CA1154022A - Adducts containing hydroxyl groups from mononuclear hydantoin glycidyl compounds and non-aromatic dicarboxylic acids - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

An advanced addition product containing hydroxyl groups is prepared from the reaction of specific mononuclear hydantoin glycidyl compound with non-aromatic dicarboxylic acids of 9 to 44 carbon atoms and, optionally mono-carboxylic acids of 6 to 18 carbon atoms. The above advanced addition products are heat curable with suitable curing agents for hydroxyl containing materials to afford cured compositions exhibiting excellent weathering, color stability and chalking resistance.

Description

The so-called"advancement" of relatively low molecular and low-melting or liquid epoxide resins by reaction with polyfunctional compounds of which the functional groups react with epoxide groups, to give relatively higher molecular, higher melting epoxide resins is known.
Such a so-called "advancement" is above all intended to improve or modify, in the desired direction, the technical processing proper~ies for certain end uses. For some end uses, for example in sintering powders, compression moulding powders and the like, an increase in the softening point or melting point can be desirable. The so-called "advancement" produces, in parallel to the increase in size of the molecule, a lowering of the epoxide group content per kilogra~ of resin and hence a reduction in the reac~ivity. This has an atvantageous effect, for example when using the product as a casting and impregnating resin, in that the shrinkage on reaction becomes less and reduces the danger of ca~ity formation, above all in the case of larger castings.

The following represent typical patents which disclose such advancement products. U.S. ~atents 3,779,949, 3,793,248 and 3,799,894 teach that certain binuclear N-heterocyclic compounds containing one endocyclic NH group in each nucleus can be employed for advancement of a number of epoxy resins including non-aromatic resins such as N,N'-diglycidyl hydantoin products.

U.S. 4,209,516 and U.S. 4,210,744 also ti~close advancement of diglycidyl hydantoin compounds with binuclear ~is-hydantoin compounds.
It is to be noted that the latter sdvanced products exhibit active epoxy groups through which curing occurs. U.S. 4,119,595 discloses adducts of an epoxy resin and a polymerized fatty acid. The latter materials are non-heterocyclic, require excess strong acid catalyst and do not provide good weatherability performance characteristics.

. . , ~lS~

The sub;ect of the present invention is an advanced addition product containing hydroxyl groups, which is obtained by heating a mixture comprising:

(a) one equivalent of a mononuclear hydantoin glycidyl compound selected from the group consisting of (1) a compound of the formula I
Rl O

H2C-~HCH2-N ~ N-CH2CH-~H2 (I);
O O O

(2) a compound of the formula II

~:~ O
R4 ~ Rs H2C-/CHCH2-N ~ N-CH2CH-O-CH2 ~H-~ H2 (II) O O O

(3) a compound of the formula III

R7 ~ R8 H2C~-~ H-CH2- ~ -CH2CH-OH . (III);

t4) any combination of compounds of the formulae I, II, or III, wherein Rl, R2, R3, R4, R6 and R7 are independently alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 to 6 carbon atoms or Rl and R2 together, R3 and R4 together and R6 and R7 together are tetra-~ethylene or pentamethylene, and R5 and R8 independently are hydrogen ' 1~54~

or methyl;

(b) 0.7 to 2.0 equivalents of a non-aromatic dicarboxylic acid of 9 to 44 carbon atoms; and (c) O.O. to 0.5 equivalents of a monocarboxylic acid of 6 to 18 carbon atoms.

The hydantoin of the formula IV

R" O
R' ~ /
. ~ (IV), wherein R' and R" are independentty alkyl or cycloalkyl or R' and R"
are tetramethylene or pentamethylene, can be prepared by the well-known Bucherer synthesis employing a given ketone, sodium cyanide and ammonium carbonate. Hydantoins of the formula IV are known to react with alkylene oxides in a molar stoichiometry to afford 3-hydroxy-alkyl hydantoins of tbe formula V
R" a R'_ ~ R " ' . ~ ~-CH2CHOH (V) wherein R"' i9 the alkyl radical obtained from removing the epoxide moiety from the alkylene oxide or hydrogen in the case of ethylene oxide. Hydantoins o~ the formula IV are also known to react with epihalohydrins to for~ 1,3-diglycidyl hydantoins of formula I.
Similarly, the glycidylization of hydroxyalkyl hydantoins of the ` .

, , l~S~O~;~

formula V afford, in the addition to diglycidyl hydantoins of the formula II, monoglycidyl-hydantoins of the formula III.

Mixtures of the mononuclear hydantoin glycidyl compounds may be prepared in a number of alternative methods. First, mixtures of the mononuclear hydantoin glycidyl compounds may simply be prepared by combining the individual mononuclear hydantoin glycidyl compounds.
Secondly, a mixture of the mononuclear hydantoin glycidyl compounds of the formulae I, II and III, wherein the substituents in the 5,5 position of the hydantoin moiety are the same, can be prepared by the glycidylization of a mixture of hydantoins of the formula IV, and hydroxyalkyl hydantoins of the formula V, prepared by the partial reaction of a hydantoi~ of the formula IV with less than a stoichio-metric amount of alkylene oxide. Alternative methods of producing mixtures of the mononuclear hydantoin glycidyl compounds are quite apparent to the s~illed artisan.

The preferred mononuclear hydantoin glycidyl-:compounds are those compounds of fonmulae I, II or III wherein Rl, R2, R3, R4, R6 and R7 are independently alkyl of 1 to 8 carbon atoms and R5 and R8 are independently hydrogen or methyl. The most preferred mononuclear hydantoin glycidyl compounds are as follows:
1,3-diglycidyl-5,5-dimethylhydantoin;
1,3-diglycidyl-5-ethyl 5-me~hylhydantoin;
1,3-diglycidyl-5-sec-amyl-5-ethylhydantoin;
l-glycidyl-3 (glycidyloxy-2'-propyl)-5,5-dimethylhydantoin;
l-glycidyl-3-(2'-hydroxypropyl)-5,5-dimethylhydantoin; and mixtures thereof.

The preferred non-aromatic dicarboxylic acids are those containing 17 to 36 carbon atoms. The most preferred non-aromatic dicarboxylic acids are those selected from the group consisting of aliphatic dicarboxylic acids, dibasic fatty acids and a dicarboxylic acid of the formula VI

~15~

Hl3C6 ~ C7Hl4co2H (VI).
~2 H

Examples of the aliphatic dicarboxylic acids which may be employed in the instant invention are azelaic acid, sebacic acid, l,10-decanedi-carboxylic acid, l,ll-undecanedicarboxylic acid and undecanedioic acid.
Examples of dibasic fatty acids are obtained by the dimerization of olefinic fatty acids employing known synthetic me~hods. The olefinic fatty acids which may be dimerized to form the dibasic fatty acids include oleic acid, ricinoleic acid, petroselinic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, punicic acid, licanic acid, parimaric acid and the like or mixtures thereof. The dibasic fatty acids which are commercially available consist essentially of the dimerized fatty acids containing 36 carbon atoms with minor amounts of monobasic fatty acids of 18 carbon atoms and tribasic fatt~ acids of 51 carbon atoms.

The C21 dicarboxylic acid of the formula VI

Hl3C~ ~ ~ C7Hl4C02H (VI) is commercially available from Westvaco Chemical Division, Chaleston Heights, South Carolina, under the name Westvaco Diacid 1550 and prepared via a Diels-Alder cycloaddition of acrylic acid with a conjugated mono-acid of the formula H13C6-CH~cH-cH~cH C7H14 C2 ..

~, ~. . .

li5451;~

Examples of the monocarboxylic acid which may be employed with the non-aromatic dicarboxylic acid in the instant invention include caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, decylenic acid, dodecylenic acid, oleic acid, ricinoleic acid and linolenic acid.

The new adducts of this invention are manufactured by heating the non-aromatic dicarboxylic acid or a mixture of the non-aromatic dicarboxylic acid and the monocarboxylic acid with the mononuclear hydantoin glycidyl compounds at a temperature between 100 and 250C and preferably 150 to 200C. Preferably, 0.8 to 1.2 equivalents of the non-aromatic dicarboxylic acid is reacted with one equivalent of the mononuclear hydantoin glycidyl compound.

The reaction can be accelerated by adding suitable catalysts. Such catalysts are for example alkali hydroxides such as sodium hydroxide or alkali halides such as lithium chloride, potassium chloride and sodium chloride, bromide or fluoride; tertiary amines such as triethylamine, tri-n-propylamine, benzyldimethylamine, N,N-dimethyl-aniline and tricthanolamine; quaternary ammonium hydroxides such as benzyltrimethylammonium hydroxide; quaternary = onium salts such as tetramethylammonium chloride, tetraethylammonium chloride, benzyl-trimethylammonium chloride, benzyltrimethylammonium acetate or methyl-triethylammonium chloride; hydrazines having a tertiary nitrogen atom, such as l,l-dimethylhytrazine, which can also be employed in th~
quaternized form.

Depending on the choice of the starting substances the reaction takes place, quantitatively, so rapidly that no addition of catalyst is necessary. Whilst the starting substances may be mixed with one another at room temperature and then brought to the reaction temperature, it is advantageous in the case of very viscous and li~i4()~'~

reactive components for the non-aromatic dicarboxylic acid or the mixture of the non-aromatic dicarboxylic acid and the mono-carboxylic acid to be heated to the requisite reaction temperature and the nononuclear hydantoin glycidyl compounds gradually added. The progress of the reaction can be followed by titration of ~he epoxide groups using samples taken during ~he reaction; the end product will contain a defined, constant epoxide group content of less than 0.7 equivalent/kg, and preferably 0.0 to 0.5 equivalents/kg.

The advanced addition products of the instant invention have a molecular weight range from 600 to 15,000, and preferably 800 to 3,000.
The advanced addition products are usually viscous liquids at ambient temperature but, in the case of the higher molecular weight products, may be solid. The advanced addition products contain a high content of hydroxyl groups as evidenced by a hydroxyl number of 80 to 160. The color of these advanced addition products i8 generally a light amber.

Because of their high content of free hydroxyl groups, these adeanced attition protucts react with the usual curing agents for hydroxyl containing compounds, and can, therefore, be crosslinked or cured by atting such curing agents~

A preferred curing agent includes the so-called amino resins of amino-plasts containing -NH2 groups derived ~rom urea and melamine.
Suitable amino-containing resins are prepared by reacting urea or melamine with formaltehyte under well-known contitions to form a reaction monomer first and then, by condensation polymerization, a large number of varying types of polymeric intermediates are formet.
The preparation of urea-formaldehyde and melamine-formaldehyde resins is well known in the art and forms no part of the present invention.
Their use in crosslinking epoxy resins mostly through methylol groups is also well known. Accordingly, a large number of amino-plast and ~159~0~2 g phenol-plast resins, i.e., urea-formaldehyde and melamino-formaldehyde resins, are commercially available under such trade designations as Plaskon, Beetle, Cymel, Fiberite, Resimene, Curacron and Beckamine, among many others.

The amount of curing agent employed to cure the advanced addition products may vary with respect to the type of advanced addition product to be cured and the curing agent to be employed. Generally, a weight ratio of advanced additi~n product to aminoplast resin employed would be fro~ 95:5 to about 70:30, and preferably from 90:10 to about 75:25.

The above compositions containing the advanced addition product and curing agent are heat curable at emperatures over 150C, and preferably cured at temperatures between 180 and 250C.

To accelerate the curing process an acidic curing-accelerator, well known in the art~ can be added to the heat curable mixture. Examples for accelarators are strong organic and inorganic acids such as para-toluene sulfonic acid, sulfuric acid and phosphoric acid or derivatives thereof such as the = onia or amine salts. The amount of the curing accelerator may be less than 2 percent by weight of the advanced addition product, preferably less than 1 percent by weight.

The expression "cure", as used here, denotes the conversion of the above adducts, containing hydroxyl groups, into insoluble and infusible crosslinked products, as a rule with simultaneous shaping to give shaped articles such as castings, pressings or laminates, or to give two-dimensional structures such as coatings, enamel films or adhesives bonds.

~lS40~2 The heat curable compositions are employed mainly in ~he field of surface protection. The resultant cured coatings are suitable for application areas such as coil, appliance, automotive and metal decorating. The present coating composit~on?-~may be applied to a suitable substrate by any suitable means such as spraying, dipping, brushing~ painting or roller coating. After the desired film thickness is applied to a suitable substrate, the coated substrate is baked at temperatures over 150C for sufficient time to cure the films.

The resultant cured coatings are void-free and possess excellent physical properties and chemical resistance. Specifically, the coatings are highly resistant to chalking, salt spray ~nd humidity. The cured coating also exhibit excellent weather resistance.

The following examples are illustrative of the instant invention. All parts are based on parts by weight.

A - 1,3-diglycidyl-5,5-dimethylhydantoin ~ - 1,3-diglycidyl-5-ethyl-5-methylhydantoin C - 1,3-diglycidyl-5-sec-amyl-5-ethylhydantoin D - l-glycidyl-3-(glycidyloxy-2'-propyl)-5,5-dimethylhydantoin E - l-glycidyl-3-(2'-hydroxypropyl)-5,5-dimethylhydantoin A. Preparation o~ ad~anced additlon products Example 1 The dicarboxylic acid of the formula VI (415.6 parts) was charged into a one li~er, 3 neck round bottom flask equipped with a thermometer, nitrogen inlet tube, ant a mechanical stirrer. The acid was heated ~o a temperature of 175 - 183~C with stirring in a nitrogen atmosphere.

~lS40~

A mixtu~e of glycidyl compound C (199.3 parts), glycidyl compound D
(135.5 parts) and glycidyl compound E (58.1 parts) was added portion-wise over a period of 20 minutes to the heated acid (0.83 equivalents of acid to 1.0 equivalent of glycidyl compounds). After the addition was complete, the reaction was monitored by periodic epoxy value determination. rhe reaction was essentially complete after 16 minutes when the epoxy value of 0.57 equiv./kg was obtained. The resulting advanced addition product (Adduct J) had an acid number of 8 and a hytroxyl number of 117. Adduct J (80 parts) was dissolved in methyl ethyl ketone (20 parts) to afford a coating composition.

Exam ~
Adduct K, Adduct L and Adduct M were prepared employing 0.83 equivalents of the dicarboxylic acid of the formula VI with 1.0 equivalents of the glycidyl compounds in the following table according to Example 1.

Glycidyl Epoxy Value Hydroxyl Acid Compound Adduct Equiv. Number Number --~
B K 0.45 152 8 D (70 parts) L 0.56 91 --E (30 parts) A (70 parts) D (21 parts) M 0.62 125 2 E (9 parts) Example 3 Adduct N was prepared according to Example l except a dihasic fatty acid of 36 carbon atoms (578 parts) was employed in place of the dicarboxylic acid of formula VI (0.83 equivalents of acid to 1.0 equivalent of glycidyl compounds). Adduct N had an epoxy value of 0.63 equiv.~kg, an acid number of 9 and a hydroxyl number of 95.

.
. : ~

11540~

Example 4 The dicarboxylic acid of the formula VI (187.0 parts) and oleic acid (28.3 parts) were combined in a one liter , 3-neck round bottom flask equipped with a thermometer, a nitrogen inlet tube, and a mechanical stirrer. The mixture was heated to a temperature of 170-175C with stirring in a nitrogen atmosphere.

A mixture of glycidyl compound C (83.1 parts) and glycidyl compound D
(80.7 parts) was added portion-wise over a period of 20 minutes to the hea~ed acid (1Ø equivalent of acid to 1.0 equivalent of glycidyl compounds). After the addition was complete, the reaction was monitored by periodic epoxy value determination. The reaction was essentially complete after 32 minutes when the epoxy value of 0.32 equiv./kg was attained. The resulting advanced addition product (Adduct 0) had an acid number of 26.6 and a hydroxyl number of 148.
Adtuct 0 (80 parts) was dissolved in methyl ethyl ketone (20 parts) to af~ord a coating comRosition.

Example 5 The dicarboxylic acid of the formula VI (270.8 g) was charged to a one liter, 3-neck round bottom flask equipped with a thermometer, a nitrogen inlet tube, and a mechanical stirrer. The acid was heated to a temperature of 175-183C with stirring in a nitrogen atmosphere.

A mixture of glycidyl compound A (127.5 parts), glycidyl compound D
(38.3 parts) and glycidyl compound E (16.4 parts) was added portionwise at this temperature over a period of 28 minutes (1.0 equivalent of acid to 1.0 equivalent of glycidyl compunds).

After the addition was complete, the reaction was monitored by periodic epoxy value determination.

-l~S9~

The reaction was essentially complete after 25 minutes when the epoxy value of 0.62 was attained. The resulting advanced addition product ~Adtuct P)~had an acid number which was undetectable and a hydroxyl number of 125. Adduct P (80 parts) was dissolved in methyl ethyl ketone (20 parts ) to afford a coating composition.

Example 6 The dicarboxylic acid of the formula VI (498.8 parts) was charged to a one liter, 3-neck round bottom flask equipped with a thermometer, a nitrogen inlet tube and a mechanical stirrer. The acid was hea~ed to 175-180C with stirring in a nitrogen atmosphere.

Glycidyl compound B (267.4 parts) was added pro~ionwise over a 20 minute period to the heated acid (1.2 equivalents of acid to 1.0 equivalent of glycid-~l compound). After the addition was complete, the reaction was continued for 85 minutes further. The advanced addition product (Adduct Q) had an epoxy value of 0.07 eq./k~., an acid number of 37 and a hydroxyl number of 147. Adduct Q (80 parts) was dissolved in methyl ethyl ketone t20 parts) to afford a coating composition having a Gardner bubble viscosity of Z3-Z4.

Example 7 The dicarboxylic acid of formula VI (311.7parts)was charged to one liter, 3-neck round bottom flask equipped with a thermometer, a nitrogen inlet tube, and a mechanical stirrer. The acid was heated to a temperature of 185-190C with 9tirring in a nitrogen.atmo9phere.

A mixture of glycidyl compound D (112.9 parts) and glycidyl compound E
(48.4 parts) was added portionwise at this temperature over a period of 33 minutes (0.75 equivalents of acid to 1.0 equivalent of glycidyl compounds). The reaction was essentially complete after a period of 2 hours when an epoxy value of 0.27 eq./kg was attained. The resulting advanced addition product (Adduct S) had an acid number of 60 and a hydroxyl number of 119.

~154~

Example 8 Adduct T was prepared according to Example 7 except glycidyl compound B (133.7 parts) was employed in place of the mixture of glycidyl compounds (0.75 equivalents of acid to 1.0 equivalent of glycidyl compound). The reaction was essentially complete after a period oEone hour when an epoxy value of 0.26 equiv./kg was attained.
Adduct T had an acid number of 60 and a hydroxyl number of 126.

Example 9 The dicarboxylic acid of formula VI (415.6 parts) was heated to a temperature of 175-180C. The equipment and condition used were the same as those o~ Example 5.

A mixture of glycidyl co;mpound A (99.6 parts) glycidyl compound D
(30.0 parts) and glycidyl compound E (13.1 parts) was then added portionwise over a period of 21 minutes to the heated diacid (2.0 equivalents of acid to 1.0 equivalent of glycidyl compounds).
After the addition was complete, the reaction was monitored by periodic epoxy value determination. The reaction was essentially complete after 70 minutes when an epoxy value of 0.02 equiv./kg was attained. The resulting advanced addition product (Adduct M) had an acid number of 92 and a hydroxyl number of 95.

Exa~pl_ 10 Adduct V was prepared according to Example 9 except glycidyl compound C (166.1 parts) was employed in place of the mixture of glycidyl compounds (2.0 equivalents of acid to 1.0 equivalent of glycidyl compound). Adduct V has an epoxy value of 0.02 equiv./kg~
.
an acid number of 89 and a hydroxyl number of 95.

Exam~ e 11 Adtuct W was prepared according to Example 9 except a mixture of llS40~2 glycidyl compound D (112.9 parts) and glycidyl compound E (48.8 parts) was employed in place of the mixture of glycidyl compounds A and D
(2.0 equivalents of acid to 1.0 equivalent of glycidyl compound).
Adduct W had an epoxy value which was undetectable, an acid number of 88 and a hydroxyl number of 97.

B. Application and Testin~

Example I
Adduct J was formulated into a high solids enamel by blending on a paint shaker: Adduct J (160.00 parts) (80 % weight solids in methyl ethyl ketone); Cymel 303, an alkylated melamine-formaldehyde resin from American Cyanamid (32.00 parts); FC 430, flow control agent from 3M Company (0.06 parts); Curing Agent "C", morpholine salt of p-toluene sulfonic acid from American Biosynthetics; and me~hyl ethyl ketone (8.00 parts). The above formulation (200.40 parts) was combined with Titanox 2060 (80.00 parts), a titanium dioxide pigment from NL Industries, and ground with sand to Hegman Gauge of 8.
The pigmented formulation was then let down with additional methyl ethyl ketone (39.40 parts).

The above high solids enamel possessed the following properties:

Fo = lation Propert-'es Hardener Cymel 303 Resin~Hardener Ratio 80/20 Binder/Pigment Ratio ' 2:1 % Solids in MEK (by Weight~ 75 Viscosity, sec.(~4'F'ord Cup)l 28 Curing Agent "C" 0.5 %

Determined according to ASTM 1200.

1154V~;~

The formulated material was drawn into films on Alodine 12002 treated aluminum and cured at a peak metal temperature ~PMT) of 232C~for 50 seconds. The resulting films possessed the following properties:

Film properties obtained Industry Requirements Pencil Hardness F F (HB minimum) "T" Bend 2-3T 2T maximum MEK P~ubs, double 50 50 Cross-Cut Adhesion ~xcellent Excellent Reverse Impact (C~ ~g)- i7-23- - -- 34-57 (18 minimum) Cure Schedule, P.M.T., 232GC 50 sec. 45-60 sec.
Dry Film Thickness 1-1.2 mils 0.8-l mil Fuming Factor 3Z~ 5 Chromium oxide conversion coating.
3 Test utilized to determine degree of deformation of a coated sheet of metal coil Test described in Paint Testing Manual, ed. G.G.
Sword, p. 334, Section 5.4.4.2.
Continental Can Company, Inc. procedure for determining percent 1088 of solids due to non-solvent volatilization when enamel baked at 232C.

ResiRtance to yellowing These films were tested for color stability exposure to accelerated weathering studies in a commercial dew cycle~ carbon arc Weatherometer.

: .

:- :

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C_lor difference readingsl Hydantoin-Based Acrylic-Based Bisphenol A Epo~7 Resin Resin Resin ... . -- -- --Rd 2) b Rd b Ra b Initial 79.6 +0.9 75.0 +1.3 84.0 +0.9 3 Months 80.5 ~0.8 75.4 +0.9 82.8 +1.9 6 Months 79.9 +1.1 74.9 +1.1 80.7 +4.2 Tested according to ASTM D2244-68 + ~ Rd = Lighter - ~ Rd ' Darker + ~ b - Yellower (less Blue) : - A b - Bluer (less Yellow) Accelerated weatheri~g study The films were also subjected to an accelerated weathering study in a commercial dew cycle Weatherometer using a carbon arc light source.
Controls were a commercially available acrylicl and a conventional bisphenol A-base epox~ system.
60 ~

Substrate Initial 500 Hrs 1000 Hrs (1) Hydantoin-Baset AA 81 75 74 68 Resin R-37 86 82 79 78 (2) Acrylic-BasedM 72 69 45 65 Resin B-37 79 76 67 65 (3) Bisphenol A Epoxy AA 85 25 20 9Resin B-37 89 30 21 8 No chal~ing or yellowing was observed with resins 1 and 2.
Heavy chalking and noticeable yellowing was obser~7ed with resin 3.

.

- , - ., , , .-- . . -- -,, - . , :
- . : . -- : . ' ~ ' :

' - . : ' ': : ~
- . . :
.- - : ' - ~

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Acryloid oL-42 from Rohm and Haas M - Alodine 1200 Aluminum B-37 - Bonderite Steel ~37 Salt spray and humidity resistance testing The films were tested for salt spray tASTM B117) and humidity resistance (ASTM D 2247); results are tabulated in Table I, above~
Acryloid OL-42 from Rohm and Haas ~erved as the control.

Except where noted, no blistering, chalking or peeling occurred.

Table I
Test . . ~
Hydantoln Based Resin (1) . _ __ . . .
Hours: Substrate Initial500 1000 2000 3000 Salt Spray (5 Z Solution) M 82 85 83 80 tSlight (Haavy Blis- Blis-tering) tering) Humidity Cabinet AA 83 87 87 79 74 11~4~ Z

Acrylic Bas~ Resin (2) ~ . . . _. .
Hours: Substrate Initial 500 lOOG 2000 3000 Salt Spray (5 % Solution)AA 61 72 72 75 (Sligh~ (Heavy Blis- Blis-tering) tering) ~umidity AA 55 67 65 72 66 Cabinet B-37 82 91 86 83 72 (Surface covered with tiny blisters) Example II
Adduct L was formulated into a high solids formulation according to the procedure followed in Example I of the testing section. The resulting formulation possessed the following properties:

Formulation pro~_rties Hardener ~ - Cymel 303 Resin/Hardener Ratio 80/20 Binder/Pigment Ratio 2:1 2 Solids in MEK (by weight~ 75.3 Viscosity, ~ec. (~4 Ford Cup) 31 Curing Agent "C" 0.34 2 The formulated material was drawn into films on Alodine 1200 treated aluminum and cured at a peak metal temperature (PMT~ of 232C for 60 sec. The resulting films possessed the following properties:

~ - - - . . . .

-.

~54~

Film properties obtained Pencil Hardness HB
"T" Bend 0-l T
MEK Rubs, Double 50 Cross-Cut Adhesion Excellent Reverse Impact, (cm kg) 23 Cure Schedule, P.M.T., (232C) 60 sec.
Dry Film Thickness 0.9-1.0 mil (22.5-25.0 ~m) Fuming Factor 5-6%

Example III
Adduct J (74.38 parts) (80 ~ weight solids in methyl ethyl ketone) was combined with Cymel (10.50 parts), methyl ethyl ketone ~15.12 parts) and Curing Agent "C" (0.1 parts) to produce a one component, clear high solids formulat;on. This was placed in stability testin~ at 25C. The formulation exhibited an initial Gardner viscosity of H and vi~cosity of I-J after 10 months.

A similar formulation containing glycidyl compound A exhibited an initial Gardner viscosity of K-l anl a viscosity of N-0 after 10 months.

Example IV
Gloss retention and chalk resistance . . _ . _ _ . _ _ . . .
The adduct S was formulated with Cymel 303 according to Example 1 and cured at a PMT of 232C. for 50 second~. The substrate was Alodine 1200 aluminum.
.
The cured films were tested for gloss retention and chalk resistance after exposure in a dew cycle, carbon arc ~eatherometer.

~lS~ 2 _ 60 ~ Gloss Readings Initial _ 96213 453 525785_ _ _ _ (1) Hydantoin-Based81 82 8082 76 79 71 Resin (3) Bisphenol A Epoxy 90 89 86 78 47 23 20 Resin Chalking was observed after 453 hours with the bisphenol A epoxy resin. None was observed with the hydantoin-based material.

Resistance to yellowing Adduct S was formulated with Cymel 303 according to Example 1 and cured at a temperature of 450F for 50 seconds. The substrate was Alodine 1200 aluminum.

The cured films were tested for resistance to-yellowing after Weatherometer exposure.

Color difference readings*
Hydantoin-Based Bisphenol A Epoxy Resin Resin _ Exposure Time ~Hours) Rd b Rd b _ . _ Initial 79 +1.1 84 +0.9 24 81 -0.2 84 +0.9 96 80 -0.2 84 ~1~0 213 81 -0.2 84 +1.1 453 80 -0.5 83 +1.4 525 80 -0.1 83 +1.6 785 80 -0.4 82 +1.9 1409 82 -0.4 80 +3.6 ~ . -1154V;~

*Tested according to AST~ D2244-68 ~ ~ Rd = Lighter - ~ Rd = Darker + Q b = Yellow r (less Blue) - ~ b = Bluer (less Yellow) Summarizing, it is seen that this invention provides advanced addition products which afford cured compositions exhibiting excellent weathering characteristics, color stability and chalking resistance. Variations may be made in proportion materials and procedures without departing from the scope of the invention as defined in the following claims.

Claims (11)

What is claimed is:

1. An advanced addition product containing hydroxyl groups, which is obtained by heating a mixture comprising:
(.alpha.) one equivalent of a mononuclear hydantoin glycidyl compound selected from the group consisting of (1) a compound of the formula I

(I);

(2) a compound of the formula II

(II) (3) a compound of the formula III

(III);

(4) any combination of compounds of the formulae I, II, or III, wherein R1, R2, R3, R4, R6 and R7 are independently alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 to 6 carbon atoms or R1 and R2 together, R3 and R4 together and R6 and R7 together are tetra-methylene or pentamethylene, and R5 and R8 independently are hydrogen or methyl;

(b) 0.7 to 2.0 equivalents of a non-aromatic dicarboxylic acid of 9 to 44 carbon atoms; and (c) 0Ø to 0.5 equivalents of a monocarboxylic acid of 6 to 18 carbon atoms.

2. An advanced addition product according to claim 1 wherein R1, R2, R3, R4, R6 and R7 are independently alkyl to 1 to 8 carbon atoms and R5 and R8 are independently hydrogen or methyl.

3. An advanced addition product according to claim 1 wherein the mononuclear hydantoin glycidyl compound is selected from 1,3-diglycidyl-5,5-dimethylhydantoin, 1,3-diglycidyl-5-ethyl-5-methylhydantoin, 1,3-diglycidyl-5-sec-amyl-5-ethylhydantoin, 1-glycidyl-3-(glycidyloxy-2'-propyl)-5,5-dimethylhydantoin, 1-glycidyl-3-(2'-hydroxypropyl)-5,5-dimethylhydantoin, and mixtures thereof.

4. An advanced addition product according to claim 1, wherein the non-aromatic dicarboxylic acid contains 17 to 36 carbon atoms.

5. An advanced addition product according to claim 1, wherein the non-aromatic dicarboxylic acid is selected from the group consisting of aliphatic dicarboxylic acids, dibasic fatty acids and a dicarboxylic acid of the formula VI

(VI).

6. An advanced addition product, according to claim 1, prepared by heating a compound or mixture of (a) 1,3-diglycidyl-5,5-dimethylhydantoin, 1,3-diglycidyl-5-ethyl-5-methylhydantoin, 1,3-diglycidyl-5-sec-amyl-5-ethylhydantoin, 1-glycidyl-3-(glycidyloxy-2'-propyl)-5,5-dimethylhydantoin, 1-glycidyl-3-(2'-hydroxypropyl)-5,5-dimethylhydantoin, and (b) a dicarboxylic acid of the formula VI

(VI).

7. An atvanced addition product according to claim 1, prepared by heating a compound or mixture of (a) 1,3-diglycidyl-5,5-dimethylhydantoin, 1,3-diglycidyl-5-ethyl-5-methylhydantoin, 1,3-diglycidyl-5-sec-amyl-5-ethylhydantoin, 1-glycidyl-3-(glycidyloxy-2'-propyl)-5,5-dimethylhydantoin, 1-glycidyl-3-(2'-hydroxypropyl)-5,5-dimethylhydantoin, and (b) a dibasic fatty acid of 36 carbon atoms.

8. An advanced addition product, according to claim 1, prepared by heating a mixture consisting essentially of (a) one equivalent of the mononuclear hydantoin glycidyl compound; and (b) 0.8 to 1.2 equivalents of the non-aromatic dicarboxylic acid.

9. A heat curable composition which comprises an advanced addition product containing hydroxyl groups according to claim 1 and a curing agent therefor.

10. A heat curable composition according to claim 9, wherein the curing agent is an aminoplast.

11. A heat curable composition according to claim 10 wherein the aminoplast is a melamine-formaldehyde resin or an ureaformaldehyde resin.