions based on crosslinked
acrylic polymar particles dispersed in a non-aqueous medium having
a polymeric dispersion stabilizer. The polymeric dispersion
stabilizer can be an alkyd which is formed by the self condensation
of 12-hydroxystearic acid follow2d by a capping reaction with
glycidyl methacrylate. U.S. Patent 4,206,099 teaches non-aqueous
dispersions of crosslinked polymer particles in a non-aqueous
medium having an amphipathic steric stabilizing agent. The steric
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. Pa~ent 3,77~,977 teaches non-aqueous dispersions
of an acrylonitrile copolymer in a liquid butadiene homopolymer or
copolymer in a non-polar organic hydrocarbon liquid.
Previous work of ours has shown that selecting alkyds which
have speci~ic properties for use as the steric stabilizing media
for an NAD can lead to high solids, low VOC stable NAD's which
exhibit acceptable viscosities. In the present invention, we have
found a means ~or producing NAD's which utilize conventional, lower
solids alkyds as the steric stabilizing media. our present NAD's
have excellent stability, filterability, gloss, low grit, viscosity
and tack-free and dry hard times when formulated as air dry coatiny
compositions. Surprisingly, when produced at the same solids
content as the alkyd used to make the NAD's, they exhibit
substantially equivalant or lower viscosity than that alkyd. Thus,
the potential ~or lowering the VOC o~ the coating exists. The
NADIs of this invention also air dry ~aster than the alkyds used
to make the NAD.
These NAD's-utilize conventional, traditional alkyds as the
dispersing media and steric stabilizer. These NAD's require a
specific selection process wherein certain aritical parameters,
described fully below, must be observed in order to improve the
coating.
- i ~ 2~ 5
SUMMARY OF THE INVENTION
This invention relates to improved non-aqueous dispersions
(NAD's) and a process for producing these improved non-aqueous
dispersions. The improved NAD's of this invention comprise a
conventional alkyd as the dispersing medium and steric stabilizer
for the polymerization product of specific monomers, which polymers
are predominantly non soluble in the alkyd medium. The improved
NAD's of this invention are the product of a process which utilizes
a conventional alkyd steric stabilizer in the dispersing media, a
combination of monomers wherein at least one monomer is selected
from the group consisting of acrylonitrile, methacrylonitrile,
hydroxy ethyl acrylate and methacrylate, methyl acrylate and
methacrylate, acrylamide, methacrylamide, vinyl chloride,
vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid,
maleic acid, fumaric acid, the methyl esters of itaconic, maleic
and fumaric acid, and mixtures thereof, wherein at least one
monomer is a hydroxy-functional free radical addition monomer, and
wherein the polymerization is conducted in the presence of a chain
transfer agent. ThiG yields NADIs which ara 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 combinatio~ with other minor amounts of
other alkyd, modified-alkyd, or hydrocarbon disp~rsing media, for
the polymerization of monomers, which polymers are predominantly
insoluble in the alkyd medium. The particular means for the
production of the alkyd are not o~ import to this invention. Thus,
the alkyd can be produced according to any of the traditional
processes for the production of alkyds which are readily available
from the art. However, as a conventional alkyd, thP alkyd
stabilizer has an Mz of greater than about 150,000,`an NVM solids
content of less than about 70%, more preferably of between about
40~ and about 70%, and a viscosity in the above NVM range and at
25 degrees C of no greater than about lO,000 cps.
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. A critical parameter
which must be followed is that at least one monomer must be
selected from the group consi~ting of acrylonitrile,
methacrylonitrile, hydroxy ethyl acrylate and methacrylate, methyl
acrylate and methacrylate, acrylamide, methacrylamide, vinyl
chloride, vinylidene chloride, acrylic acid, methacrylic acid,
itaconic acid, maleic acid, fumaric acid, the methyl esters of
itaconic, maleic and fumaric acid, and mixtures thereof. A second
critical parameter is that at least one monomer must have hydroxy-
functionality. A third critical parameter which must ~e ~ollowed
~ 5
is that the polymerization must take place i~ the presence of a
chain transfer agent.
We have ~ound that by following these key critical parameters,
explained in more detail below! one can formulate an NAD which is
stable, non-gritty, filterable, with a substantially equal or lower
viscosity at the same solids level than the alkyd which was used
to make the NAD and which dries fas~er than that alkyd. We have
found that failure to ~ollow these key critical parameters when
using a conventional alkyd as the dispersing media re~ults in NADIs
which do not exhibit the equivalence or improvements in viscosity
or dry time vis-a-vis the alkyd used to make them and/or are
unstable, gritty, non-filterable or have excessively low
conversions.
Accordingly, it is an object of this invention to teach
improved non-aqueous dispersions which utilize conventional alkyds
as the dispersing medla.
It $s another object of this invantion to teach a non-aqueous
dispersion having improved air dry times.
It is a further ob;ect o~ this invention to teach a process
for producing non-aqueous dispersions havinq improved air dry
times.
It is a further ob;ect o~ this invention to teach coating
compositions containing the non aqueous dispersions of this
invention.
DETAILED D~SCRIPTION OF THE INVENTION
As stated above, the process for pxoducing the NAD's of this
invention comprises selecting a conventional alkyd; and using this
alkyd as the dispersing medium, either alone or in combination with
some minor amount o~ solvent or other dispersi~g ~edia, for the
polymerization of monomers, which polymers are predominantly
insoluble in the alkyd medium. The alkyd used in these NAD's is
formed by any of the traditional processes such as fatty acid
esterification or alcoholysis of a drying oil with later reaction
with a di- or tri- basic acid. The alkyds of this invention are
selected from conventional alkyds for the paint `and coatings
industry. Conventional alkyds are defined herein as alkyds having
a z-average molecular weight greater than about 150,000, preferably
between about 250,000 and about 1,000,000, and an NVM solids
content of less than about 70~, preferably between about 40% and
about 70%.
Typical raw materials for the ~ormation of alkyds include
triglyceride oils or t~e 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 thosè
oils and acids containing unsaturation in the glycexide chains.
Particularly preferred are soya oil, dehydrated castor oil and
linseed oil and the fatty acids thereof.
Multi-functional alcohols, and mixtures thereof, are al80
common raw materials for the production of alkyds. one suitable
b. ~ '~5
~ ~.
hexafunctional alcohol includes dipentaerythritol~ One suitable
tetrafunctional alcohol includes pentaerythritol. Suitable
tri~unctional alcohols include the group con6isting of trimethylol
propane, trimethylol ethane, glycerine, tris hydroxyethyl
isocyanurate, and mixtures thereof, either alone or in combination
with a difunctional alcohol selected from the group consisting of
ethylene glycol, propylene glycol, cyclohexane dimethanol, and
mixtures thereof. Addition~lly, dimethyl~l propionic acid can be
used in combination with the trifunctional alcohol. Multi-
~unctional alcohols, trifunctional alcohols, and mixtures thereof
are particularly preferred due to the degree o~ branching they
allow. Difunctional alcohols, if used, are preferably u~ed as a
minor component in combination with tri~unctional alcohols. A
portion of monofunctional alcohol, or monobasic acid such as soya
fatty acid, linseed oil fatty acid, ben~oic acid or crotonic acid,
up to about 20~ by weight 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 f ormation of alkyds
iB multi-functional carboxylic acids or anhydrides. Suitable
trl~unctional carboxylic acids include trlmelletic acid, trimesic
acid, 1,3,5-pentane tricarboxylic acid, citric acid and others
whereas suitable trifunctional anhydrides include trimelletic
anhydride, pyromelletic anhydride and others. Di~unctional
carboxylic acids include phthalic acid, isophthalic acid,
terephthalic acid,-maleic acid and fumaric acid and mixture~
thereo~. 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, a z-average
molecular weight, Mz, greater than about 150,000, pre~erably
between about 250,000 and a~out l,OOo,000. It should be
appreciated that the longer these materials are allowed to react,
the greater the resultant molecular weight of the alkyd. The alkyd
should have an oil length o~ between about ~0% and 75%, an acid
value less than about 20, and a hydroxyl number less than 100,
preferably between about 40 and about ~0. The NVM should be below
about 70%, preferably between about 40% and about 70%.
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 0O02% by weight of oil.
The NAD's made according to this invention typically have
Brookfield LVT #3 (6/12 rpm) viscosities less than about 10,000 cps
at 25 degrees C, preferably lees than about 7,000 cps. They can
easily be formulated to have volatile organic contents less than
400 g/l, many times less than 380 g/l, and exhibit excellent air
dry times using conventional drier compounds. Interestingly, the
NADIs o~ this invention, at the same solid~ level, exhibit
viscosities substantially equal to or lower than the alkyds used
to prepare them. They also hava very ~ast dry times when compared
to thP alkyds used to prepare them.
As stated above, any-conventional alkyd as herein de~ined can
s
be used in thi~ invention. Particularly suitable commercially
available alkyds for use in this invention include the alkyds
available from Cargill, Inc. such as 5070 (soya oil alkyd), 5054
(linseed oil alkyd), 5091 (tall oil fatty acid alkyd), 5076 (soya
oil in odorless mineral spirits alkyd), and 5074 (isophthalic soya
oil alkyd). One particularly preferred alkyd is the reaction
product of soya oil, pentaerythritol, maleic anhydride and phthalic
anhydride as shown in Example I, below.
When preparing non-aqueous dispersions accor~ing to this
invention, the monomers should be selected from monomers which
would produce a polymer via the free radical addition reaction
mechanism, which polymer is predominantly insoluble in the alkyd
medium. It is essential that at least one of the monomers be
selected from the group con~isting of acrylonitrile,
methacrylonitrile, hydroxy ethyl acrylate and methacrylate, methyl
acrylate and methacrylate, acrylamid~, methacrylamide, vinyl
chloride, vinylidene chlorideJ acrylic acid, methacrylic acid,
itaconi¢ acid, maleic acld, fumaric acid, the methyl es~ers of
itaconic, maleic and fumaric acid, and mixtures thereof. It is
also essential that at least one of the monomers have hydroxy
functionality. More pre~erably, between about 5% and 35% by weight
o~ the total reactor solids comprises hydroxy functional monomers.
Most preferably, between about 10% and about 25% by weight of the
total reactor solids comprises a hydroxy ~unctional monomer such
as hydroxy ethyl acrylate or hydroxy ethyl methacrylate.
In addition to pure monomer~, pre~ormed polymer~, 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 abouti20 and 40~, and the hydroxy ethyl
acrylate is present in an amount o~ between about 10 and 25%, by
weight of total reactor solids.
Additional monomers selected ~rom the group consisting of
hydroxy propyl acrylate and methacrylate, ethyl acrylate and
methacrylate, butyl acrylate and methacrylate, lauryl acrylate and
methacrylate, 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, can be included in the reactor charge in relatively minor
amounts, so long as they are not added in percentages sufficient
to adversely affect the viscosity and/or odor of the NAD. Certain
monomers are to ba avoided such as styrene because of an
unacceptable resultant increase in NAD viscosity. Also to be
avoided are divinyl benzene, vinyl naphthalene, and vlnyl toluene
because these are generally soluble in alkyds. Vinyl acetate is
unacceptable for inclusion as it does not polymerize under the
conditions taught herein~ These monomers have been found to
cont~ibute to a decrease in yield, additional grit, and/or a
lessening.of stability over time.
To prepàre the NAD's of this invention, the alkyd disper~ing
a ~ 1~ 2 ~ J ~ ~ ~ 5
medium is used as the polymerization medium ~or the monomer charge.
The alkyd medium can be diluted with mineral spirits or other
solvent if desired, with ~he primary limitation being concern for
the VOC of the composition and the viscosity increase which
accompanies the swelling and solubilization of the dispersed phase
in stronger solvents.
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 35% to about 75~, p~efera~ly from
about 40% to about 60%, by weight of the total reactor solids. The
~ree radical addition monomer charge should, after completely added
to the reaction vessel, account for approximately 65% to about 25%,
preferably between about 60% to about 40~, by weight of the total
reactor solids.
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 601ids. Most
preferred is 2-mercapto ethanol.
An initiator which will not oxidize the chain transfer agent
is selected from the group consisting o~ organic peroxides such as
benzoyl peroxide, iauroyl peroxide, di-t-butyl peroxide, acetyl
peroxide, t-butyl peroctoate, t amyl peroctoate, and t-butyl
perbenzoate, or selected from the group consisting of nitrile
initiators such as a,a~-azobisisobutyronitrile, and mixtures
therèof and i8 also added in an amount up ko about 3% by weight of
L ~ ~ 5
the total monomer charge.
All free radical addition reactants are preferably added via
dropwise 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
prior to addition to the dispersing medium. The amount of alkyd
used for such a dispersion should be included in the calculation
of the overall amount of alkyd present in the reaction vessel. Any
additional ingredients such as acrylic polymers and copolymers,
macromonomers, silicones, XI-loo from Monsanto (poly allyl
glycidyl ether), alkyds, uralkyds, urethane-modified oils,
polyesters, and epoxy esters can be included in the reactor charge
provided they are solubilized in either the monomer charge or the
alkyd dispersing media.
The temperature of the contents of the reaction vessel should
be maintained between about 200~F and 250aF for the entire period
that monomer charge is being added. A nitrogen blanket i5 also
highly preferred. Upon completion o~ the monomer addition, up to
about 0.1~ by weight of total reactor charge an activator selected
fro~ the group consisting of the iron, copper, vanadium, cobalt and
manganese naphthenates, octoates, hexanates and iæodecanoates is
added to the reactor vessel and from about 0.5% to about 5.0~ by
weight of total reactor solids of a hydroperoxide chaser
composition selected ~rom the group consisting o~ cumene
hydroperoxide,-t-butyl hydroperoxide/ t-amyl hydroperoxide, and the
like is added dropwise over a period o~ about 90 minutes. The
12
r
2q ~ 9 5
hydroperoxide chasers are preferred because they oxidize the
remaining mercaptan from the chain transfer agent and thus
eliminate the odor from the sulfur. Upon completion of the chase,
the temperature should be maintained between 200~F and 2~0~F for
approximately one hour. At the end of that hour, the heat is
removed and the contents of the vessel are filtered.
Tha non-aqueous dispersions o~ this invention can be used
alone as coating compositions. Or, they can be blended or used in
combination with other alkyds or NAD~s. They can be combined with
other film-forming compositions such as acrylic polymers and
copolymers, macromonomers, silicone alkyds, XI-100 from ~onsanto,
alkyds, uralkyds, urethane-modified oils, polyesters, epoxy esters,
polybutadiene, and polyallyl glycidyl ether. They can be
formulated with other readily available, standard paint ingredients
and components such as crosslinking agents, catalysts, rheology
modifiers, thixotropes, extenders, colors and pigments, solvents,
anti-skinning agents, drying agents, dispersants and surfactants,
fungicides, mildewcides, preservatives, W absorbers, anti-marring
agents, anti-cratering agents, flow and leveling agents,
fragrances, defoaming a~ents, chelating agents, flattening agents,
and anti-rusting agents.
Suitable rheology modifiers are well known in the art and can
comprise organoclays, fumed silica, dehydrated castor oil organic
derivatives texemplary tradenames: Thixatrol (~), NL Industries;
Flowtone (R), English China Clay), polyamides, polyamide modi~ied
alkyds, MPSA-60, Rheox, alkylbenzene sulphonate derivatives,
~_ - ` 2~'$~ ~5
aluminum, calcium and zinc stearates, calcium soyate, and the like.
Suitable extenders are also well known in the art and can
comprise amorphous, diatomaceous, ~umed, quartz and crystalline
silica, clays, aluminum silicates, magnesium aluminum silicates,
talc, mica, delaminated clays, calcium carbonates and silicates,
gypsum, barium sul~ate, zinc, calcium zinc molybdates, zinc oxide,
phosphosilicates 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
titanate, 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 seleation iæ limit~d
primarily by the desire to maintain the overall VOC level of the
coating composition as low as possible without resulting in an
unacceptable increase in viscosity.
Anti-skinning agents such as methyl ethyl ketoxime, o-cresol,
and hydroquinone can b.e included.
Drying agents can comprise standard metallic and rare earth
driers such as cobalt, calcium, potassium, barium, zinc, manganese,
14
- z~ 5
_~"~ ' ~. ~?` - ~
tin, aiuminum, zirconium and vanadium napthenates, octoates,
hexanate~, and isodecanoates. A particularly preferred dri~r
c~mpoSition iS a combination of cobalt, calcium~ and zirconiu~
driers present in an amount from about 0.1% to about 2.5% by waight
of the coating composition.
Suitable dispersants and surfactants can comprise any of the
readily available dispersants and surfactants to the coatings
industry, including the anionlc and nonionic sur~actants, soya
lecithin, alkyl ammonium salts oP 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
of this invention.
` ~ EXAMPLE I: PREPARATION OF ALKYD
Charge a reactor equipped with inert gas, mechanical stirrer,
and condenser with 2591 lbs alkali refined ~oybean oil and 753
lbs of pentaerythritol. Heat to 400 degrees F under inert gas
blanket. ~dd 5.1 lbs of lithium hydroxide catalyst and heat to
470 degrees F. Hold ~or approximately two hours untll clear. Add
1133 lbs of soybean oil and cool to 390 degreeff F. Add 28 lb~ of
maleic anhydride, 1375 lbs of phthalic anhydride and 144 lbs o~
xylene. Heat to 490 degrees F and hold for a ~iscosity of Z-Z2
using the Gardner-Holdt method and an acid value of les~ than about
10 at 70~ NVM in mineral spirits. Cut with 2300 lbs-of mineral
2~ 5
i ` ,.
spirits to produce a 70% Nv~ alkyd.
The resulting alkyd should have an Mz of between about 250,000
to about 1,000,000, an NVM of about 70% and a viscosity of about
5700 to 5900 Cp6 at 25 degrees C.
The following procedure was used to make the NAD's of Examples
A through ~ from the alkyd of Example I:
Charge about 1/2 of the alkyd to a reactor equipped with a
mechanical stirrer. Heat to 100C. Disperse the monomer/chain
transfer agent solution in the remainder of the alkyd along with
an initiator solution comprising t-butyl peroctoate and begin a
three hour dropwise addition of the solution to the reactor. Upon
completion of the addition of the solutions, hold for approximately
one hour and then add vanadium naphthenate to the reactor. Begin
a 90 minute addition of a "chase" comprising mineral spirits and
cumene hydroperoxide. Hold the temperature at lOO~C for
approximately ~ to 1 hour after the chase has been completely
added. Shut off heat and filter the contents of the reactor
through a 15 micron polyester filter bag.
The following N~D's were made according to the above procedure
(parts by weight), with the following properties reeulting
t~erefrom. The Hegman scale is used to measure the level of
grittiness of the NAD priox to filtration, with a value of "8"
representing no grit and a value of "0" representing all grit.
Viscosities were measured using the Brookfield Viscometer LVT #3
spindle at 12 rpm.
2 ~ x 5
EXAMPLE A
50 parts alkyd
35 parts methyl methacrylate
15 parts hydr~xy ethyl acrylate
0.28 parts 2-mercapto ethanol
NVM: 6~.1%
Visc: 2850 cps
Hegman: 8
EXAMPLE B
~0 parts alkyd
. 50 parts methyl methacrylate
0 parts OH-functional monomer
0.28 parts 2-mercapto ethanol
NVM: 71.0%
Visc: 186,000 cps
Hegman: 2
EXAMPLE C
50 parts alkyd
35 parts methyl methacrylate
15 parts hydroxy ethyl acrylate
0 parts chain transfer agent
NVM: 68.3%
Visc: 2000 cps
~egman: 2
EXANPLE D
50 parts alkyd
50 parts mathyl methacrylate
0 parts OH-functional monomer
0 parts chain transfer agent
NVM: 67.1~
Visc: 15,800 cps
Hegman:
EXANPLE E
50 parts alkyd
O parts methyl methacrylate
50 parts hydroxy ethyl methacrylate
0.28 parts chain transfer. agent
17
2~
NVM: 71.5%
Visc: 10,400 cps
Hegman: 8
EXAMPLE F
50 parts alkyd
35 parts methyl methacrylate
; 15 parts ethyl acrylate
o parts OH-functional monomer
0.28 parts chain transfer agent
` Result: Paste
EXAMPLE G
50 parts alkyd
45 parts methyl methacrylate
5 parts acrylic acid
O parts OH-functional monomer
0.28 parts chain transfer agent
NVM: 6~.0~
Visc: 7,000 cps
Hegman: 8
EXAMPLE H
50 parts alkyd
35 parts methyl methacrylate
15 parts styrene
O parts OH-functional monomer
0.28 parts chain transfer agent
NVM: 67.7~
Visc: 18,300 cps
Hegman: 4.5
Paint compositions were made from the alkyd of Example I and
from the NAD o~ Example ~ as follows:
EXAMPLE II--PAIN~ CON~AINING ALKYD OE EXAMPLE I
Add 246.23 lbs of alkyd from Example I to a mixing vessel.
Begin the grind phase by adding 11.38 lbs of aliphatic naptha and
3.64 lbs o~ soya lecithin. Start the mill and add 111.50 lbs of
18
rutile titanium dioxide ~nd 5.00 lbs of organophilic clay. Run on
high for l minutes. Reduce the speed of the mill and stabilize
with 45.20 lbs of aliphatic naptha and 29.49 lbs of alkyd from
Example I. Add 0.64 lbs 12% cobalt catalyst, 3.83 lbs 18~
zir~onium 2-ethylhexanoate and 1.38 lbs 10% calcium driers. Add
l.Oo lbs of methyl ethyl ketoxime and 11.74 lbs of aliphatic
naptha.
The resultant paint has KU and ICI viscosities at 25 degrees
C of 80 and 4.4, respectively. The "dry-to-set" time, as measured
by the ~yk-Gardner circular drytime recorder, at 25 degrees c and
50% relative humidity, is approximately 2.5 hours. The "surface-
dry" time, as measured the same instrument under the same
conditions i~ approximately 2.25 hours. The "thru-dry" time, as
measured by the same instrument under the same conditions is
greater than 12 hours. The "dry-hard" time, as measured by the
same instrument under the same conditions is greater than 12 hours.
EXAMPLE III--PAIN~ CON~AINING N~D OF ~XAMPLE A
Add 294.90 lbs of an NAD (composition of 45 parts by weight
alkyd of Example I, 40 parts methyl methacrylate, 15 parts hydroxy
ethyl acrylate and 0.28 parts 2-mercapto ethanol, produced
according to the procedure used ~or Examples A-H, above) to a
mixing vessel. Begin the grind phase by adding 21.45 lbs of
aliphatic naptha and 7.28 lbs of soya lecithin. Start the mill and
add 223.00 lbs of rutile titanium dioxld~ and 10.00 lbs of
organophilic clay. Xun on high for 15 minutes. Reduce the ~peed
19
2~ 5
of the mill and stabilize with 109.01 lbs of aliphatic nap~-ha and
260.79 lbs of NAD. Add 0.92 lbs 12% cobalt catalyst and 9.18 lbs
10% calcium driers. Add 2.00 lbs of methyl ethyl ketoxime and
23.47 lbs of aliphatic naptha.
The resultant paint has KU and ICI viscosities at 25 degrees
~ of 86 and 2.7, respectively. The "dry-to-set" time, as measured
by the syk-Gardner circular drytime recorder, at 25 degrees C and
50~ relative humidity, is approximately 0.75 hours. The "surface-
dry" time, as measured the same instrument u~der the same
conditions is approximately 1.0 hours. The "thru-dry" time, as
measured by the same instrument under the same conditions is
approximately 1.5 hours. The "dry-hard" time, as measured by the
same instrument under the same conditions is approximately 3.5.
