Note: Descriptions are shown in the official language in which they were submitted.
106~3S~
....
U.S. Patent 3,519,559, issued to Quinlan,
July 7, 1970, discloses polymers of tert.-butyl gly-
cidyl ether (hereinafter TBGE) and copolymers with
alkylene oxides and teaches that the terminal hydroxyl
S groups thereof can be esterified with polycarboxylic
acids to produce polymeric esters useful in breaking
water-in-oil emulsions.
British Patent 1,267,259, published March 15,
1972, discloses the condensation of TBGE with a variety
of co~pounds having at least one active hydrogen atom
and, in a second step, the removal of the tert.-butyl
groups, thus producing linear polyglycidols.
U.S. Patent 2J680,109, issued to Stevens et
i al., June 1, 1954, discloses the polymerization of
glycidyl methacrylate through the epoxy group to pro-
duce a linear polymer that can then be further poly-
merized and crosslinked through the methacrylate groups.
U.S. Patent 3,509,074, issued to Kamio,
April 28, 1970, discloses the copolymerization of iso-
butylene oxide and glycidyl methacrylate ~95:5 by `
weight).
French Patent 1,438,201 tC.A., 66, 2877,
#29874 m) shows copolymerization of a mixture of
i ethylene oxide, propylene oxide and glycidyl meth-
:.
acrylate.
` U.S. Patent 3~446,757, issued to Edwin J.
~andenberg, May 27, 1969, discloses the homopol~meriza-
tion and copolymerization of silicon esters of glycidol
~ollowed by hydrolysis to remove the esterifying group,
.
thus producing homopolymers and copolymers of glycidol.
:' .
' ~t ' ,',' .
17,110/213/252-F -1- ;
.
.. : . : .
^ \
~6~358 ::
The latter may then be cross-linked by reaction with a
polyfunctional acid, anhydride, isocyanate or epoxide.
U.S. Patents 3,578,719; 3,595,924 and 3,666,671,
issued to Kalopissis and Vanlerberghe, May 11, 1971,
July 27, 1971 and May 30, 1972, disclose the "hydroxy-
lation" of homopolymers or copolymers of epichlorohydrin
by the reaction of potassium acetate and a glycol with
the polymers. Small, incidental amounts of acetylated
material are also thereby formed and are hydrolyzed in
a subsequent step.
The invention is directed to compositions of
the formula
_ _ ..
R (R'O)mX_
n
wherein R is the residue left by removal of n hydrogen ~;
atoms from n hydroxyl groups of an initiator selected
from compounds of the formula R~OH, in which R5 is
hydrogen; alkyl of 1 to 12 carbons which may be substi- : ;
tuted by a further 1 to 5 hydroxyl groups; aralkylaryl
of up to 20 carbon atoms which may be substituted by a : . .
further 1 to 3 hydroxyl groups; or a radical of the
formula HO-R6-(OR7)W in which R6 and R7 are alkylene of
2 to 6 carbons and w is 1 to 10; R' is an alkylene radical . :
selected from ethylene, trimethylene, tetramethylene,
1,2-butylene and groups of the formula
-CH2CHCH2A
where each A independently is~ H or OX; X independently
is H or the acyl radical of a carboxylic acid selected
from acrylic acid, ~-lowe-r alkyl acrylic acid and acids
of the formula
.~ .
17rll0M-F ~ -2-
`
35~3
R8 ( COO~ ) y
wherein R8 is alkyl or alkenyl of up to 20 carbons, or
phenyl, and y is 1 or 2, with the proviso that at least
one R' is 3-hydroxy-1,2-propylene and at least one is ;
a group of the formula
--OEI2CHCH20X
wherein X is the acyl radical of acrylic acid or a-lower
alkyl acrylic acid; and m and n are integers such that
the total number of R'O groups is at least 2.
`:'
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17,110M-F -2a-
r , ~
~(:116~35~3
,
The term "linear", as used hereinJ refers to
each of the polyoxyalkylene backbone chains attached to
the initiator residue, R. Obviously, i~ n in the above
formula exceeds 2 the molecule as a whole could be con-
sidered to be branched.
The invention also comprises a convenient :;
method for maXing the compounds of the above formula.
One method for preparing the linear copolymers is by
acylating the desired proportion of the hydroxyl groups
in substantially linear polyglycidol or a copolymer of
one or more alkylene oxides with glycidol, said copolymer ~ :
being initiated by the initiator, RHn. Methods for the ;
pxeparation of such intermediates are described in the
references cited ahoveJ exept Vandenberg, and in U.S. :
Patent 3,578J719 and 3,595,924 both previously identified. ~.
In a preferred method the tert.-butyl groups .
of a polymer or copolymer of text.-butyl glycidyl ether
(TBGB) are removed and the desired proportion thereof
directly replaced with ester groups by heating the polymer
or copolymer with a strong acid catalyst, preferably a
sulfonic acid, in the presence of either the acid cor-
responding to the desired ester, or the acid anhydride
or acyl halide. .
Those tert.-alkyl groups not converted to .:
ester groups are predominantly converted to primary
hydroxyl group~. These reactions may be illuctrated .
as follows:
CH2CEI~~
~/ CH2CR ~; :
~-w CH2CHO, ~ ~,
CH20R ~
~ ' CH~CHO~ ~
.
~ CH20H '.
.
` 17,110/213/252-F -3-
~135~
wherein R is tert.-alkyl~ R'COOH is a carboxylic acid
and the wavy lines represent the polyoxyalkylene back-
bone of the polymer. The proportion o:E the tert-alkyl .
ether groups that are converted to ester or to hydroxyl
groups, respectively, is determined by the proportion of
esterifying acid used and/or the amount of water produced
in the reaction.
Many o the unique properties and uses of the -`
above compounds prepared from the unsaturated acids arise
from the presence of both hydroxymethyl and polymerizable
acyloxymethyl groups as substituents on the backbone
chains of the compounds. These substituent~ are more ~.:.
or less randomly arranged and may be present in a very
wide range of proportions, as indicated by the above
formula.
~ very small proportion, of polymerizable
I acyloxymethyl groups, or even a single such group, is
sufficient to render the compounds copolymerizable with
other vinyl-type monomers that polymerize by a free
:` 20 radical mechanism and to render coatings comprising the
compounds curable by exposure to free radicals, as by
expo~ure to heat and/or radiation or contact with or- ;
ganic peroxides or other free radical generators.
. The presence of one or more hydroxymethyl
groups likewise opens many possibilities for modifi- .
. cation of the compounds. Any or all of them can be
esterified with one or more acids, isocyanates, or the
like. By use of hydrophobic acids, such as long-chain
. fatty acids, the hydrophobic-hydrophylic balance of the
compounds can be controlled over a wide xange. Thus,
`::
. .
17,110/213/252-F -4-
., '
~06~35~3
for instanceJ hydrophobic coating materials can be made
by e~terifying a portion of the hydroxymethyl groups
with stearic acid. Such materials can then be cross-
linked and rendered solvent resistant by polymerization
through the unsaturated acid moieties as described above. -~
Similarly, dialdehydes~ particularly glyoxal, can be
used to link two of the hydroxyl groups through hemiacetal
linkages. Such linking is reversible by treatment with
aqueous base. Under more severe conditionss irrever~ible ~ -
~0 acetal cros~links can be formed.
The compounds of the invention prepared from
saturated acids are oily liquids or ~emisolids which are
useful as coating materialsJ lubricants~ plasticizers,
textile antistatic agent~ and surfactants. Thi~ wide
range of utilities is made possible by the fact that
the compounds can be "tailor-made" within broad limits
of structure and properties. Thus~ by varying the num-
ber of free hydroxyl groups and the number and carbon
chain length of the acyl groups~ the hydrophobic-
hydrophylic balance can be adjusted to any desired valueJ
thus providing a wide range of surfactants useful as
emulsifiers and wetting agents. Those compounds having
a multiplicity of fatty acyl groups o~ up to about ten
carbon atoms are preferred for use as softeners and
lubricants for leatherJ textilesJ paper and the like
and as plasticizers for cellulose ether resins. Those
having fatty acyl groups of about eight to twenty or
more carbon atoms are useful as lubricants and antistatic
agent~ for polyvinyl chloride re~ins and polye~ter and
polyamide films and fibers. Those compounds having a
"".
'~
17JllO/213/252-F -5-
~L~6~L35~
;,
a plurality of free hydroxyl groups are useful as inter-
mediates for making polymerizable vinyl monomers by
esterification with an acid having a polymeriæable vinyl
group, such as acrylic, methacrylic, chloroacrylic,
cyanoacrylic, maleic and itaconic acids. The resultant
esters are polymerizable by free radical initiaters to
produce resins useful as coatings and for molding or
casting solid objects.
The preferred compounds of the invention axe
those wherein R is the residue of an initiator compound,
RHn, which is a hydroxy compound free of substituents
reactive with an alkylene oxide other than alcoholic
hydroxyl groups. Suitable such compounds include the
alkanols, such a~ methanol, butanolJ octanol, dodecanol
and octadecanol; the alkenols, such as allyl alcohol,
10-undecen-1-ol, oleyl alcohol; alkylene glycols, such -~
as ethylene, propylene, butylene, l,4-tetramethylene
and 1,3-hexylene glycols; the higher aliphatic polyols ;`-~
such as glycerol, pentaerythritol, sorbitol, sucrose,
hexanetriol, phenols, such as phenol, cresols, xylenols,
hydroquinone, resorcinol, naphthols, and aralkanols, such
as benzyl alcohol and phenethyl alcohol. It is pre~erred
that the initiator have not more than 8 active hydrogen
atoms, and preferably not more than 3. Expecially pre-
ferred initiators are water and the glycols. Water
reacts with alkylene oxides or tert.-butyl glycidyl
ether 5TBGE) to open the oxirane ring, thus producing
a glycol which may then be regarded as a glycol initiator
prepared in situ. Analogous reactions take place with
oxetanes and tetrahydrofurans.
17 J 110~213/252-F -6-
-
~6135~
The substantially linear polymer or copolymer
of glycidol that can be used to make the compounds of
the invention may be made in any convenient manner. For
instance, a polymer of TBGE or a copolymer thereof with
one or more alkylene oxides may be mad~ by the polymeriza~
tion of the monomers, as described in IJ.S. Patent 3,519,559,
previously identified. The tert.-butyl groups may then
be removed by warming the material in the presence of an
arylsulfonic acid, as is shown in British Patent 1,267,259,
previously identified, thus replacing the tert.-butoxy ~ ;
groups with hydroxy groups. Any desired proportion of
the latter can then be esterified with a carboxylic acid.
~he terminal hydroxyls may be likewise esterified.
In a preferred method, TBGE, in conjunction
with one or more alkylene oxides if desired, is condensed
with an initiator compound (which may be the moisture `
incidentally present in the reactants and/or apparatus),
and then the tert.-butoxy groups are removed and the
desired proportion of ester groups are simultaneously
attached by warming the polymer with an arylsulfonic
acid or similar catalyst, in catalytic amounts, in the
presence of su~ficient carboxylic acid to produce the
desired proportion of ester groups. Examples o YUit-
~ able catalysts include benzenesulfonic, toluenesulfonic ;~
i 25 and naphthalenesulfonic acids.
If any substantial part of the acid to be used
in the esterification step is a polycarboxylic acid, it
is preferably used in the form of its anhydride and in
the proportion of one mole of anhydride per equivalent i
of hydroxyl to be esterified~ thus producing a partial
: , .
. .
17,110/213/252-F -7-
:~0~;~358
':
ester of the acid. If one attempts to totally esterify
such an acid, its polyfunctionality causes branching and,
ultimately, crosslinking of the substrate. Moreover,
because of the liklihood of transesteri.fication and
resultant crosslinkage, the polycarboxylic acid anhydride
should be reacted separately and only aLfter the reaction
of any monocarboxylic acid, unless the latter also is
used in the form of the anhydride. If so, the anhydrides
can be mixed and reacted simultaneously, and the by-
product acid removed under conditions that avoid further
esterification o the partial esters of the acids.
The acids useful to make esters according bD
the invention include substantially any carboxylic acid.
The monocarboxylic acids produce esters having the same
polymer backbone as the tert.-alkyl ether starting material,
the diference being that most or all of the tert.-alkyl
groups have been removed and, to the desired extentJ re- ~`
placed with the acyl group of the reactant acid. Those
not so replaced are converted to hydroxyl groups. Dicar-
boxylic acids extend the chain length of the backbone of
the polymer and may also initiate branching and, ultimately,
cross-linking of the polymer. Polycarboxylic acids of
functionality greater than two, even when used in small
amounts, quickly cross-link and gel the polymer; hence,
they are ordinarily used in very small amounts if at a~
The preferred monocarboxylic acids are the sat-
urated fatty acids, such as acetic, butyric, lauric and
stearic acids; the olefinic fat~y acidsJ such as acrylic,
methacrylic, undecylenic, oleic and linoleic acid~; the
aromatic acids, such a benzoic, alkylbenzoic and naphthoic
' , ..
17,110/213/252-F -8-
~' ' , : , '' ` ` "` ,` ~ .'
,: . , ' , : . :
~061;~SI!~ :~
acids, and the chloro- and bromo-analogs of the foregoing.
It is, of course, possible to use the anhydrides of the
acids rather than the acids themselves. They are particu-
larly useful w~ere partial esters of polycarboxylic acids `
are desired as the final product~ in which case a mole of
the anhydride is used for each carboxyl group desired in
the product and the esterification is run under mild condi-
tions so as to minimize the formation of diesters of the
acid derived from the anhydride. Suitable polycarboxylic
acids, and anhydrides include the alkanedicarboxylics, such
as succinic, adipic and sebacic; the alkenedicarboxylics,
such as maleic, itaconic, citraconic and glutaconic; and
the aromatics, ~uch as phthalic, isophthalic and tere- ;
phthalic.
lS In practicing the invention, a polyoxyalkylene
compound c3ntaining tert.-alkyl glycidyl ether moieties,
i.e., groups of the formula.
-cH2cHo- , .. ..
OR
wherein R is a tert.-alkyl group, is prepared by known
means. This is conveniently done by the homopolymeriza-
tion of a tert-alkyl glycidyl ether or the copolymeriza-
tion of such an ether with one or more other cyclic ethers,
such as ethylene oxide, propylene oxide, butylene oxide,
trimethylene oxide, tetrahydrofuran, epichlorohydrin,
2,2-bis(halomethyl)oxetane, or the like. Such polymeriza- -
tions may be conducted with various catalysts, such as
alkali metal hydroxides, Friedel-Crafts catalysts, alum-
inum alkyls, zinc alkyls or other known catalysts for the
polymerization of alkylene oxides. If conducted in the
"
.
17,110/213/252-F -9-
~ [)6~L358
presence of an initiator compound having one or more
active hydrogen atoms, polymer chains are initiated at
the sites of these at~ms/ as is well known in the art. ~ -
Such polymers have terminal hydroxyl groups whieh may, i~
desired, be esterified prior to or simultaneously with
the sites of the tert.-alXyl ether groups.
The essential step of the process of the inven-
tion, i.e., the s~multaneous dealkylation and esterifica-
tion reaction~ is carried out by heating the polymer having
tert.-alkyl ether groups with the acid or anhydride that
is to be esterified in the presence of a Rtrong acid
catalyst and simultaneously removing the alkene corres-
ponding to the tert.-alkyl group and any water ormed in
the reaction. The reaction may be conducted by simply
mixing the reactants and the catalyst and heating to
reaction temperature. Removal of the by-product alkene
may be facilitated by operating under reduced pressure
and/or sparging a stream of inert gas through the reaction
mixture. These techniques likewise aid in removal of any
water produced in the reaction. Removal of water is further
facilitated by using as a reaction solvent a water-
immiscible organic solvent, such as a hydrocarbon or
halohydrocarbon of suitable boiling point such that at
reflux its azeotrope with water is distilled and the water
removed. Upon completion of the reaction, as indicated
by the evolution of olefin and/or water, the product is
obtained by removal of the catal~st, solvent and unreacted
acid if any.
Since the polyether reactant is more or less
polymeric in nature~ khe esteri~ication reaction with a
. ~
,:
~ 17~110/213/252-F -10-
,,
~063L~5~ :
carboxylic acid becomes slow toward the end and tends to
be incomplete unless vigorously pushed~ Where it is
important to accomplish complete esterification it is
often expedient to add the a~hydride of the acid near the
end of the reaction, since it i5 much more reactive than
the acid itself. Use of a stoichiometric excess of the
acid or anhydride also favors complete esterification.
The c~mpounds o~ the invention prepared from the -
unsaturated acids are polymers which range from oily
liquids to ~olids depending on molecular weight, the
nature of the initiator moiety and the identity, pro
portions and arrangement of the various other moieties
pre~ent. Those compounds that are initially liquid can
be converted to solid form by polymerization or copoly-
merization through the polymerizable double bond of the
a,~-unsaturated acid. These materials are useful as
curable resins t~at can be formed into coatings or
shaped articles which can then be cured by exposure to
heat, radiation or source of free radicals, thus being
rendered harder and more resistant to heat and solvents.
The following examples illustrate the invention.
. Preparatlon of TBGE Polymers and Copol~mers
Monomeric tert.-butyl glycidyl ether (TBGE)
was homopolymerized or copolymerized in various propor-
tions with ot~er cyclic ethers in known manner, the pro-
ducts and their preparation being summarized in Table 1.
The indicated initiators were the active hydrogen com-
pounds used to initiate the polymer chains. In all runs,
the reaction was continued until all TBGE and other
alkylene oxides fed to the reactor had reacted, thus
.~ ' '.
~' ''' ~
17,110/213/252-F -11-
:
,
106~3S~3 ~
assuring that the molar proportions in the product were
the same as in *~he reactor f eed . Molecular weights of
the products were estimated by the acetic anhydride method,
baeed on the expected number of hydroxyl groups per molecule.
17/ 110/213/252-~ -12-
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~613S13
B. Dealkylation and Esterification of the Polymers
Listed in Table I
The polymers of Table I have n terminal hydroxyl
groups, where n is the functionality of the initiator
RHn. These hydroxyl groups can be esterified without
disturbing the tert.-butoxy groups by reaction with an
acid anhydride or, in the presence of a base, by use of ;~
an acyl halide. Attempts to esterify them with carboxylic
acids in the presence of strong acid catalysts result
in dealkylation (106s of isobutylene) together with
esterification of the resultant primary hydroxyl groups.
ThusJ a particular feature of this invention is the
discovery that the tert.-butyl glycidyl ether polymers
and copol~mers can be terminally esterified independently
of the tert.-butoxy group~ and that the latter groups
can be simultaneously and in a single step dealkylated
an~, to any desired exte~t~ esterified by reaction with
a carboxylic acid. The latter reactions are catalyzed
by strong acid catalysts, especially the arylsulfonic
acids.
I Esteri~ication of the terminal hydroxyl groups
of the tert.-butyl ether polymers and copolymers by use
of acyl halides or half-esterification of acid anhydrides
can be accomplished under mild conditions, such as
30-90C., whereas dealkylation and/or esterification
of carboxylic acids requires acid cataly~is and temperatures
of about 90 ox more for a convenient rate of reaction.
Generally~ temperatures of about 125-150 are preferred.
When using highly polymerizable acids such as acrylic or
methacrylic acid, it is necessary to u~e a polymerization
. , .
~ , '
: '`,:.
17~110/213/252-~ -16- `
1~613SI~ -
inhibitorJ such as Cu2O or a hydroquinone. Lower tem-
peratures, such as about 90-110 may be used, however
because of their higher reactivity. The progres~ of
the reactions can be followed by measuring the amount of
isobutylene and/or water produced. Removal of water can
be facilitated by use of a solvent, such as toluene,
that refluxes at a convenient temperature and forms an
azeotrope with water. Since the desired ~inal products
ha~e some unesterified hydroxyl content, this i~ usually
assured by putting into the reaction mixtuxe the amount
of acid or anhydride that is needed to esterify the de-
sired proportion, though it is al~o possible to use excess
acid, follow the esterification by monitoring ~he amount
of water produced, and stop the reaction at the clesired
point. Removal of isobutylene and/or water may be facili-
tated by sparging a slow stream of inert gas through
the reaction mixture during the reaction.
Because of the desirability of some primary
. .
hydroxyl in the products, the above examples show only
partial esterification of the polymers. However, es~en-
tially complete esterification is readily accompli~hed
by use of at least the stoichiometric amount of acylating
agent and continuing the reaction until essentially com-
plete. ThuR, the reaction of Run No. 49 was repeated
except that 46 moles of stearic acid were used, the
product was essentially fully esterified and contained
essentially no primary hydroxyl.
Table II summarizes the results of a series
of experiment~ wherein the polymers listed in Table I
were dealkylated and partially esterified as described
::'
17,110/213/252-~ ~17-
.
:
~l~613Si~ ~
above. The starting material is identified by the Run
No. as shown in Table I. The amounts of acids used in
the esterification reactions are shown as moles/mole
of starting material. It may be noted that in most
instances excess acid was used. When t.he esterification
was conducted stepwise with two differe!nt acids, the
acid used in the first step was completely reacted, then
the second acid was added and reacted either partially
or entirely (e.g., Runs 45J 49J 55 and 61). In all
runs which both acrylic acid and maleic anhydride were
usedJ the two were mixed and~ hence reacted simultaneouslyO
In Table II the products are characterized
by the number ~ unsaturated acyl groups, the number of
any other acyl groups that may be present and the number
of primary hydroxyl groups (glycidol units) per molecule
of the product. The ester groups were determined by
NMR and the hydroxyl groups were calculated by difference,
all calculations being based on the molecular weights
shown in Table I.
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17,110/213/252-F -18-
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In Table III are shown the results of another
series of experiments, where the products are character-
ized by the number of acyl groups and ~he number of
primary hydroxyl groups ~glycidol units) per molecule ~ :
of the product. The ester groups were determined by NM~ :
and the hydroxyl groups were determinecl by reaction with
trifluoroacetic acid, all calculations being ~ased on .;:
the molecular weight8 ~hown in T~bl? I.
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17, 110/213/252-F -23-
35~ ;
The products shown in both Tables II and III
are not pure compounds, but rather are mixtures having
the average compositions shown. Where the number of
primary hydroxyl groups is less than one, this signifies
that some molecules contain such a group while others do
not. It has been found that the advantageous propertles
and utilities of the products are often present in such
mixtures even if on average only a small proportion,
such as 10%, of the molecules contain the unsaturated
ester and the primary hydroxyl groups.
The esters ~hown in Table II were oily liquids
to resinous solids, depending on molecular weight and
functionality. All were readily soluble in most organic
solvents but many were insoluble or only slightly soluble
in water, depending on the number and size of the hydro-
phobic groups present. `;
To show the utility of the esters shown in
Table II, they, alone or in admixture with another pol~meri~
zable monomer, were applied to Bonderite 37 treated
cold-rolled 20 gauge steel plates as a film approximately i~ ;
0.001 inch thick (0.025 mm.). The sheets were then ;
exposed to 1-3 megarads of radiation in the ~orm o~ a
two million-volt electron beam. The ~esulting films
were found to be harder and more water-resistant after
irradiation than before.
The above compositions were also applied as
coati~gs on paper and on aluminum sheets and cured by
l-second exposure to U-V light ~rom a 100 w. mercury
arc light at a distance of 5 cm. Again the films were
harder and more water-resistant after exposure, thu~
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17,110/213/252-F -24- ~
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evidencing polymerization and/or crosslinking by the
U-V exposure.
In other experiments, the polymers of Table II
were acidified with phosphoric acid and mixed with 15% by
weight of a 40% by weight aqueous solution of glyoxal.
The solutions were applied as films to an aluminum surface
and dried at room temperature or at 60C. In either case
a tack-free water~insoluble coating was obtained which
was readi~y soluble in aqueous alkali. If the films were
irradiated with U-V or an electron beam they became
insoluble in alkali.
In the above coatings tests, the compounds
of Table II were used alone or with up to 98% of one or
more other polymerizable vinyl monomer. Such other
lS monomer3 included butyl acrylate, 2-hydroxypropyl -
acrylate, methyl methacrylate, acrylonitrileJ methaaryl-
onitrile and styrene. In each case, a crosslinked
polymer was obtained.
The esters shown in Table III were oily
liquids or solids, depending on molecular weight and
funçtionality. Most were readily soluble in most or-
ganic solvents and some were soluble to slightly soluble
in water.
~he utility as surfactants of several of the
compounds listed in Table III is illustrated by the
following series of experiments.
A commercial clay powder was coated with
0.1% by wt. o the compound to be tested and the wet-
ting time of the clay wa3 then determined. In th~
test the wetting time was the time reguired for a sample
17,110/213/252-F -25-
,
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.
3~i8
of the clay to sink to the bottom of a l-liter grad-
uated cylinder containing l liter of water, the time
being measured from when the clay was placed on the
surface of the water.
Results are summarized in the following table.
The compounds are identified by the Run ~o. assigned to
them in Table III.
TABLE IV
Compound
Run ~o.o. From Table IIIWettinq Time, sec.
88 73 5
89 74 4
go 77 4
91 78 3
92 81 3 `;
93 None >25
By virtue of their free hydroxyl groups, ~
the compounds of the invention are re~ctive with, and -
; readily cross-linkable by, polyfunctional compounds -
reactive with hydroxyl groups~ such as formaldehyde,
glyoxal and organic polyisocyanates. By use of such
curing agents, curable coatings can be applied to var- ;
ious substrates and then cured in place to provide firmly
adherent, solvent-resistant coatings. Such techniques
are illustrated by the following examples.
The compounds used are identified by their
Run ~o. as shown in Table III. In each experlment the
compound was mixed with the indicated percentage by
weight o hexakis (methoxy-methyl)melamine. The co~po- - -
sitions were then applied to aluminum plates and cured
by placing the plates in an oven at 180~C. for 5 min.
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, 17,110/213/252-F -26-
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The cured coatings were smooth and strongly adherent. `~`
Immersion in water for 1 hour showed no los~ of adhe-
sion or other visible effect. Resi~tance to organic
solvents was indicated by wetting the surface with
methyl ethyl ketone (MEK) and rubbing it with a finger
until visible loosening, tearing or other impairment
of the film was observed. Results are tabulated in
Table V.
TABLE V
' `'- ' '
Compound %~o. Rubs - '~
Run ~o. ~ _n No.. Table III HMM* in MEK
94 80 21 24
95 81 22~100
9~ 82 22>100
*Hexakis(methoxymethyl)melamine
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17,110/213/252-F -27-
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