Note: Descriptions are shown in the official language in which they were submitted.
196
SPECIFICATION
The invention concerns a polymer and the method of
using the same to prepare articles of manufacture, the com-
position comprising a water-soluble salt of a polymer con-
taining pendant groups derived from an unsaturated drying
oil fatty acid hydroxyamide, carboxy groups, carboxy ester
groups and optionally the residues of other unsaturated addi-
tion polymerizable monomers, the carboxy units being present
in a critical amount and the polymer having a critical glass
transition temperature, molecular weight and the like. The
groups derived from the hydroxyamide have the structure of
formula V given below.
In the past, similar polymers have been known for
coatings and for other utilities such as putty-like caulking
compositions. The caulking compositions are shown in Kottke
U.S. Patent No. 3,759,915 whereas the coating compositions
are shown in Hopwood et al, U.S. Patent No. 3,590,016. This
invention is basically an improvement upon the Hopwood et al
patent. In that patent, as in the present application, the
polymers contain an acrylic backbone having pendant carboxy
units, post-reacted in the preferred embodiment with N-
hydroxyalkylamides. In the patent, the acid moiety of the
hydroxyamide can be saturated or unsaturated, and the polymers
disclosed in the examples are exceptionally brittle, having a
high glass transition temperature (Tg). The polymer of the
Hopwood et al patent can be water-soluble or water-insoluble.
Salts of the polymer containing carboxyl groups, disclosed in
the patents can be neutralized with ammonia, certain amines,
or bases, including ones inoperable according to the present
invention, when a metal drier salt is utilized in accordance
with the invention. Problems encountered with the polymers
11'~0196
include the formation of gel, poor glass when dried under high
humidity conditions, slow development of block resistance,
and unstable dispersions.
It has now been found that certain parameters and
features of the polymer are critical for utilization of the
polymer as a water-soluble air-curing material. The finished
coating must have a Tg of below about 65C., preferably below
60C. The calculated Tg of the prepolymer or backbone polymer,
before esterification by the hydroxyamide to give units of
Formula V, infrar, should be below about 50C., although it
can be up to 85C., if large quantities of the amide are
present.
The present invention provides a method which com-
prises coating an article with an aqueous alkaline solution of
an addition polymer solubilized in said solution by a volatile
amine or ammonia, said pol~mer having the structure:
r~ ~5
C=O
R4
wherein
Rl is H, a lower alkyl radical having one to five
carbon atoms, halogen, -CN, or -CH2COOR, -COOR,
or -CH2COOH, R being a lower alkyl radical
having from one to eight carbon atoms;
R is (CR72)n wherein R7 is -H or -CH3 and n is 1
~'
11;~0196
or 2;
R is H, or a lower alkyl radical having from one
to 8 carbon atoms;
R is an unsaturated, air-curable alkyl radical;
R5 is H, -COOHg -CON ~, or -COOR, wherein R is a~
above;
R is H, or an aliphatic or cycloaliphatic radical
having from one to 20 carbon atoms; and
X is optional and when present i9 derived from at
least one vinyl monomer different than the
resïdues depicted;
the units in brackets being in any order, portions of the R6
radicals being as hereinafter defined in units of the formula:
_
R5 R
- CH C
C =O
oR6 .
II
R6 being H ln a sufficient number of units of Formula II to
provide the polymer with a carboxy content of 0.5 - 3 meq/g.
of polymer, the quantity of carboxy groups being sufficient,
when in the form of salt groups with said amine or ammonia,
to confer water solubility upon the polymer, the amount of
csrboxy-containing units of Formula II wherein R6 is H being
between 5 and 20 parts by weight o~ the total polymer; a por-
tion of the radical R6 in the units-of Formula II being at
least one aliphatic or cycloaliphatic radical wherein said
portion of the units of Formula II is derived from at least
one ester which when homopolymerized gives a polymer having
~ 0 19~
a Tg of between -80 C. and 120 C., ~aid e~ter unit~ maklng
up between 20 and 90 parts by weight of the polymer; the
polymer having between about 5 and 60 parts, preferably
between about lO and 40 parts by weight of units of the
formula:
. R5
- CH C
O
. . l2
~ 7 R3
CR4--
- V - l
wherein Rl, R2, R~, R4, and R5 are as identified above, any
balance of the polymer being the units -X- of addition p^ly-
merized ethylenically unsaturàted monomers other than saidunits of Formulas II and V, the total parts of all said units
being lO0, the ~v of the polymer being between about lO,000
and lO0,000, the Tg of a cured film of the polymer being
between about -20 C. and 65~ C., the Tukon Hardness of the
cured film being between about 0.2 and about lO, in which the
composition optionally includes a metal compound drier in an
amount up to 0.5~, on a metal basis; of the total polymer
weight in the composition; applying a coating of the solution
to a substrate, and drying and curing said coating in the
presence of air. Preferably, the polymer is used in the form
of a coating, from 0.1 mil to lO mils in thickness, when dry.
The unit X is derived from at least one other
-- 4 --
11;~0196
optional copolymerizable vinyl monomer (defined here~nbsl.o~/)
other than the one or ones from which ths right hand group i!l
brackets of Formula II is derived. It i~ to be under~tood
that when Rl and/or ~ contain free carboxy group~ (-COO~),
the hydroxyamide will react therewith to give pendant ester
groups equival.ent to the structure of Formula 5.
Examples of R and R5 are:
1 5 Acid For
R R Carboxyl Source
H H Acrylic
CH3 H Methacrylic
H COOH Maleic, fumaric
H CO ~ Maleamic
Cl COOH Chloromaleic
15C ~COOCH3 H Methyl acid
itaconate
C ~COOH H Itaconic
CH2COOH COOH Aconitic
H COOCH3 Half ester of
maleic
The matter in the right hand bracketed group of
Formula I or Fcrmula III, represents that portion of the
addition polymerized polymer backbone having free carboxyl
groups a~ well as carboxyl groups which are esterified by
the various alcohol~ conventionally used. The optional
portion -X-, is derived from any of the well-known unsaturated
addition polymerizable vinyl monomers, defined below, in addi-
tion to those which give units of Formula II above. --
Ths backbone polymer, before esterificati~n by thehydroxyamide, h~ the formula:
- 5
)196
R5 R I
~ X~ - - CH I ~ _
, oR6
III
and the fatty acid amide has the formula:
R3
H0 -- R2 _ N - C - R4
IV
wherein the symbols used have the same meaning as given above.
Preferred compositions contain polymer units of:
a) 10-50 parts by weight of a monomer selected from
esters of acrylic acid or methacrylic acid, which
when homopolymerized gives a polymer having a Tg
of between about 0 C. and -80 C., pre~erably
below -10 C.
b) 20-70 parts by weight of a monomer selected from
esters of acrylic acid or methacrylic acid, vinyl
aromatic hydrocarbons and unsaturated nitriles
which when homopolymerized gives a polymer having
a Tg between about 20 C. and 120 C., preferably
between about 50 C. and 120 C.
. c) 5-15 part~ of an ethylenically UB aturated car-
boxylic acid, optionally with up to 20 parts of a
different ethylenically unsaturated monomer which
confers hydrophilicity to the poly~ler and enhànces
its ~olubility in aqueous liquid~, the quantity of
ethylenically unsaturated acid being between about
o.6 and 2.5 meq/g. of polymer,
-- 6 --
ll~C~l9~
and
d) 5-30 parts by weight of units of Formula V, and the
total of a), b), c), and d) being 100.
Still more preferably, the polymer is one wherein:
a) is selected from one or more of ethyl acrylate,
butyl acrylate, 2-ethylhexyl acrylate, sec-butyl
acrylate, isobutyl acrylate and isopropyl acry-
late,
b3 is selected from one or more of methyl methacry-
late, styrene, ethyl methacrylate, acrylonitrile,
butyl methacrylate, isobutyl methacrylate, and
vinyl toluene,
c) is selected from one or more of acrylic acid, meth-
acrylic acid, maleic acid and itaconic acid,
optionally with up to 20 units of one or mDre of
the hydrophilic monomers hydr~xyethyl or h~xy-
propyl (meth)acrylate,
and
d) is present in the amount of be~ween about 5 and 30
parts,
the polymer consisting essentially of a), b), c), and d), and
in which the Mv is between about 20,000 and 80,000, preferably
between about 30,000 and 50,000.
In a preferred polymer in Formula V, n is 2, R3 is
-H, -CH3, or -CH2CH3, and R is the residue of one or more of
the drying oil acids selected from tung oil acids, linseed
oil acids, dehydrated castor oil acids, safflQwer oil acids,
conjugated safflower oil acids, soybean oil acids and oiticica
oil acids. An especially preferred combination of unsatu-
rated drying oil acids are 50~ - 90% of the acids of dehydrated
-- 7
~?~
0196
castor oil, sa~flower oil, con~ugated safflower oll, or soy-
bean oil mixed with 10-50~ by weight of the acl~s from tung
oil.
It is possible to utilize a single acrylate or
methacry]ate ester, there being no necessity to use a com-
bination if the suitable hardness and glass transition tem-
psratures can be obtained otherwise. An example of a poly-
mer of this type is one which contains polym~rized units
consisting essentially of:
e) 45-90 p~rts by weight of butyl methacrylate
f) 5-15 parts of an ethylenically unsaturated
carboxylic acid,-~he quantity of ethylenically
unsaturated acid being between about o.6 and 2.5
meq/g. of polymer,
g) 5~~ parts by weight of units of Formula ~,
and
h) optionally with up to 20 parts of a dif~erent
ethylenically unsaturated monomer which confers
hydrophilicity to the polymer and enhances its
solubility in aqueous liquids,
the total of e), f), g), and h) being 100.
The baGkbone polymer, prior to esterification with
the hydroxy~mide, is a water-insoluble vinyl polymer contain-
ing the requisite proportion of carboxyl (-COOH) groups as
de~cribed herein. The backbone polymers psr se are well
known in the art and form no part of the present invention.
The proportions of monomers in the backbone-are
such that there is at least 5~/o and no more than 20~o~ prefer-
ably less than 15~oJ of unsaturated carboxylic acid, by weight,
as units of Formula II wherein R6 is -H. An especially
-- 8 --
19~
preferred range is from about 8% to 15~, and the optim~n is
considered to be in the range of 10~ to 12~. It i~ essential
to have a substantial proportion of free carboxyl groups for
proper adhesion and, for maximum long term flexibility, a
minimum of the drying oll functionality.
rrhe preferred backbone polymers are those of vinyl
addition polymer ~ype, including as an essential component
the a,~-unsaturated carboxylic acid, preferably acrylic acid
or methacrylic acid. Other useful copolym3rizable acids are
named in U.S. Patent Nos. ~,og8,760 and ~,261,796, additional
examples being given below.
To amplify, the unsaturated carboxylic acid may be
a simple monocarboxylic acid, a poiycarboxylic acid, or may
be a partial ester or half amide of such a,~-unsaturated
polycarboxylic acids, and salts thereof with a volatile base
such as ammonia, or with a volatile monoamine, which form
water-soluble salts with the copolymer acid, such as dimethyl-
amine, triethylamine, diethanolamine, triethanolamine, mor-
pholine, N-methyl morpholine, picoline, and the like, but not
polyamines, which may interact with the metal of the sîcca-
tive. Examples of copolymerizable ethylenically unsatura~ed
monocarboxylic or polycarboxylic acids are sorbic, acryloxy-
acetic, acryloxypropionic, cinnamic, vinyl furoic, a-chloro-
sorbic, methacryloxypropionic, methacryloxyacetic, p-vinyl-
benzoic, acrylic, methacrylic, maleic, fumaric, aconitic,atropic, crotonic, and itaconic acids, or mixtures thereof,
with itaconic acid and the a,~-unsaturated monocarboxy-lic
acids, particularly methacrylic acid and acrylic acid, bein~
preferred. Other copolymsrizable acid mon~mers include the
alkyl half esters or p~rtial e~ters of unsaturated
_ g _
11'~0196
polycarboxyllc acids such as of itaconic acid, maleic acid,
and fumari.c acid, or the partial amides theroof. Preferred
half este;rs are the lower alkyl (Cl to C6) ester~s such as
methyl acid itaconate, butyl acid itaconate, methyl acid
.fumarate, butyl acid fumarate,.methyl acid maleate and butyl
acid maleate. Such parti.al esters, as well as p~rtial amides,
are considered to be "a,~-unsaturated monocarboxylic acids,"
and the term as used herein includes such ester~ and amides.
The term "vinyl monomer" as used herein means a
monomer comprising at least one of the following groups:
vinylidene C ~ =C ¦
vinyl C ~ =CH-, and
vinylene -CH=CH-,
whether homopolymeri~able or not, giving units corresponding
to X and to formula II. Examples are the a,~-ethylenically
unsaturated monocarboxylic acids and esters and amides
thereof, a,~-ethylenically unsaturated aldehydes, a,~-ethyl-
enically.. unsaturated dicarboxylic acids and esters, amides, 'i
half esters, and half amides thereof, a,~-ethylenically ~n- ¦
saturated nitriles, hydrocarbons such as a-olefins, conju-
gated diolefins, vinylaryl compounds, vinyl alkyl ethers,
vinyl halides, vinylidene halides, vinyl sulfides, vinyl
acyloxy compounds (esters of saturated carboxylic acids and
ethylenically unsaturated alkanols), vinyl amines and salts
thereof, vinyl ureido monomers, vinyl compounds having
heterocyclic nitrogen-containing (HN < ) groups, and halogen,
hydroxyalkyl, or aminoalkyl substituted derivatives thereof,
whether homopolymers or copolymers. The vinyl backbone
polymers and methods for their preparation for~n no part of
3o the present invention, and any such polymer may be 'reated
-- 10 -- ,
~ 9 6
in accordance with the pre~qnt invention. For examples of
w~ known vinyl polymers and methods of preparing tne sam~,
see "Polymer Processes," Schildknecht, Interscience, N.Y.
(1956), pp. 111-174. Mixtures of di~ferent polymers are
useful
Specific examples of suitable monomers which may
be copolymsrized to obtain the water-insoluble polymers for
use according to the invention in addition to the unsaturated
acid monomers and esters thereof with alkanols having one to
20 carbon atoms, such as msthanol, ethanol, butanol, penta-
decanol and the like, are acrolein, methacrolein, ethylene,
propylene, isobutene, butadiene, isoprene, chloroprene, sty-
rene, vinyl toluene, vinyl methyl ether, vinyl isobutyl ether,
vinyl chloride, vinyl bromide, vinylidene chloride, vinyl
sulfide, vinyl acetate, vinyl propi~nate, the vinyl pyridines;
primary amino compounds such as ~-~minoethyl vinyl ether,
aminopentyl vinyl ether; secondar~ amino-containing compounds
such as t-butylaminoethyl methacr~te; tertiary amino con-
taining compounds such as dimethy~aminoethyl methacrylate,
and the allied amine salts such a~ the chloride or hydroxide,
and ureido monomers such as are d~closed in U.S. Patent No.
~,~56,627 to Scott. Copolymers a~ gra~t, block, or segmented
polymers are included. Conventio~æl methods of obtaining the
- backbone polymers are utili7ed.
As is described below, ~se vinyl monomers include
the acids mentioned above and est~r~ thereof, as well as
known "soft" and "hard" monomers.
Another of the essenti2~ monomers, in addition to
the acid monomer, usually utiliz~ in a substantial propor-
tion to prepare the backbone pol~er, i3 a resiliency-
-- 11 -- .
11~019~
imparting or soft monomer- which may be represent~d by the
following formula:
R O
H2C=C ~-ORll
wherein R is H or alkyl having 1 to 4 carbon atoms and R is
the stra.ight chain or branched chain radical of a primary or
~econdary alkanol, alkoxyalkanol or alkylthiaalkanol, and
having up to about 14 carbon atoms, examples being ethyl,
propyl, n-butyl, 2-ethylhexyl, heptyl, hexyl, octyl, propyl,
2-methylbutyl, l-methylbutyl, butoxybutyl, 2-methylp3ntyl,
methoxymethyl, ethoxymethyl, cyclohexyl, n-hexyl, isobutyl,
ethylthiaethyl, methylthia.ethyl, ethylthiapropyl, n-octyl,
6-methynonyl, decyl, dodecyl, and the like, said radicals
Rll, when alkyl, having from two to about 14 carbon atoms,
preferably from three to 12 carbon atoms, when R is H or
methyl. When R is alkyl and R 1 is alkyl, Rll should have
from about 6 to about 14 carbon atoms and when R is H and R
is alkyl, Rll should have from about two to about 12 carbon
atoms, in order to qu~lify as a soft monomer.
Other ethylenically unsaturated copolymerizabls
vinyl monomers, the homopolymers of which have a much higher
Tg, are used in combinations with the above m3ntioned soft
monomers provided they do not adversely affect the desired
properties of the product (e.g., unduly raise the overall Tg).
The "hard" acrylics may be represented by the formula:
R O
H2C=C2 C~R22
wherein R is as above, R is preferabLy alkyl. and is methy~
~hen R ls H, and is alkyl of from one to about fivs carbon
atoms or alkyl of from about 15 to about 20 carbon atoms
_ 12 -
il~Ol9~
when R is met,hyl. Examples of ~he~e hard monomers and o~her
hard monomers ir~clude: methyl acrylate, acrylamide, acrylo-
nitrile, isobutyl methacrylate, vinyl acetate, tetradecyl
acrylate, pentadecyl acrylate, methyl methacrylate, ethyl
methacrylate, t-butyl acrylate, butyl methacrylate, styrene,
pentadecyl methacrylate, vinyl toluene, methacrylamide, and
N-methylolacrylamide.
As is known, for a given number of carbon atoms in
the alcohol moiety, the extent and type of branching markedly
influences the Tg, the straight chain products giving the
lower Tg.
As is apparent, an important property of the back-
bone polymer is the Tg thereof, and consequently the selec-
tion of monomers and proportions thereof depends upon their
influence on the Tg. "Tg" is a conventional criterion of
polymer hardness and is described by Flory, "Principles of
Polymer Chemistry," pp. 56 and 57 (1953), Cornell University
Press. See also "Polymer Handbook", Brandrup and Immergut,
Sec. III, pp. 61-63, Interscience (1966). While actual
measurement of the Tg can be used, it may be calculated as
described by Fox, Bul'. Am. Physics Soc. 1,~, p. 12~ (1955),
or by the use of "Rohm and Haas Acrylic Glass Temperature
Analyzer" Publication No. CM-21~ L/cb, Rohm and Haas Company,
Philadelphia, Pa., 19105. While the actual Tg of the pre-
polymers is much lower than the calculated Tg because of lowmolecular weights, the calculated Tg is a relevant indicia
of the relative Tgs of different polymers. Examples of the
Tg of high molecular weight (~>1,000,000) homopolymers and
the inherent Tg thereof wnich permits such calculations are
as follow~:
9~
~Iomopolymer of Tg
n-octyl acrylate -80 C.
n-decyl methacrylate -60 C.
2-ethylhexyl acrylate -70 C.
n-butyl acrylate -56 C.
o~tyl methacrylate -20 C.
n-tetradecyl msthacrylate -9 C.
methyl acrylate 9 C.
n-tetradecyl acrylate 20 C.
t~butyl acrylate 4~ C.
methyl methacrylate 105 C.
acrylic acid 106 C.
These or other monomers are blended to give the desired Tg of
the copolymer.
The polymeric backbone is desirably obtained by
solution polymerization of one or more of the ethylenically
unsaturated acids with other unsaturated monomers including,
among the more preferred vinyl monomsrs, the esters of acrylic
acid or methacrylic acid with benzyl alcohol, phenol, or a
saturated monohydric aliphatic alcohol, espscially an alkanol
having one to 18 carbon atoms, such as cyclopentanol, cyclo-
hexanol, methanol, ethanol, n-propanol, isopropanol, n-butanol,
methoxyethanol, ethoxyethanol, msthoxyethoxyethanol, ethoxy-
ethoxyethanol, isobutanol, sec-butanol, tert-butanol, any of
the pentanols, hexanols~ octanols, decanols, dodecanols, hexa-
decanols, and octadecanols, baaring in min~ the required Tg
and acid monomsr. Preferred vi.nyl monomers, in additio:n to
the acid, include one or more of an sster of an ~ ~nsaturated
carboxylic acid, or, whsn those from which X is derived areo used, an unsaturated nitrile, a vinyl halide, a vinylidene
- 14 -
11;~0196
hal:Lde, a v:Lnyl aro;llatic, a vinyl alcohol ester, or an un-
saturated h~drocarbon. Other praferred comon~mers inclu~e
acrylonitrile~ methacr-ylonitrile, vinyl acetate, styren3,
vinyl toluena (o, _, or p), vinyl chloride or vinylidene
chloride, to give the X in ths foregoing formula. Blend3 of
copolymers may be used.
The substrates with which ths invention is con-
cerned are of all types, insluding siliceous substrates sush
as glass sheets, fiberglass textiles, asbestos shaets,
asbestos cement products, concrete, stone, stucco, sLate,
sandstone, granite, seramics, and porce'Lain, also ~iber re-
in~orced p~a3tic article3 such as canoes, boat hulls, or
other formed articles made out of fiberglass reinforced poly-
esters or other plastic materials; metals such as aluminum,
steel, iron, brass; wood and other structural materials;
metal oxide layers such as those of aluminum oxide and iron
oxide; leather; textiles of cellulose such as of cotton,
linen, silk, wool, rayon, cellulose esters such as cellulose
acetate, nylons, polyesters such as polyethylene glycol
terephthalate, acrylonitrile polymers, vinylidene chloride
polymers and other vinyl or acrylic ester polymers; films,
pellicles, sheets and~other shaped articles of plastic
systems such as of cellulose ethers or esters incl~ding
hydroxyethyl cellulose, methyl cellulose, cellulose acetate,
cellulose acetate butyrate, polyesters such as pelyethylene
glycol terephthalate, nylons, vinyl chloride or vinylidene
chloride polymers and copolymers, methyl methacrylate-poly-
mers and copolymers, aminoplast or phenoplast ~esins,~
organopolysiloxane resins, or rubber.
The products of the present invention are
- 15 -
11;~0196
particularly valuable in that they usually can be used
directly on any of the substrates without the need of a
priming coat.
; The solvents used in the polymerization may be
such organic solvents and mixtures thereof such as benzene,
toluene, xylene, solvent naphthas of aliphatic, aromatic, or
naphthenic type such as mineral spirits, ethers, esters,
acetone, dioxane, etc. Preferred solvents are the monoalkyl
(Cl-C4) ethers of diethylene glycol, ethylene glycol, or
propylene glycol, sold under the trademarks "Carbitol"
"Cellosolve", and "Propasol", respectively. Of course, other
modes of polymerization can be used. The amount of solvent
in the polymer is from 0% to 80% based on polymer solids,
preferably, from 10~ to 65%.
Among the drying oils from which the drying oil
fatty acid amide is derived are linseed, tung, tall, saf-
flower, conjugated safflower, isano, soya, dehydrated castor,
oiticica, menhaden, and similar oils, as well as acids not
derived from drying oils and of a synthetic origin, with a
carbon chain preferably of about 20 carbon atoms or less and
having unsaturation therein which can be caused to air cure
in a manner analogous to linseed oil. The preferred oils are
those in which the major component contains two or more sets
of olefinic unsaturation, in either a conjugated or alterna-
ting occurrance, including in addition to oiticica and de-
hydrated castor oils, those which contain linoleic and/or
linolenic acids as the predominant ones.
The preparation of the fatty acid hydroxyamide is
carried out by well known procedures, as is the esterification
of the carboxyl groups on the polymeric backbone by the
- 16 -
ll;~Vl9~i
hydroxy~mide. Exemplary o~ publications de~cribing these
ara The Journal of the American Oil Chemist~' Society,
Volume 46, pages ~55-~64, publi~hed in 1969, which discloses
the use of diethanolamine to produc~ fatty acid hydroxyamide
rather than the monoethanolamine which is preferred in the
present invention, German Patent No. 1,940,471, and Bb~gian
Patent No. 757,271 and corresponding U.S. Patent No. ~,590,01
noted above, the latter two relating to hard coatings such as
paints. The U.S. and Bslgian patents are to the same type
of polymer generally, although the products taught therein
have several defects making them unsuitable for many uses.
For example, all of the backbone polymers disclosed are
brittle or hard polymers. Thus, it appears that the softest
polymer backbone, of the patent examples, would be of styrene
and/or methyl methacrylate that would have a glass transition
temperature (Tg) of 100 C. or above.
Any of the conventional driers or siccatives, such
as the linoleates, naphthenates, and resinates of cobalt,
zirconium, manganese, lead, cerium, chromium~ iron, nickel,
uranium, and zinc are suitable. Inorganic acid salts can
also be used.
The amount of drier, if used, based on the weight
o~ the hydroxyamide of Formula IV can be as low as 0.01~ to
as high as ~% or more. Good results are~often obtained with
combinations of driers, such as zinc naphthenate and cobalt
naphthenate in quite small amounts, for example, from .01~ to
0.5% of the zinc naphthenate togeth~r with 0.01% to Q.1%
cobalt naphthenate are particularly useful. Co++ as cobalt-
ou~ acetate is also useful, alone or with compounds providing
~o Mn++, Zn++, Zr++, or Pb++.
- 17 -
11~019~
The materlal~ of the invention are particularly
useful as additives for latexes as illustrated by Example ~.
Suitable latexes are aqueous addition polymer dispersion~,
generally obtained most conveniently by direct emulsion poly-
merization. The most important of these dispersions used in
making water-based paints are polymers including homopolymers
and copolymers of: (1) vinyl esters of an aliphatic acid
having 1 to i8 carbon atoms, especially vinyl acetate; (2)
acrylic acid esters and methacrylic acid esters of an alcohol
having 1 to 18 carbon atoms, especially methyl acrylate,
ethyl acrylate, butyl acrylate 2-ethylhexyl acrylate, methyl
methacrylate, ethyl methacrylate and butyl methacrylate; and
(3) mono- and di-ethylenically unsaturated hydrocarbons, such
as ethylene, isobutylene, styrene, and aliphatic dienes such
as butadiene, isoprene, and ch~oroprene.
Poly(vinyl acetate) and copolymers of vinyL acetate
with one or more of the following monomers: vinyl chloride,
B vinylidene chloride, styrene, vinyltoluene, acrylonitrile~ j
methacrylonitrile, one or two of the acrylic and methacr~lic
acid esters mentioned above are well known as the film-fQrming
component of aqueous base paints. Similarly copolymers of
one or more of the acrylic or methacrylic acid esters ment-oned
above with one or more of the following monomers: vinyl ace-
tate, vinyl chloride, vinylidene chloride, styrene, vinyl-
toluene, acrylonitrile and methacrylonitrile are also more o~
less conventionally employed in aqueous base paints. Homo-
polymers of ethylene, isobutylene and styrene, and copol~.ers
of one or more of these hydrocarbons with one or more esters,
nitriles or amides of acrylic acid or of methacrylic acid or
with vinyl esters, such as vinyl acetate and vinyl chloride,
- 18 -
1.
11~0196
or with vinylidene chloride are also used. The di~ne poly-
mers are generally used in aqueous base paints in the form of
copol~mers ~ith one or more monomers following styrene, v~nyl-
toluene, acrylonitrile, rnethacrylonitrile, and the above men-
tionsd esters of acrylic acid or methacrylic acid. It is alsoquite common to include a small amount, such as 1/2 to 5% or
more of an acid monomer in the monomer mixture used for making
the copolymers of all three general types mentioned above by
emulsion polymerization. Acids used include acrylic, meth-
acrylic, itaconic, aconitic, citraconic, crotonic, maleic,fumaric, the dimer of methacrylic acid, and so on.
These aqueous dispersions may be made using one or
more emulsifiers of anionic, cationic, or non-ionic type.
Mixtures of two or more emulsifiers regardless of type may be
used, except that it is generally undesirable to mix a cat-
ionic with an anionic type in any appreciable amounts since
they tend to neutralize each other. Furthermore, many cat-
ionic types of emulsifier are incompatible with the polymers
of the invention. The amount of emulsifier may range from
about 0.1 to 5~ by weight of sometimes even more based on the
weight of the total monomer charge. When using a persulfate
type of initiator, the addition of emulsifiers is often neces-
sary and this omission of the use of only a small amount, e.g.,
less than about, 0.5~, of emulsifier, may sometimes be desir-
able from the cost standpoint (elimination of expensive emul-
sifier), and less sensitivity of the dried coating or impreg-
nation to moisture, and hence less liability of the-coated
substrate to be affected by moisture, which, for instance~
would produce coating less liable to swelling or softening,
~o particularly when subjected to h~mid atmosphere~. The aver-
age particle size or diameter of these dispersed polymers may
be from
- 19 --
~ 0196
about 0.03 to 3 microns or e-~en larger. The particle slze,
whenever referred to herein, is the "weight average diameter!'.
Thi~ number, axpressed in micronsJ is determin~d using the
ultra-centrifuge. A description of ths method can be found
in the Journal o~ Colloid Science 15, pp. 563-572, i960
(J. Brodnyan). In general, the molecular weight of the~e
~ emulsion polymers are high, e.g., from about 100,000 to
: 10,000,000 viscosity averageJ most commonly above 500,000.
Suitable proportions are 10-70~, preferably 10-50~ of the
soluble polymer with 30-90~, preferably 50-90~ latex polymsrJ
solids basis. They are insoluble in aqueous media at a pH of
~-11 .
To assist those skilled in the art to practice the
present invention, the following modes of operation are
suggested by way of illustrationJ p~rts and percentages being
by weight and tL1e tempsratuLYe in C. unless otherwise speci-
fically noted.
In the exampLes the abbreviations for monomers hav~
the followin~ meanings:
BA - butyl acrylate HEMA - hydroxyethyl methacrylate
MMA - methyl metL~crylate ~AA - meth~crylic acid
A~ - acrylic acid B~A - butyl methacryLats
S - styrene EA - ethyl acrylate
AN - acrylonitrile iBMA - isobutylmethacrylate
_ 20 -
9 6
Tha follo.~ing abbreviations qre ~or the e~terified units of
Formula V of the specified ~atty acid amine, of N-~.ethyl-N-
hydrox~Jethyl amide as fol~ows:
MEnELAE - linseed oil acids
~DEES.~E - soybean oil acids
MHESAFAE - safflower oil acids
MXED~AE - dehydrated castor oil acids
MHETAE - tung oil acids
MHESTAE - stea~ic acid - a non-drying acid
The following abbreviations are also utilized in
the examples:
HELAE - N-hydroxyethyl linseed oil acid amide ester
HESAFE - N-hydroxyeth~l safflower oil acid amide ester unit
In the following Table, the prepolymers 'na-~ing a
sollds content of 8,-~o~ were made by solution polymerization
in butyl ~ellosolve ~ which was followed by post-polymeriza-
tion esterification, b~ the drying oil N-methyl-N-(~-hydrox~-
ethyl)amide, of a portion of the copolymerized unsaturated
aci~. mhe synthesis details are set ~orth in Table IJ with
a typical procedure being set forth following Table III.
* Ethylene glycol monobutyl ether,
_ 21 -
~,
11;~0196
C
51 1 a~
0 ~ o o o o o o o o o
~ ~' o o o o o o o o o
c, ~0 O r~ O o ~ o o Lr~ o
~ ~1 ~ ~ ~
. H ~ O C~ ~r Ci\ 1~ :) ~) C`J N X
O ;2 0~) ~ ~ ~1 ~ 1~ L('`\ C~l ~ ~
.'
~ t, ~ .
00 . 0
.,~
~ . . . . . . . . . .,~
~b
~ o o o o o o o o o ~
s~ ~ o o o o o o o o o
a) Cd ~ ~ ~ L~ ~ ~ ~ L
~ s~
P, a) ~
o ~ P,
~E~ O
. .~
. al
H S~ U~
D~ 1~ C~ O C~ L~ LO L~ ~ I
~1 ~3 ~o o o o ~i o o o o o ~
S~ ~ ~:,
E~ ~ . '
. ~ ~
bO
O ~
O ~ ~
C~l ~d O O O O O O O O O .,l S~
~J r; ~i r; ~r\ r; ~ ~ r; ~ C) ~ O
~1 a~ r~ cd
~-I S~~ O
a) ~ c)
~! S~ O
r-l O ~ O O O O r-lS~ r~l ¢
~ \ \ ~ aD 0 C~
~ O O O O O O O O O ~
~ ~ ; o q) s~
~ O O O O O O O C~l CU ~ ~ O I b~ ~
~ ~ ~ ~ ~ Ir~ ~ ~ ~ ~ p, ~ r~ cd ~
¢ ~ ~ \ ~ ~ ~ ~ \ \ Sl ~J 0 a:~ o s~ o
O O O O O O O O O ID O ~ O r~
~r ~ C~l ~ ~ C~l ~ ~ 0
m ' ~ ~ o ~,~
o ~ .~, ~
~ ~ D~ O
Cl; ~ S~ tO O
~ c~ a) c) c~ ~0
o ~ v ~ ~ 1~4 ~ ~ H ~1
L~ O L~
)196
At the hi~her dryin~ oil level~, the molecular weight of the
uncured polymer increases somewhat.
rrhe polymsrs having a ~v in the neighborhood of
40~000 require significantly less pendant drying oil func-
tionality, in the neighborhood of 20% for good curingcharacteristics than do polymers of about 20,000 ~v, which
show efficient curing at about 40~ pendant drying oil func-
tionality.
~ure rate is a function of drying oil type. Cure
efficiency is also a function of drying oil type and quantity.
Some polymers containing styrene or acrylonitrile are shown
to cure at a slightly reduced rate; analogous polymers con-
taining hydroxyethy] methacrylate (HEMA) exhibit an enhanced
cure rate.
The viscosity average molecular weights as deter-
mined herein ara in general agreement with gel psrmeation
chromotography (gpc) molecular weight determinations. In most
cases, gpc molecular weights were determined on methylated
prepolymsrs, methylated to reduce the copolymer acid for
more reliable measurements. "Prepolymers" are the polymers
before esterification with the drying oil hydroxyethyl amides~
also called backbone polymers. The molecular weights listed
were calculated from the prepolymer molecular weights plus
the weight of the drying oil amide. In one example (F) the
gpc molecular weight was determined directly on the methylated
final polymer. The good agreement between E and F inlicaies
that few crosslinks are formed between drying oil ch&ins
- during the post-polymerization esterification. ~-~
- ?3 -
.
ll;~V196
D~
~d ~
. cl ~ .cl
, ~ h ~
. . ~ ~ ~
51 C~l O~ L~ ~ ~. ~ ~ ~ ~d
~1 O ~ ¦ co o ~ ~ ~ L~
,~ ~ +
C~
O C~
~ ~: ~ t ~ ~I C`~l ~ ~ o
a) ~ ~:
~ ,1 ~ ~
~ ~rL ~
H ~) ~; o H
~ . ~ ~ ~ ~
E I bO ~ ~d ~d
~ rl~ O
S~ ~ ~ ~ O ~ ~
~ ~ O O C ~ ~
~ ~1 ~ C ~:
~: ~ ~ ~ ~ O O
~ ~ ~ CU ~ d ~d
O ~i ~ ~.
O
o~ ~3 c3 a) a
,~ O ~1
a) a)
~d c) ~d ~d
~d c~
O ~ o
C~
o ~ a) ~ ~
C~ d 3
~ ~
~ O C~
~0 C) O
.
. ~ ~ S~
O ¢ ~ V ~ ~ ~ ~ ~ ~ 01)
~; ~
U~ O Lr~
,,),
t```. ~1;Z0196
The soluti.on viscosities of water-soluble copoly-
mers can be markedly reduced by the addition of a cosolvent.
It has been concluded that (a) tha solubility parameter and
hydrogen bonding class of a cosolvent have no relAtionship
` to the eAfficiency OA~ the cosolvent in reducing solution vis-
cosity, and (b) among the better cosolvents (acetonitrile,
isoprcpanol, isobutanol acetone, methyl ethyl ketone) all are
approximately equally effective in reducing solution vi~cosity
Other useful cosolvents include butyl "Cellosolve", butyl
"Carbitol", "Propasol" B,*"Propasol" P,* and diacetone alcohol.
It is important to promptly cool the batch after
the esterification is completed. The reason is that, if the
batch is not promptly cooled, gelation may occur. Temparature
reductions can be achieved by refluxing a water-~lene azeo-
trope during esterification and by ~ubsequent removal of theazeotrope by the use of a vacuum without applyin~ additional
heat. Esterification temperature and time arè also i~portant.
When a temperature of 165 is used, esteri ication must b~
co~pleted in a much shorter time, for example lO minutes, in
order to have a reasonable gel-free time as compared to ester-
ification at 145 C., where substantial gel-frse time is ob-
tained even when the esterification is carried out~over a
period of 45 minutes. Other factors contribu'ing to ~el-frea
time are copolymerized acid content, in that a lo~er contenr
f acid gives a longer gel-free ti~e and the total solids,
in that the lower solids content products hav~ a Longer cel-
free time. Another factor is the nature of the drying oil
acid. The order ~f susceptibility to geLation is as follows:
dehydr~ted castor ~tung >linseed = safflower ~30y~ stearic.
Additives which ~ Auench the gelation effect ars sometimes
- 25 -
* Trademark for n-butoxypropanol ~
** " " n-propoxypropanol,
196
usef~iL. The~e additive~ lnclude carboxylic acids and ~nillne.
Examples o~ the acids are: monochloroacetic acid and benzoic
acid.
To assist those skilled in the art to practice the
present invention, the following modes of operation are
suggested by way of illustration, parts and percentages being
by weight and the temperature in C. unless otherwise
specifically noted.
The following gives a sample calculation for deter-
mining the relative weight ratios of units of Formula II, VII,and X in the final polymer.
Sample Calculation:
This illustrates the preparation of 30~A/42MMA/
20MHEIAE/8AA by reacting the carboxy-containing backbone
L5 polymer with N-methyl-N-hydroxyethyl linseed oil acid amide.
C17H31C-NCH2cH20H + -COH C17H31C-NCH2CH2-C- + H2
Average Molecular 337
Weight = 337 Average + 72 (AA)
molecular - 18 (H20)
weight = 391
A prepolymer of composition 35.86BA/50.19MMA/13.95AA (calcu-
lated Tg = 8 C.) is reacted with 20.59~, orl the basis of pre-
polymer weight, of N-methyl-N-hydroxyethyl linseed oil acid
amide (MHELA). Thus, 100 g. of prepolymer is reacted with
20,59 g. of N-methyl-N-hydroxyethyl linseed oil amide.
20 59= o6ll m~leS arnide
337 ._
72 x .0611 = 4.40 gm~. AA in .0611 moles.
18 x .0611 = 1.10 gm~. H20 in .0611 moles.
3G Wt. of MHELAE units of Formula V 2 20.59 +
4.40 - l.L0 = 23.89 g.
- 26 -
~l~Olg6
F~nal Comp3~itiurJ
~m~
~ 5.86 30
MMA 50.l9 42
AA 13.95 - 4.40 - 9-55 8
MHEI~E 23.89 20
ll9.49
The polymer compositions herein were calculated in a similar
manner.
Example 1 - Preparation of 40RA/30MMA/20MHELAE (linseed oil)/
lOAA having an ~v of about 40~000)
A monomer mixture of the following materials was
prepared:
Parts
Butyl acrylate 326.0
Methyl methacrylate 244.6
Acrylic acid 1lO.4
Mercaptoethanol 3 1~
An initiator solution of the following materials
was prepared:
Butyl Cellosolve ~ 35.4
Lupersol ~ PMS
(t-butyl peroctoate) 13.6
The following materials were charged into a reaction
vesseL fitted with a stirrer, condenser, nitrogen sweep, and
two gradual addition apparatuses:
Butyl Celloso]ve 88.o
Monomer mixture 40.8 - .
The batch was heated to 110 C. and ~ of--the ini-
tiator solution was added. Following a fi~teen minute hold
period the remainder of the monomer mixture and the initiator
- 27
ll;~V~96
solution was added proportionally over four hours while
maintaining 110 + 30C. Following these additions a mixture
of 1.8 parts "Lupersol" 70 (t-butyl peracetate) and 5.8 parts
butyl "Cellosolve" was added to the batch and the temperature
increased to 170C. The resulting acrylic backbone polymer
or prepolymer (47.87BA/35.91MMA/16.21AA) has a calculated T
of 7C. At 170C. a mixture of 134.5 parts N-methyl-N-
hydroxyethyl linseed oil fatty acid amide and 65.0 parts
xylene was added. The temperature decreased to 153C. During
the next 45 minutes, while maintaining 150-155C., 76 parts
of a two phase clear solution was distilled from the batch
by application of a partial vacuum. Following distillation
the batch was cooled to 95C. and a mixture of 68.5 parts
28% aqueous ammonia and 600 parts of deionized water was
added to the batch while maintaining good agitation. At
75C. the batch was removed from the reaction vessel and
packaged in a glass container where the temperature was
allowed to fall to room temperature.
The product of this proc~ss was a clear aqueous
solution with a solids content of 51.4% and a viscosity of
281,000 centipoises. The viscosity average molecular weight
was determined to be 42,300. A thin film (1-3 mils) of the
above polymer solution containing 0.1~ Co++ (as cobaltous
acetate) became tack free within five hours and cured in
one week at room temperature to slightly yellow, alkali
insoluble films. The glass transition temperature of the
cured film was about +20C.
Example 2 - Preparation of 40BA/30MMA/20MH~LAE (linseed oil)/
lOAA having a Mv of about 80,000
The method of Example 1 was repeated but the
mercaptoethanol was reduced to 1.7 parts. The product of this
~r - 28 -
` ~"!
11;~0196
process was a clear aqueous solution with a solids content of
50.7% and a viscosity of 342,000 centipoise. The viscosity
average molecular weight was determined to be 80,000. A thin
film of this material cured similarly to the film described
in Example 1, and has a T of about 25C. in the cured form.
Example 3 - Preparation of (20BA/42MMA/30MHELAE (linseed oil)/
8AA having a Mv of about 20,000
A monomer mixture of the following materials was
prepared:
- Parts
Butyl acrylate 181.5
Methyl methacrylate379.5
Acrylic acid 120.5
Mercaptoethanol 6.8
This monomer blend (26.6BA/55.7MMA/17.7AA) gives a prepolymer
having a calculated Tg of about 43C.
An initiator solution of the following materials
; was prepared:
Butyl "Cellosolve" 35.4
"Lupersol" PMS 40.8
The following materials were charged into a reac-
tion vessel fitted with a stirrer, nitrogen sweep, C`ondenser
and two gradual additional apparatuses:
Butyl "Cellosolve" 88.0
Monomer mixture 40.8
The batch was heated to 142C. and 6% of the
initiator solution was added. An exotherm to 151C. was
observed. This temperature was maintained for 15 minutes
following which the remainder of the monomer mixture and
the initiator solution was added over four hours while
maintaining 150 + 3C. Fifteen minutes after completion
- 29 _
,~
11~0196
of these additions a mixture of 1.8 parts "Lupersol" 70 and
5.8 parts butyl "Cellosolve" was added to the batch. The
temperature was maintained at 150 + 2C. for an additional
fifteen minutes after which a mixture of 224 parts N-methyl-
N-hydroxyethyl linseed oil amide and 69.0 parts xylene was
added gradually over fifteen minutes while still maintaining
150 + 2C. The temperature was then allowed to rise slowly
to 155C. over thirty minutes and 30.0 parts of a two phase
clear liquid was distilled from the batch at atmospheric
pressure. Following distillation the batch was cooled to
95C. and a mixture of 50.3 parts 28% aqueous ammonia and
587 parts deionized water was added to the batch while
maintaining good agitation. At about 70C. the batch was
removed from the reaction vessel and packaged in a glass
container where the temperature was allowed to fall to room
temperature.
The product of this process was a clear aqueous
solution (referred to below as Copolymer 3 solution) with a
solids content of 53.1% and a viscosity of 11,230 centi-
poise. The viscosity average molecular weight was determined
to be 22,500. A thin film (1-3 mils) of the polymer solu-
tion containing 0.1% Co++ (as cobaltous acetate) became
tack free within five hours and cured in two weeks at room
temperature to a slightly yellow, alkali insoluble film
with a Tukon Hardness of about 1.5 and a glass transition
temperature of about 25C.
A pigment grind was prepared using a "Cowles "~
dissolver and the following materials:
- 30 -
~1~0196
Pigment Grind Parts
Dispersant, * 25% TS 1.9
Copolymer 3 solution, 53.6~ TS 12.3
Deionized water 20.3
TiO2, R-900 HG 65.5
* A copolymer of maleic anhydride and diisobutylene, in a 1:1
mole ratio.
A very smooth pigment grind was obtained on addi-
tion of the TiO2 to the liquid ingredients. The mix was
stirred on the "Cowles" mixer at 3500-4000 ft/min. for 30
minutes. The grind was let down as follows, using a conven-
tional stirrer:
Grind A 34.5
Copolymer 3 solution at 25%
TS w/0.1% Co++ (as the ace-
tate) on total polymer solids 65.5
The resultant paint had a viscosity of 2700 cps.,
a pH of 8.5, and on drawdown had a 60 gloss of 80 with a
slight yellowish tint. Its tack free time was significantly
better than that of commercial solvent alkyl paints with
similar gloss properties.
Removal of the dispersing agent resulted in a per-
fectly satisfactory pigment grind. The ratios employed:
Pigment Grind B Parts
Copolymer 3 solution, 53.6% TS 12.5
Deionized water 20.7
TiO2, R-900 HG 66.8
As above, a "Cowles" dissolver was used at a peri-
pheral speed of 3500 to 4000 ft/min. to disperse the pigment.
The resultant grind was quite smooth, and was much more
easily prepared than conventional semi-gloss grinds. The
grind was let down with additional water-soluble polymer,
- 31 -
11~0196
as follows:
Pigment Grind A 34.5
Copolymer 3 solution, 25%
TS with 0.1% cobaltous ace-
tate on total polymer solids 65.5
This paint at an approximate volume solids of 30% and a PVC of
25% with a viscosity of 1750 cps at a pH of 8.5 had good brush-
ability with good flow and levelling, excellent gloss, and a
slightly yellowish tint.
Conventional propylene glycol/polyelectrolyte disper-
sant grinds can also be used; in this case the soluble polymer
replaces the latex in the let down stage. A typical grind:
Pigment Grind C Parts
Dispersant, *25% TS 3.1
"Nopco'~ NDW Dispersant (a
nonionic defoaming and dispers-
ing agent) 5.6
Propylene glycol 19.5
TiO2, R-900 HG 76.8
*Maleic anhydride - diisobutylene copolymer
As in the other cases, a "Cowles" dissolver was used in prepar-
ing the grind.
The let down stage performed with a conventional
stirrer consisted of the following:
Pigment Grind C 27.3
Deionized water 5.6
Copolymer 3 solution, 30% TS 67.1
The metallic drier in the Copolymer 3 solution was
varied as tabulated below:
Paint #3 -1 -2 -3 -4 -5 -6
drier 0.1% 0.05% 0.05% 0.05%0.05~ 0
Co++ Co+~ Co++ Co++ Co++
" - 0.05% 0.05% 0.05%0.05% 0
Mn++ Zn++ Zr++ Pb++
% Metal on total Copolymer 3 solids
r~ ~ 32
llZ0196
The resultant paints had very good gloss, particularly
depth of gloss or image gloss, reflected in 20 gloss measurements.
These are summarized below along with 60 gloss and pain
viscosity and pH.
Paint #3 -1 -2 -3 -4 -5 -6
pH 8.5 8.5 8.5 8.4 8.3 8.4
viscosity,
cps 43003750 4500 3700 3450 3600
20 gloss 67 71 61 59 67
60 gloss 84 81 79 78 84 86
A conventional latex control, had 60 gloss of 65; the
20 value would typically be 20-25.
An additional variant with good gloss properties is a
blend of the water-soluble polymer with a conventional acrylic
latex (EA/MMA/MAA 57/42/1) on a 20/80 basis. The followi.lg
proportions were used:
Parts
Pigment Grind C 33.2
Deionized water 6.8
Latex, 46.5% TS 39.5
Copolymer 3 solution, 30% TS
w/0.1% Co++ 20.5
This paint exhibited 20/60 gloss of 31/80, not as
good as for the examples above incorporating only the water-
soluble polymer, but significantly better than the gloss of a
paint formulated without copolymer C as follows:
Pigment Grind C 36.1
Latex, 46.5% Total Solids 57.3
Propylene Glycol 5.0
"Texanol" ~ 1.6
which had a 60 gloss of 65. (Its 20 gloss was not measured,
* Trademark for 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.
- 33 -
il;~Oi96
but typical values observed fox equivalent formulations averaged
28).
Example 4 - Preparation of (20BA/42MMA/30MHESAE)(soybean)/
8AA Polymer having a ~v of about 20,000
The method of Example 3 was repeated with an equal
weight of N-methyl-N-hydroxyethyl soybean oil acid amide in
place of N-methyl-N-hydroxyethyl linseed oil acid amide. The
product of this process was a clear aqueous solution with a
solids content of 53.4% and a viscosity of 19,000 centipoise.
The copolymer acid titer was 1.13 meq/gram of polymer. A
thin film (1-3 mils) of the above polymer solution containing
0.1% Co++ (as cobaltous acetate) cured in two weeks at 60C.
to a slightly yellow alkali insoluble film of Tukon Hardness
about 2Ø
Example 5 - Preparation of (40BA/20MMA/20MHELAE)(linseed oil)/
20AA Polymer having a Mv of about 20,000
The method of Example 3 was repeated with the butyl
acrylate changed to 326 parts, the methyl methacrylate to 163
parts, the acrylic acid to 191.5 parts, the mercaptoethanol
to 3.41 parts, the N-methyl-N-hydroxyethyl linseed oil amide
to 134.5 parts, the aqueous ammonia to 138 parts and the de-
ionized water to 542 parts. The acrylic backbone (47.9BA/
24MMA/28.lAA) has a calculated Tg of 8C.
The product of this process was a clear aqueous
solution of solids content 50.7~ and a viscosity of 14,500
centipoise. The viscosity average molecular weight was deter-
mined to be 21,000.
Example 6 - Preparation of 20BA/42MMA/30MHELAE (linseed oil)/
8AA Polymer having a Mv of about 20,000; Triethyl
Amine Neutralization
The method of Example 3 was repeated with 111.1
parts of triethylamine in place of the 28% ammonia solution
- 34 -
0~96
and the deionized water decreased to 526.6 parts. The pro-
duct of this process was a slightly hazy aqueous solution of
solids content 53.6% and a viscosity of 11,650 centipoises.
A thin film (1-3 mils) of this polymer cured similarly to
the polymer described in Example 3.
Example 7 - Preparation of (5BA/42MMA/45MHELAE)(linseed oil)/
8AA Polymer having a Mv of about 20,000
The method of Example 3 was repeated with the
butyl acrylate changed to 53.8 parts, the methyl methacrylate
to 456.0 parts, the acrylic acid to 172.4 parts, the N-methyl-
N-hydroxyethyl linseed oil amide to 403 parts, the 28~ aqueous
ammonia to 66.7 parts and the deionized water to 571 parts.
The acrylic backbone (7.9BA/66.8MMA/25.3AA) has a calculated
Tg of 84C.
The product of this process was a hazy aqueous
solution of solids content 56.7~ and a viscosity greater than
100,000 centipoise, and is hereinafter referred to as Copolymer
7 solution. A thin film (1-3 mils) of this polymer solution
containing 0.1% Co+~ (as cobaltous acetate) cures to a yellow
alkali insoluble film of Tukon Hardness about 3.0 and a Tg of
approximately 50C. after two weeks at 25C.
Copolymer 7 solution was incorporated in the pre-
ferred grind for these water-soluble vehicles, incorporating
only pigment, polymer, and water and eliminating the need for
coalescent, wet edge aids, dispersants, as follows:
_igment Grind D Parts
Copolymer 7 solution, 25~ TS 49.2
Deionized water 1.6
TiO2, R-900 HG 49.2
Standard techniques using the "Cowles" dissolver were followed.
11;~0196
The grind wa~ let down with additlonal water-soluble ~olymer
incorporating v~rying level~ of metallic drier. The overall
recipe for this series included:
Paint #7 -1 -2 -~ -4
-
Pigment Grind D 44.1 44.1 41.4 36.4
Copolymer 7 solu-
tion, 24~ TS +
Drier 55.9 55-9 52 1~ 46.o
Deionized water 0 0 6.2 17.6
rier levels for Paint Nos. 7-1, 2, ~, 4J were 0, 0.1, 0.25
and 0.5~ Co++ on polymer solids resp3ctively, as cobaltous
acetate.
These paints had pH's, viscosities, gloss (range of
82 94) and other properties characteristics of the earlier
paint series. In addition, the alkali scrub resistance was
measured using a Gardner ~ scrub machine with 1 lb. boat, 1
Tide ~ (detergent) solution for 500 eycles; the 60 gloss
before and after scrub was monitored. The substrates were 7
mil drawdowns on black vinyl charts. Paint No. 7-1 (no drier)
was completely removed from the panel after a three day air
dry; after one week ~0~ of the film was removed. After a one
day air dry the gloss of Paint No. 7-4 (0.5~ Co++) went from l~;
92 to 81 after the 500 cycle scrub, whereas after 7 days air i1
dry the gloss change was from 89 to 82 or -8%. Two days dry
time was sufficient for 90% gloss retention at 0.25~ Co++.
Example 8 - Preparation of ~OBA/~OMMA/20M~ELAE)(Linseed)/
lOAA Polymsr having a ~ of about 40,000
The method of Example 1, with the exception that
the butyl acrylate ~as changed to 245 parts and the methyl
methacrylate to ~27 parts, was employed through completion of
the addition of the monomer mixture to the reaction vessel.
- ~6 -
.
l~Z0~3~;
rrhis monome.r mTx (35.9BA/47.9M~/16.2AA) gives ~ calculated
Tg of ~6 C. ~ollowing ~he monomer mixture addition the
batch was heated to 15-0 C. and a mixture of 1.8 part3
Lupersol '~0 and 5.8 parts butyl Cellosolve was added and the
; 5 temperature maintained. After fifteen minutes a mixture of
134.5 parts N-methyl-N-hydroxyethyl linseed oil amide and 6
parts xylene was added gradually over about 10 minute~ while
maintaining 150 _ 2 C. The temperature was then allowed to
rise slowly to 155 C. over thirty minutes and 24 parts of a
two phase clear liquid was distilled from the batch at atmos-
pheric pressure. Following distillation the batch was cooled
to 98 C. and a mixture of 68.5 parts 28~ aqueous ammonia and
600 parts deionized water was added to the batch while main-
taining good agitation. At 69 C. the batch was removed from
the reaction vessel and packaged in a glass container where
the temperature was allowed to fall to room temperature.
The product of this process was a clear aqueous
solution with a solids content of 47.9~ and a viscosity of
67,500 centi.poises. The copolymer acid titer was letermined
to be 1.~4 meq/gram of polymer and the viscosity average
molecular weight 58,ooo. A thin film of this polyme~ solu-
tion containing 0.1~ Co++ (as cobaltous acetate) (copolymer 8
solution) cured in two weeks to a slightly yellow, alkali
insoluble film with a Tukon Hardness of about ? 5 and a glass
transition temperature of about + 40 C.
Excellent pigment grinds and paints were prepared
from this polymer. A standard Cowles grind was prepar-ed as
follow~
0196
Part~
Copolymer 8 solution, 47.9~ 25.1
D~ionized water 26.7
TiO2, R-900 HG 48.2
The grind was let down with additional Copolymer 8 ~olution
and water carefully added until the consistency appeared
right for brushout. The final mix contained:
Pigment Grind 66.5
Copolymer 8 solution, 23.5% 26.8
Deionized water 6.7
This paint had brushability, gOoa gloss, and good
flow/levelling, comparable to earlier paints prepared from
copolymers 3 and 7.
Example 9 - Preparation of ~OEA/40MMA/20MHESAFAE(safflower)/
lOAA Polymer having ~v of about 40,000
The metho~ of Example 8 was used with the excep-
tion that N-methyl-N-hydroxyethyL safflower oil amide was
substituted for N-methyl-N-hydroxyethyl linseed oil amide.
The product of this process was a clear aqueous
solution of solids content of 51.7~ and a viscosity of
176,000 centipoise. A thin film of this material cured in
the manner described in Example 8 exhibited similar film
behavior with the exception that the cured film was of lighter
color.
Example 10 - Prep~ration of 30BA/40MMA/15MHED~AE(dehydrated
castor)/5MHETAE(tung)/lOAA Polymer having a Mv
of about 40,000
The method of Example 8 was used with the excep-
tion that a mixture of 168 parts N-methyl-N-hydroxyethyl de-
3o hydrated castor oil amide and 56 parts N-methyl-N-h`ydroxyethyl
tung oil amide wa~ used in place of 224 parts of N-methyl-N-
hydroxyethyl linseed oil amide.
- 38 -
11;~0196
The product of this process is a clear aqueous
solution of solids content 48.7% and a viscosity of 257,000
centipoise. The copolymer acid titer was determined to be
1.37 meq/gram of polymer. A thin film (1-3 mils) of this
polymer containing 0.1% Co++ (as cobaltous acetate) became
tack-free within five hours and cured in six days to a
s]ightly yellow, alkali insoluble film of Tukon Hardness
about 3.4.
Example 11 - Preparation of 30BA/40Styrene/20MHELAE (linseed)/
lOAA Polymer (Mv about 40,000)
The method of Example 8 was used with the excep-
tion of substitution of styrene for methyl methacrylate,
giving a calculated Tg for the acrylic prepolymer (35.9BA~
47.9S/16.2AA) of 26C.
The product of this process is a clear aqueous
solution of solids content 49.7% and a viscosity of 304,000
centipoise. The copolymer acid titer was 1.44 meq/gram of
polymer. A thin film (1-3 mils) of this polymer containing
0.1% Co++ (as cobaltous acetate) cured in six weeks at 25C.
to a slightly yellow, alkali insoluble film of Tukon Hardness
about 7.5.
Example 12 - Polymer of 43BA/27AN/20MHELAE (linseed oil)/
lOAA (Mv about 40,000)
The method of Example 8 was used with the excep-
tion that the butyl acrylate level was increased to 350 parts
and acrylonitrile substituted for methyl methacrylate at a
level of 221 parts. The backbone acrylic polymer (51.4BA/;
32.4AN/16.2AA) has a Tg (calculated) of 0C.
The product of this process is a clear aqueous
solution of solids content 49.4% and a viscosity of 490,000
centipoise. A thin film (1-3 mils) of this polymer cured in
- 39 -
2~
11;~0196
six weeks at 25 C. to a sligh-tly yellow, alkali inso'uble
film of Tukon Hardness about 5Ø
Example 13 - Polymar of 27~ 4MMA/20M~E~E(linseed)/14 ~ ~h/
- _AA (~v about `~0,000)
~he method of Example 8 was employed with the
exception that the monomer mixture was composed of the
following: butyl acrylate 200 parts, msthyl methacrylate
277 parts, hydroxyethyl methacrylate 114.7 parts, acrylic
acid 69.5 parts, marcaptoethanol 3.4 parts. Ths a~u~ous
ammonia was reduced to 34.4 parts and the deionized water
increased to 634 parts. The backbone (32.3BA/40.7M~Q/16.8
HEMA/10.2AA) has a calculated Tg of 27 C.
The product of this process is a clear aqueous
solution of solids content 49.2~ and a viscosity of 465,000
centipoise. The copolymer acid titer was o.83 meq/gram poly-
mer. A thin film (1-3 mils) of this polymer containing 0.1
Cot~ (as cobaltous acetate) cures in two weeks at 25 C. to
a slightly ~ellow, alkali insoluble film of Tukon Hardness
about 2.5.
Example 14 - Polymer of 70BMA/20MHETAE (tung)/lOMMA (~v about
The method of E~a~ple 8 was employed ~ith the
exceptions that: 1) the monomer mixture (83.4BMA/16.6i~A)
which gives a calculated Tg of 38 C. was composed of the
following: butyl methacrylate 568 p~rts, methacrylic acid
113 parts, mercaptoethanol 3.4 parts; 2) 129.9 p~rts N-methyl-
N-hydroxyethyl tung oil amide was used in place of the N-
methyl-N-hydroxyethyl linseed oil amide; 3) the aqueous
ammonia and deionized water changed to 57.1 parts and 630
parts resp3ctively and 4) an additional 500 parts of butyl
Cellosolve was added to the final polymer solution.
- 40 -
11;~0~96
The product of this process was a clear solution ofsolids content 40.2% and a viscosity of 3,370 centipoises.
The copolymer acid titer was 1.14 meq/gram polymer.
A thin film (1-3 mils) of this polymer containing
0.1% Co++ (cobaltous acetate) cures in two weeks at 25C. to
a slightly yellow, alkali insoluble film of Tukon Hardness
about 10 and with a glass transition temperature of about
60C.
Example 15 - Polymer of 40BA/40MMA/lOMHETAE (tung)/lOAA (Mv
about 40,000
.
The method of Example 8 was employed with the excep-
tion that 1) the monomer mixture was composed of the follow-
ing: butyl acrylate 297 parts, methyl methacrylate 297 parts
acrylic acid 87.2 parts, mercaptoethanol 3.4 parts, and 2)
61.2 parts N-methyl-N-hydroxyethyl tung oil amide was used in
place of the N-methyl-N-hydroxyethyl linseed oil amide, and
3) the aqueous ammonia and deionized water changed to 62.5
parts and 548 parts respectively. The acrylic prepolymer
of 43.6BA/43.6MMA/12.8AA has a calculated Tg of 15C.
The product of this process was a clear solution of
solids content 48.8~ and a viscosity of 308,000 centipoise.
A thin film (1-3 mils) of this polymer containing 0.1% Co++
(as cobaltous acetate) cured in two weeks at room temperature
to a slightly yellow, alkali insoluble film of Tukon Hardness
about 1.5. A polymer of lOBA/27.5BMA/40iBMA/lOMHETAEJ12.5AA
had similar properties.
Comparative Example A - Polymer of 20BA~42MMA/30MHESTAE
(Stearate)8AA (Mv about 20,000)
This is a saturated fatty acid which is disclosed
in U.S. Patent No. 3,590,016.
The method of Example 3 was repeated with 456 g. of
a 49.2~ solution of N-methyl-N-hydroxyethyl stearamide in
~ 41 _
Oi96
xylene in place of the N-methyl-N-hydroxyethyl linseed amide
in xylene solution. The product of this process was a cloudy
solution which clarified on heating to 60C. The solids
content ~as 53.4%. The viscosity at room temperature was
37,200 centipoise. A thin film (1-3 mils) of this polymer
solution containing 0.1% Co++ (as cobaltous acetate) remained
soft, tacky and alkali soluble indefinitely.
Comparative Example B
This is Example 16 of U.S. Patent No. 3,590,016.
The acrylic prepolymer (89.4MMA/10.6MAA), having a calculated
Tg of above 105C. is reacted with the hydroxyethyl amide of
safflower oil fatty acids, to give a polymer of the composition
79.2MMA/14.5HESAFE/6.3MMA.
This example was repeated as described in the patent
with the exception that prior to the final dilution with water
and KOH the batch was split into two portions. One portion
was neutralized with KOH/H2O as described in the patent and
the other with an equivalent amount of ammonia/water.
According to the patent, the prepolymer is obtained
as a solution (col. 12, line 45) but in this attempt to re-
peat the example a heterogeneous mixture was obtained. The
mixture eventually becomes homogeneous on additions of the
amide and solvent.
- - 42 -
l~Z0196
Results
-
Portio~ I-B Portion II-B
(KOH Neut.) (NH3 Neut-)
Appearance slightly h~zy cloudy
% T.S. 42.0 44.2
~i-sc. (cps) 18,500 38,
Titer maq. NH /g.
T.S. ~ -- o,457*
meq. acid/g.
T.S. 0.710** 0.706**
* Nots: This level of am~onia doas not fuLly nsutralizs the
polymer. It is equimolar with ths level of KO~ used
in the patsnt. Addition of en~gh ~ore NH~ to fully
neutralize the polymer yields a clear 'no~o~enous
solution.
** The Patent - o.696 ~q. acid/~. T.S.
Theory (100~ reaction) - 0.710 ~eq. acid/g. T.S.
Comparative Example C
Final Compo3ition 35.80 S~'56.65 HELAE/7.54 A~
- hydroxyethyl Linseed amide ester
E~rQle 17 of U.S. Patent N~. 3,590,016 was repeated as - ~
described in the patent with the exception that prior to ths
fin~l dilutio~ with water (col. 13, line ~0) the b&tch was
dividsd into three portions. Portion A was neutralized and
diluted with KCH (~ .25 equivalents on polymer acid) and
water with a~itation as described in the patent. This
yielded a pol~ner dispersion. Portion B was treated as the
fi~st except that an equi~olar leveL of a~monia was used in
p'ace of KOH. This aLso yieLded a polytner dispersion. Portion
3o ~ was dilu'ed with a full equivalent of am~onia (on ~ol~r.e~
acid) and o~ly enough water to yiel~ a clear soLution o,~ ~bo~1t
47% T.S.
Both lispersions WQre very un~table. Gross
- 43 -
~V196
~edimantation wa~ observed wlthin 18 ho~. Al~o the odor
of all three samples was extremely ~trong. This odor ~a~ a
characteri~tlc mercaptan odor and is probably due to the
t-dodecyl mercaptan used in the polymerization.
5Results
Portion I-C Por~ion II-C Portion III-C
Appearance milky white* milky white* clear solution
%T.S., exclu-
ding Sediment 10% 10~ 46.7
Visc. (cps) 100 100 9,200
Titer meq.
NH~/gm T.S. ** ** 1.18 -
acid meq/gm.
T.S. 1.33*
I5 * Di~persion sedimented within 18 hours
** Titer of dispersion meaningless as compared with solution
*** Theory (100% reaction) - 1.01 meq. acid/gm T.S.
The Patent - 1.~9 meq. acid/gm T.S. ( 70% reactlon~
Oven Stability (10 days/60 C.)
Copolymer acid titer
Viscosity (cps~ ~meq/gm li'.S.~
Portion Initial 10 days/60 C. Initial 10 days/60 C.
I- B 18,500 22,000 0.710 0.832
II-B 38,000 40,200 o.706 o.708
III-C 9,200 8,900 1.33 1.4
Cure Study
Data on the cure of polymers prepared by Comparative
Examples B and C are given in Table I~. The last product is a
typical polymer of this invention.
Conclusions
ExampLe B: The sample~ prepared according to this example are
unsatisfactory for the following reasons:
- 44 -
~ZOlg6
1) Films are too hard and brittle
2) Not eno~h cure to develop satis~actory
alkali resistance
3) The sample neutralized with KOH has poor
hydrolytic-stability as indicated by the
increased acid titer on heat aging.
Example C: The dispersed samples were unsatisfactory because
of the poor sedimentation stability. In fact the
samples sedimsnted so rapidly it was not possi'ole
to complete their evaluation. The solubilized
; variation of this example exhibited adequate cure
and hydrolytic stability; however, the obnoxious
odor of the solution plus the excessive hardness
and color of the cured film make this polymer un-
acceptable.
- 45 -
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