CA1061358A - Linear copolymers of glycidol process for making polyglycidyl esters-copolymers of glycidol and glycidyl esters - Google Patents

Abstract

A B S T R A C T
Copolymers of glycidol, glycidyl esters of car-boxylic acids and, optionally, alkylene oxides, are prepared by the reaction of a saturated or unsaturated carboxylic acid with a polymer or copolymer of tertiary butyl glycidyl ether in the presence of an acid catalyst.
The polymers prepared from unsaturated carboxylic acids are polymerizable and copolymerizable with vinyl monomers and are useful as curable resins. Many of them can be used to make water-resistant or water-insoluble coatings for metals or other substrates.
The polymers prepared from saturated carboxylic acids are useful as coatings for metals and as surfactants.

Description

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.
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17,110/213/252-F -1- ;

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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 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 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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~(: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 "".

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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-~' ' , : , '' ` ` "` ,` ~ .' ,: . , ' , : . :

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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 . ~

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~ 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 .~ ' '.
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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.

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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 . , .

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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-.

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~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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-- ~0613S~3 -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~ :
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the molecular weight8 ~hown in T~bl? I.

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17, 110/213/252-F -22-, , , .. . ., ., ~ . . ~ . . , ; . , .. . ' ~0~;~L3S~3 ~
.. .
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u~ O h ~ ~ . .
~ ~ P~ ~ ~ ~.
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O ~ ~ '::
~4 S-l u~ u~ OD O O
W ,1 '''~
b o~ `
u ~ ~ 0 0 0 Ln ~ n o~ ~ i Ul . . .. .... .. ,~ .
H ~i ~1 ~1 ~1 ~ 1 ~) O d' U
H ~ a ;~
a .~ U o rl . ~ U
~ ;~;
_I ~1 Id 11~ N N .
~ ~ ~ a~ I I a~ o ,1 ~
U, ~ U
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~ o C

H ~1 _I ~~ ~ ~1 ~1 r l t) `
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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~

. ... ':
17,110/213/252-F -24- ~

. , .. . , ~
. : . . .... , , ~ ; . :

106~358 .
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-, ~ . ' . , . :
. . .
.

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.

go 77 4 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-. ~ .

,. . . . , . - . , , , ~, . ,,, ~. . : , ~613Si5 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

95 81 22~100 9~ 82 22>100 *Hexakis(methoxymethyl)melamine ..

.
:' ' ' 17,110/213/252-F -27-..
, .
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, .
, ~ .

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Compositions of the formula 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 R5OH, in which R5 is hydro-gen; alkyl of 1 to 12 carbons which may be substituted 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 ethy-lene, trimethylene, tetramethylene, 1,2-butylene and groups of the formula -CH2?HCH2A
where each A independently is H or OX; X independently is H or the acyl radical of a carboxylic acid selected from acrylic acid, .alpha.-lower alkyl acrylic acid and acids of the formula R8(COOH)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 -CH2?HCH2OX
wherein X is the acyl radical of acrylic acid or .alpha.-lower alkyl acrylic acid; and m and n are integers such that the total number of R'O groups is at least 2.

2. The compositions of Claim 1 wherein X is the acyl radical of acrylic acid or .alpha.-lower acrylic acid.

3. The compositions of Claim 1 wherein X is the acyl radical of a saturated carboxylic acid having the formula R8(COOH)y, where R8 and y are as described in Claim 1.

4. The compositions of Claim 1 whereln the hydroxy compound is water or an alkylene glycol.

5. The compositions of Claim 1 wherein R is the residue of an aralkylaryl compound containing up to 20 carbon atoms which may be substituted by a further 1 to 3 hydroxyl groups.

6. The compositions of Claim 5 wherein R is the residue of bisphenol A.

7. The compositions of Claim 1 wherein R is the residue of glycerol.

8. The compositions of Claim 1 wherein at least one R' is tetramethylene.

9. The compositions of Claim 1 wherein m is 3 to 300.

10. The compositions of Claim 3 wherein the number of R' groups is at least 10, of which at least 3 are of the formula -CH2?HCH2OX
and 20 to 80 percent of the X's are acyl radicals.

11. The compositions of Claim 10 wherein the acyl radicals are derived from an alkanoic acid of 2 to 20 carbon atoms.

12. The compositions of Claim 11 wherein the acid has 8 to 18 carbon atoms.

13. The process for making the compounds of Claim 1 comprising reacting tertiary butyl glycidyl ether (TBGE) with an initiator R5OH as defined in Claim 1 to form a polymer, and then reacting said polymer with an acid selected from acrylic acid, .alpha.-lower alkyl acrylic acid and saturated carboxylic acids of the formula R8(COOH)y wherein R8 and y are as described in Claim 1, said reaction being conducted in the presence of a strong acid catalyst.

14. The process of Claim 13 wherein the catalyst is a sulfonic acid.

15. The process of Claim 13 wherein the catalyst is an arylsulfonic acid and the unsaturated acid is acry-lic or methacrylic acid.