CA1196440A - Curable molding compositions containing a vinyl ester resin - Google Patents

Abstract

13,117 CURABLE MOLDING COMPOSITIONS
CONTAINING A VINYL ESTER RESIN

ABSTRACT OF THE DISCLOSURE

Described herein are curable molding com-positions comprising a mixture of:
(a) a vinyl ester produced by the addition of an unsaturated monocarboxylic acid to a polyepoxide and having a molecular weight greater than 300;
(b) acrylic or methacrylic acid or a func-tionalized derivative thereof having a molecular weight of less than 300;
(c) an ethylenically unsaturated monomer which is soluble in and copolymerizable with (a) and (b) and which is different from (b).
The compositions can also contain one or more fibers with a melting point or a glass transition tem-perature above about 130°C.

S P E C I F I C A T I O N

Description

~ 13,117 This inYention ~s dlrected to a curable molding composition con~alning Ca~ a vlnyl ester pro-duced by the addi~ion o~ an unsaturated monocarboxylic acid to a po~yepoxide, Cb~ acrylic or me~hacrylic acid or functionalized derlva~lves thereof which are different from Ca~, and Cc~ an ethy'lenically unsaturated monomer which i9 soluble ln and copolyme~izable with (a~ and Cb) ~1 t~hich is ~iffcrQ~t fro~ Cb?
The combinatlon of components in ~he composition of this invention have been found to produce reinforced articles having a particularly good balance of mechanical propertles. Molded reinforced articles may be produced from the compositions of this invention by a very rapid mold cycle which is typically less than about 2 minutes from ~he time the cure of the resin i5 initiated.
The use of vinyl este~s withcombinations of comonomers is known in the art. For example, U.S.
Patent 3,373,075 describes a thermosetting resinous composltion con~aining certain diacrylates (vinyl esters) formed by the reaction between a polyglycidyl ether of bisphenol A and a monocarboxylic acid possessing eth-ylenic unsaturation. The diacrylates are described as readily copolymerizable with monomers containing at least one terminal ~ C=CH2 radical. Table II of this reference describes the use of various amounts of copoly-merizable monomers, such as styrene, methyl methacrylate, ethylene glycol dimethacryl~e, diallyl phthalate and triallyl cyanurate which a~e used with the diacrylates.

~ 13,117 I~ colu~n 13 o~ U.S. 3,373,075 there is des-cribed t~at the ~e~atively high molecular weight dl-acryla~es can be blended with lower molecular weight diacrylates, such as t~e di(3-methacryloxy-2-hydroxy prop~l~ether of bisp~enol A, Cdescribed as a syrupy product in Example 2~. The reference then states tha~ such a mix~ure can be readily blended with and copol~merized with copol~me~izable monomers, such as styrene and the like.
THE ~NVENTION
It has now been found that when a comonomer, .e., acr~lic or methacrylic acid or functionalized derivati~es thereof, is added to a vinyl ester resin containing a ~inyl ester and an ethylenically unsaturated monomer, the resulting resin compositions produce rein-~orced articles having substantially improved mechanical properties over those of composites which do not contain these particular comonomers.
~t has also bee~ found that certain ratios of the components of the compositions as well as particular components thereof offer enhanced cure speeds with mold closed cyclP~s ty~ically about 1.5 minutes or less from the time the cure of the resin is initiated. Such enhanced cure speeds are seen even in thick articles such as those which are 3/16 inches thick.
This combination of outstanding composite mechan-ical properties and, in many cases exceptional cure speed, make these resins especially suitable for the rapid pro-duction of glass-reinforced compositesvia the molding technology described below.

13,117 The improved curab~e molding composition of this in~en~ion co~prlses a mixture o~
(a) a vinyl ester produced by the addition of an unsaturated monocarboxylic acid to a polyepoxide and having a molecular weight greater than 300, Cb) acrylic or methacrylic acid or a func-tionalized derivati~e thereo~ having a molecular weight of less than 300 and ~ c) an ethylPnically unsaturated monomer which is soluble in and copolymerizable with (a) and (b~ and which is dif~erent from (b).
The instant resin compositions have low viscosities, i.e., less th~n about 150 centipoise, preferably less than about 100 centipoise, so that the~ can be used to produce thermoset resin articles containing up to about 75 weight percent of reinforcing fibers by a very rapid mold cycle.
The vinyl esters which may be used in this invention are produced from the addition of an unsat-urated monocarboxylic acid to a polyepoxide, and have molecular weights greater than 300. These vinyl esters are well known in the art and many are commer-clallY a~ailable.
'i'he unsatura~ed carboxylic acids which may be used lnclude acrylic acidJ methacrylic acid, crotonic acld, and aclds prepared ~rom the reaction of hydroxy-alkyl acrylates or methacryl~tes with maleic anhydride, phthalic anhydride, a~d t~e ~ike.

13,117 The polyepoxides may be saturated or unsatu-rated, aliphatic, cycloalipha~ic, aromatic or he~ero-cyclic and may be substitltted,if d~sired,~7ith non-in~erferlng substituents, such as halogen atoms, hydroxyl groups, ether radicals, and the like.

The epoxides which may be used herein include:
gl~rcidyl ethers of novolac resins, i.e., phenol-aldehyde condensates, Preferred resins o~ this type are those o~ the XormulaI, ~ 1 ~ R -~ -R
(I) R r ~ ~ ~ ~ 2 ~

w~ereln Rl is hydrogen or an alkyl radical and a has a value of from 0.1 to about 5, and preferably less than 1Ø Preparation of these polyepoxides is illustrated in, for ~a~ , TJ.S. Patents 2,216,099 and 2,658,885.
Other examples of epoxides include the epoxidized esters of the polyethylenically unsaturated monocarbo~y-lic acids, such as epoxidized linseed, soybean, perilla, olticica, tung, walnut and dehydrated castor oil, methyl linoleate, butyl linoleate, ethyl 9,12-octadecane-dienoa~e, butyl 9,12,15-octadecatrienoate, butyl eleos-tearate, monoglycerides of tung oil fatty acids, mono-glycerides of soybean oil, sunflower, rapeseed, hemp-seed, sardine, cottonseed oil, and the like.

13,117 ~ nother group of the epoxy-containing comro~mds suitable for use herein include the æ.poxidized esters of unsaturated monohydric alcohols and polycarboxylic acids, such as, for example, dlC2,3-e~Gxyoct~pi~elate, diC2,3-e~oxyoctyl~tr~h~drop~thalate, di(4,S-epoxydodecyl~maleate, di~2,3-epoxyoctyl)t~re~hthalate, di(2,3-epoxypentyl~thiodipropionate, di(5,6-epoxytetradecyl~diphenyldicarboxylate, di(3,4 epoxyheptyl)sulfonyldibutyrate, tri~2,3-epoxybutyl~1,2,4-butanetricarboxyla~e, di~5,6-epoxypentadecyl)maleate, di(2,3-epoxybutyl)azelate, di(3 J 4-epoxybutyl)citrate, di(5,6-e~oxyoctyl~cyclohexane-1,3-dicarboxylate, di(4,5-epoxyoctadecyl~malonate~
~not~e~ group o~ the epoxy-containing materials ~nclude those epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids, such as 3,4-epoxyhexyl-3,4-epoxypentanoate, 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane carboxylate, and the like.
Still another group of the epoxy-containing materials include epoxidi2ed derivatives of polyethylenically ~msaturated polycarboxylic acids, such as, for example, dimethyl 8,9 912 ,13-diepoxyeicosanediote;
dihexyl 6,7,10,11-diepoxyhexadecanedioate;
didecyl 9-epoxyethyl-10,11-epoxyoctadecane-dioate;
dibutyl 3-butyl-3,4,5,6-diepoxycyclohexane-13,117 1,2-dicarboxyl.ate;
dicyclohexyl 3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate;
dibenzyl 1,2,4,5-diepoxycyclohexane-1,2-dicarboxylate and diet~yl 5,6,10,11-diepoxyoctadecyl succinat2.

Still another group comprises the epoxidized polyester obtained by reacting a polyhydric alcohol and an unsaturated polycarboxylic acid and/or anhydride, such as, for example, the polyester obtained by reacting 8,9,12,13-eicosanedienedio-ic acid with ethyle~e glycol, the polyester o~tained by reac-~ing die~hylene glycol wlth 2 cyclohe~ene-1,4-dicarboxylic acid and the like, and mlxtures thereof.
Still another graup comprises the epoxidiæed poly-ethylenically unsaturated hydrocarbons, such as epoxidi~ed

2,2-bis(2-cyclohexenyl~propane, and epoxidized dimer of cyclo-pentadiene.
A preferred polyepoxide includes the glycidyl polyethers of polyhydric phenols and polyhydric alcohols.
Especially preferred are the diglycidyl polyethers of 2,2-bis~4-hydroxyphenyl)propane having the follow-lng formula:

(Il ) C112 CH -C112--L~CI~ ~ 82 CU--C112

3~ ~ ~
13,ll7 wherein d has values eo that the average molecular weight of the polyepoxide is from ~bout 340 to about 2000.
The vinyl esters are well known and are produced by the methods described in, for example, U.S. Patents 3,377,406;
3,637,618; 4,197,390 and 3,317,365. Acid modified vinyl ester resins may also be included in this invention. These are described, for example, in U.5. Patents 3,634,542;3,548,030 and 3,564,074.
Compon~nt (b) in the composition of this invention 1~ is acrylic or methacrylic acid or a functionalized deriva-tive thereof which is different rom (a). ~ixtures of these also may be used. Th~ functionalized derivatives are char-acterized by the presence of acrylate, methacrylate, acrylami~e,and ~ethacry~amide groups and also by the presence of func-~ional groups such as hydroxyl, amino, alkylamino, ether, and epoxide or example. The molecular weight of these monomers is typically less than 300. The preferred monomers are char acterized by the following formula:
o (III) ~CH2=C,-C-X~R3~Y-R4~c whereln R2 is independentl~ hydrogen or methyl; X
~ 5 and Y are independently -O- or -N- wherein R5 is hydrogen or lower alkyl; R3 i9 an allphatic or aromatic radical containlng from 2 to about 10 carbon a~oms, 13,117 optlonall~ containing -0- or -~-; R~ is hydrogen o~ an aliphatic or aromatic radical containing from l to 10 carbon atoms; and b and c are integers of or greater ~han 1, preferably 1 to 3.
These ~unct~onallzed deri~atives o~ acrylic or methacrylic acid lnclude 2 h~droxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 2-aminoethyl acrylate, 2-amlnoethyl methacrylate, 2-methylaminoethyl acrylate, 2-methylaminoethyl methacrylate, 2-dim~thylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-hydroxy-ethyl acrylamide, 2-hydroxyethyl methacrylamide, 2-aminoethyl acrylamide, 2-aminoethyl methacrylamide, diethylene glycol monoacrylate, diethylene glycol mono-methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, pentaerythritol monoacrylate, pentaeryth-ritol monomethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacryl-ate, glycerol monoacrylate, glycerol monomethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, glycidyl methacrylate, glycidyl acryla~e, hydroxyme~hyl acrylamide and the like, or mixtures thereof. It is understood that several isomers of many of these monomers exist and would be suitable for use hereln either as individual components or as mixtures with any of the other monomers. Similarly, lt is understood that additio~al derivatlves containing aromatlc rlngs and other alkyl groups in the acid or ester portlon of formula CII~ ma~ also be included.
9.

13,117 Component Cc~ o~ this ln~ention is an ethyl-enically ~nsaturated monomer which is soluble in and copolymerizable with ~a~ and Cb~ and which is dif~erent ~rom Cb~.
These ethylenically unsaturated monomers contain at least a single -CH=CCgroup, and preferably a CH2=C ~roup and include styrene and its derivatives and homologues, divinyl-benzene, diallylphthalate, nonfunctionalized esters of acrylic or methacryli~ acid (such as ethyl acrylate, butyl acrylate, and methyl methacrylate), unsaturated nitriles (such as acrylonitrile and methacrylonitrile), and the like. Also, ~he monomers include vinyl esters, e.g. vinyl acetate, vinyl propionate, and the like. Mixtures of the aforementioned monomers may be effectively employed in the practice of this inven~ion.
The most preferred eth~lenicall~ unsaturated monomer con-templated in the practice of this invention is styrene.
~ n the composition of this invention component (a~ is present in amounts of from about 10 to about 75, preferably from about 25 to about 60 weight percent; component (b) is present in amounts of from about 2 to about 75, preferably from about 5 to about 30 weight percent; and component (c) is present in amounts of from about 10 to about 75, preferably from about 25 to about 65 weight percent.
A ~ree-radical curing catalyst whlch initiates curing ~ia the co-reactlon of t~e Yiny~ ester resin, the acrylic or ~ethacryllc acid or functionaliæed derlvative thereof, and the ethylenically unsaturated ~onomer ~s included in this inven- -tion. These curing catalysts include azo compounds, perox-10.

13,117 ides, peresters, perketals ~md the like.
Azo and peroxide curing agents are describedby, for example, Gallagher, et al. "Organic Peroxides Review", Pl~stics Design & Processing, July, 1978, pages 38 42, and August, L97~, pages 60-67, inclusive, The choice of the specific peroxide or azo initiators for the purpo~e of curing the composition of this invention is within the purview of those having skill in ~his art and ~he manner in which such peroxides and azo initiators effect a desirable cure is generally characterized in the aforementioned articles.
Examples o such curing catalysts include l,l-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxy-butane, 2,2-di-t-butylperoxy-4-methylpentane, 2,2-dicumylperoxypropane, butyl 2,2-di-t-butylperoxyvalerate, 1,1-bis(2,2,4-trimethylpentyl-2-peroxy)cyclohexane, 2,2'-azo-bis-isobutyronitrile, dibenzoyl peroxlde, lauroyl peroxide, di-t-butyl peroxide 9 diisopropyl peroxide carbonate, t-butylperoxy-2-ethylhexanoate, t-butyl-perpivalate, 2,5-dimethylhexane-2,5-di-perethylhexanoate, t-butyl peroctoate, t-butyl perneodecanoate, t-butyl per-benzoate, t-butyl percrGtonate, t-butyl perisobutyrate, di-t-butyl perphthalate, l,l-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, bis(4-t-butylcyclohexyl)peroxydicarbonate, me~hyl ethyl ketone peroxide, 2,4-pentanedione peroxide, bis(t-butylperoxy) diisopropylbenzene, 2,4,4-trimethylpentyl-2-peroxycyclohexane carboxylate, 2-t-butylazo-2-cyano-4-methylpentane, ethyl 3,3-di(t-butylperoxy)butyrate and 13,117 the l~ke. T~ese aXe co~exc~a~ly aYailable materials.
The peres~ers a~d pe~etals may be used in comblnation with an acid cure accelerator as described in Netherlands publlshed Patent Application No. 7604405.
These acids include Bronsted acids with a PKa value lower than or equal to t~at of formic acid, such as hydrochlorlc acid, sulfurlc acid, nitric acid, phos-phoric acid, trichloroacetic acld, p-toluenesulfonic acid, and the like. Also Lewis acids or metal halides with Lewis acid properties, such as boron trifluoride and the chlorides of iron, cobalt, zinc and aluminum, may be used.
Additionally, the above described curing catalysts may be used in combination with other cure accelera~ors such as cobalt compounds. These cobalt compounds include cobalt naphthenate, cobalt-amine cure promo~ers (such as those designated as PEP 183-S
and available from Air Products Incorporated), and the like. These cure accelerators operate by decom-posing the curing catalysts at a temperature below their normal activation or decomposition temperature.
Mi~tures o~ tl~e curing catalysts may be u~ed herein, such as mixtures of peresters and/or per~etals, of perketals and azo compounds, and of peresters and azo compounds~
The concen~ration of t~e curing agent can be varied withln wide ~imits. As a representative ~ange, the concentration can vary f~om about 0~25 to about 3.0 weight percent, pre~erab~y ~rom about 0.5 to about 2.5 weight percent, and most pre~erably, from about 0.75 to about 2.0 weight percent, based on the weight of compon-13,117 ents Ca~, C~ and Cc~.
The compositions of ~his invention are prepared by solution blending the vinyl ester, the acrylic or methacrylic acid or functlonalized derivative thereof~
~e ethylenically unsatura~ed monomer, a free radical curing catalyst, and ~n~ other optional ingredients at ambient temperatures.
T~e fibers, which ~ay be used in this in~ention as reinforcing agents ha~e a melting poin~
or a glass transitlon temperature above about 130C.
These fibers include ~iberglass, carbon fibers, aromatic polyamide fibers (such as aramid fibers sold by E. I.
duPont de Nemours & Company, Wilmington, Delaware, under the trademark of Kevlar), metal fibers such as aluminum and steel fibers, boron fibers, and the like.
The carbon fibers include those having a ~igh Young's modulus of elasticity and high tensile strength. These carbon fibers may be produced from pitch, as described in U.S. Patents 3,976,729;

4,005,183 and 4,026,788, for example.
The preferred fibers are fiberglass, carbon fibers, aromatic polyamide fibers, and mixtures thereof.
The fib~rs which are suitable for use in this invention, preferably, have a length of at least 1/4 inch, and an average length of at least 1/2 inch. Fibers with different lengths exceeding 1/4 inch may be used, provlded that at least about 50 percent of the fibers have lengths greater t~an l/2 lnch. Preferred fiber lengths are from 1 to 2 or more inches. Continuous filaments ~ay also be used.

~L~ 13,117 It is also within the scope of this invention to include the use of fiber reinforcements of shorter lengths and also fillers such as milled glass.
The molded article contains from about 10 to about 75, preferably from about 40 to about 70 weight percent of the reinforcement fiber or from about 20 to about 40 weight percent of milled glass reinforcement.
It is, furthermore, desirable to utiliæe a vinyl polymeriæation inh~bitor in those cases where the resin solution is to be stored and/or shipped. Suitable vinyl polymerization inhibitors are hydroquinone, para-benzoquinone, t-butyl catechol, quinhydrone, toluhydro-quinone, mono-t-butylhydroquinone, 2,5-di-t-butyl-hydroquinone, hydroquinone monomethyl ether, the biphenol derivatives described in U.S.P. 4,158,027, and the like.
The amount of inhibitor for the purpose of preventing vinyl polymerization can be that conventionally used namely from about 100 to about 1000 ppm of the combined ~eight of components (a), (b) and (c).
The composition of this invention may also include other ingredients, such as mold release agents, and the like.
A preferred procedure for producing a molded article from the compositions of this invention is a process for rapidly fabricating fiber reinforced thermoset resin articles. The fiber reinforcement is g,~ ~, 13,117 comprised of one or more fibers with a melting point or a transition temperature above abou~ 130~C. The process comprises the steps of (a) providing one or more fibers with a melting point or a glass transition temperature above about 130C in the form of an inter-locked mass in a heatable matched metal die mold, (b) providing in one or more accumulator zones, a liquid ~ody o~ a thermosettable organic material having a viscosity determined at 120C, in the absence of curing agent therefore, of less than about 50 centipoise, and which is curable upon heating to a thermoset resin composition, the viscosity of said liquid body being maintained essentially constant in the accumulator zone by keeping its temperature below that at which curing of said material is substantial, (c) closing the mold containing the web, (d) injecting at least a portion of said thermosettable organic material under pressure from said accumulator zone(s) into the mold to thereby fill the cavity in said mold, (e) initiating the curing of said material in said mold by subjecting the material to a temperature above the temperature at which the curing of said material is initiated, by heating the mold, and (f) opening said mold and removing the cured thermoset article therefrom.

,i ~ 13,117 The apparatus comprises: (a) a heatable matched die mold containing one or more cavities therein with means for opening said mold to expose such cavities 9 and closing the same, and means for controlling the injection of a thermosettable organic liquid to such cavities when the mold is closed, (b) means associ~ted with said mold, whereby one or more fibers in the form of an interlocked mass are provided in a portion of the cavities thereof when the mold is open to expose such cavities and prior to the injection of the thermo-settable organic liquid to such cavities when the mold i5 closed, (c) accumulator means associated with said mold which can contain a thermosettable liquid transportable to means for controlling injection of said liquid to such cavities, (d) cooling means associated with the means for controlling the injection of such liquid to such cavities, whereby the temperature of the liquid in such injection means is maintained substantially below the temperature of the mold.

Examples The following examples serve to illustrate specific embodiments of this invention and it is not intended tha~ the invention shall be limited by the examples.
In the examples the flexural strength and modulus of the prepared composites were measured according to the procedure described in ASTM D-790 16~

,~
sO ,~ ,...

~ 13,117 In each example, five separate flexural bars were tested from each plaque and the values listed are the average of those tests.
In each of the following examples a thermo-couple was inserted in the mold midway through the glass mat and the cure rate was observed by measuring the time from resin injection to the time of maximum exotherm in the resin. This time span is designated below as the time to peak exotherm and the time given is an average of several runs. The apparatus used was similar to that describ~d above.
A variety of commercial vinyl ester resins, based primarily on diglycidyl polyethers of bisphenol A were used in the Examples. These resins are designated as follows in the examples:
Vinyl resin lo A vinyl ester resin containing the reaction product of methacrylic acid with a mixture of diglycidyl polyethers of bisphenol A using approximately one mole of methacryli~ acid per mole of epoxide groups. The number average molecular weight (Mn) of the reaction product was approximately 900 to 1000.
The vinyl ester resin is commercially available as a 50~ styrene solution as Derakane ~ C50* (available from Dow Chemical Co.).
Vinyl resin 2: This vinyl ester resin is similar to Vinyl resin 1 except that the vinyl ester *Trademark .1~

13,117 has an Mn of 1100 to 1200. The vinyl ester was again the reaction product of methacrylic acid and a mixture of diglycidyl polyethers of bisphenol A.
A 45 percent styrene solution of this vinyl ester is commercially available as Derakane 411-45* (available from Dow Chemical Co.). The co~mercial resin was diluted to a 50 percent styrene solution to form Vinyl resin 2.
Vinyl resin 3: A vinyl ester resin containing the reaction product of methacrylic acid with a mixture of diglycidyl polyethers of bisphenol A and glycidyl ethers of novolac resins using approximately one mole of methacrylic acid per mole of epoxide groups. The vinyl ester is commercially available as a 36 percent styrene solution as Derakane 470-36*
(available from Dow Chemical Co.).
The commercial resin was diluted to a 50 percent styrene solution to form Vinyl resin 3.
Vinyl resin 4: Thîs vinyl ester resin is similar to Vinyl resin 1. The vinyl ester resin is commercially available as a 50 percent styrene solution as Epocryl 321* (available from Shell Chemical Co.).
Vinyl resin 5: This vinyl ester resin is similar to Vinyl resin 1 except that the vinyl ester *Trademark 18.

J~`f~

13,117 ~as an ~n of ~300 to 1400. The vinyl es~er is com~ercially available as a 45 percent styrene solution as Epocryl 322 Cavailable ~rom Shell Chemical Co.~.
The com~e~c~al ~esin was dlluted to a 50 percent st~rene solution to form Vinyl resin 5.
~inyl resin 6: A modi~ied vinyl ester resin containing in part, the reaction product of methacrylic acid wi~h a mixture o glycidyl polyethers of bisphenol A using approximately one mole o methacrylic acid per mole of epoxide groups. The polyester is commercially available as a 40 percent s~yrene solution as Epocryl 480 (available from Shell Chemical Co.). The co~mercial resin was diluted to a 50 percent styrene solution to form Vinyl resin 6.
Contral ~
-Approximately 200 grams ~appro~imately ten 10 x 5 1/2 inch sheets~ Type AKM glass mat (PPE Indus-tries, Inc. Pittsburgh~ Penn.) was placed in a 10 x 5 1/2 x 3/16 inch constant volume mold preheatPd to 140C.
The mold was closed, evacuated for about 5 seconds, and a resin portion containing 100 weight percent of Vinyl resin-l, 0.5 phr Zelec UN mold release (an 19.

~ 13,117 organophosphate mold release sold by E. I. duPont de Nemours,Wilmington, Delaware), and l.S phr of 1,1-di-t-butylperoxy-3,3,5~trimethylcyclohexane Trigonox 29-E-75 sold by Noury Chemical Corp., Burt, ~.Y.3 was injected at a pressure of 300 psi into the mold.
The pressure was maintained for a dwell period of 10 seconds. A time to peak exotherm of about 75 seconds was measured. After 106 seconds, the cured glass reinforced composite was removed from the mold. The composite contained 66 weight percent glass as determined by ashing.
The composite was tested for flexural strength and modulus.
The results are shown in Table I.

Example 1 The procedure of Control A was repeated except that the resin contained the following ingredients:
80 wt. percent Vinyl resin-l, 20 wt. percent 2-hydroxyethyl acrylate, 1.5 phr Trigonox 29-B-75, and O.5 phr Zelec UN* mold release.
A time to peak exotherm of about 63 seconds was observed.
The cured composite was removed from the mold after 33 seconds and tested as described in Control A.
The results are shown in Table I.
*Trademark 20.

b ! ;, 13,117 E~ ~ple 2 The procedure of Control A was repeated except that the resin contained the following ingre-dients:
80 wt. percent Vinyl resin-l, 20 wt. percent 2-hydroxyethyl methacrylate, 1.5 phr Trigonox 29-B-75, and O.5 phr Zelec UN mold release.
A time to peak exotherm of about 70 seconds 1~ was observed.
The cured composite was removed from the mold after 98 seconds and tested as described in Control A.

The results a~e shown in Table I.
. . .
Control B
The procedure o~ Control ~ was repeated except t~at the resin contained the following ingre-dients:
100 wt. percent Vin~l resin-2, 1.5 phr of Trigonox 29-B-75, and 0.5 phr o~ Zelec UN mold release.
A time to peak e~otherm of about 64 seconds was obser~ed.
The cured composite was removed from the mold after 90 seconds and tested as describ~d in Control A.

The results are shown in Table I.
Example 3 The procedure of Control A was repea~ed 13,117 except ~hat the resin contained the following ingre-dients:
80 wt. percent of Vinyl resin 2, 20 wt. percen~ of 2-hydroxyethyl acrylate~
1.5 phr of Trigonox 29-B-75, and 0.5 phr of Zelec UN mold release.
A time to peak exotherm of about 56 seconds was observed.
The cured composite was removed.form the mold after 144 seconds and tested as described in Control A.

The results are shown in Table I.
Example 4 The procedure o~ Control A was repeated except that the resin co~ltalned the following ingre-d~ents:
80 wt. percent of Vin~l resin-2, 20 wt. percent of 2-hydroxyethyl methacrylate, 1.5 phr of Trigonox 2~-B-75, and 0.5 phr of Zelec UN mold release.
A time to peak exotherm o~ about 64 seconds was obser~ed.
The cured composite was removed from the mold after 136 seconds and tested as described in Control A.

The results are shown in Table I.
Control C
., The procedure of Control A was repeated except that th~ resin contained the following ingre-22.

13,~17 dients:
100 wt. percent of Vinyl resin-3, 1.5 phr of Trigonox 29-B-75, and O,5 phr o Zelec UN mold release.
A time to peak exotherm of about 76 seconds was observed.
The cured composite was removed from the mold af~er 155 seconds and tested as described in Control A.
The resul~s are shown in Table I.
Exa~ple 5 The procedure of Control A was repeated except that the resin contained the following ingre-dien~s:
80 wt, percent o~ ~inyl resin-3, 20 wt. percent o~ 2-hyd~oxyethyl acrylate~
1.5 phr of T~lgonox 2~-B-75, and 0.5 phr o~ Zelec UN mold release.
A time to pe~k exot~erm o~ about 64 seconds was observed, The cured composite was removed from the mold after 82 seconds and tested as described in Control A.
The resul~s are shown in Ta~le I.

The procedure of Control A was exactly repeated except that the resin contained the following lngredients:
80 wt. percent of Vinyl resin-3, 13,117 20 wt. percent of 2-hydroxyethyl methacrylate, l.S phr of Trigonox 29-B-75, and O.5 phr of Zelec UN mold release.
A time to peak exotherm of about 62 seconds was observed.
The cured composite was removed from the mold after 84 seconds and tes~ed as described in Control A.

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~a ~ h Ll ~ ~ ~ rl ~1 ~1 rl rl r~ C~ a~
~ u~ n a S I h h h h h ~I h h ,~
a) r-l r~ l ~1 ~1 ~1 ~1 ~1 ,S;
h ~ :~ :~ ¢ ~ ~ ~ ¢ P~ ~ ~ ¢
o~ ~ ¢ ~ ¢ $~X ~ a H :> :> X ~ ~ h h ~ a~ C~ N N
O r-l ~1 ~1 ~1 O O O 11 ~1 ~ D ll ~11' .,1 ~c ~: , ~ x ~

13,'117 Cont~o~,P
The procedure o~ Control A was exactly repeated except that the resin contained the following lngredlents:
lO0 wt, percent o~ Vinyl resin-4, l.5 phr of Trigonox 29-B-75, and 0.5 phr of æelec UN mold release.
A time to peak exotherm of about 78 seconds was observed.
The cured composite was removed from the mold after 96 seconds and tested as described in Control A.
The results are shown in Table II.
Example 7 The procedure of Control A was exactly repeated except that the resin contained the following ingredients:
80 w~. percent of Vinyl resin-4, 20 wt. percent of 2-hydroxyethyl acrylate, l.5 phr of Trigonox 29-B-75, and 0.5 phr of Zelec UN mold release.
A time to peak exotherm of about 64 seconds was observed.
The cured composite was removed from the mold after 90 seconds and tested as described in Control A.
The results are shown in Table II.
Ex'amp'l'e 8 The procedur~ of Control ~ was exactly repeated except that the resin contained the ~ollowing 26.

13,117 lngredients:
80 wt. percent o~ Vlnyl resin-4, 20 wt. percent of 2-~ydroxyethyl methacrylate, 1.5 phr o~ Trigonox 29-B-75, and O.5 phr o~ Zelec UN mold release.
A time to peak exotherm of about 74 seconds was observed.
The cured composite was removed from the mold after 94 seconds and tested as described in Control A.
The results are shown in Table II.
Control E
The procedure of Control A was exactly repeated except that the resin contained the Eollowing ingredients:
lO0 wt. percent of Vinyl resin-5, 1.5 phr of Trigonox 29-B-75, and 0.5 phr of Zelec UN mold release.
A time to peak exotherm of about 79 seconds was observed.
The cured composite was removed from the mold after 98 seconds and tested as described in Control A.
The results are shown in Table II.
Example 9 The procedure of Con~rol A was exactly repeated except that the resin contained the following lngredlents:
80 wt. percent of Vinyl resin 5, 20 wt. percent of 2-hydroxyethyl acrylate, 27.

13,1~7 1.5 phr of Trlgonox 29-B-75, and 0.5 phr o~ Zelec UN mold release.
A time to peak exotherm of about 72 seconds was observed.
Th~ cured composite was removed from ~he mold after 87 seconds and tested as described in Control A.
The results are shown in Table II.
Examp e 10 The pxocedure of Control A was exactly repeated except that the resin contained the following ingredients:
80 wt. percen~ of Vinyl resin-5, 20 wt. percent of 2-hydroxyethyl methacrylate, 1.5 phr of Trigonox 29-B-75, and 0.5 phr of Zelec UN mold release.
A time to peak exotherm of about 79 seconds was observed.
The cured composite was removed from the mold after 140 seconds and tested as described in Control A.
The results are shown in Table II.
Control F
The procedure o~ Control A was repeated except that the resin contained the following ingre-dients:
100 wt. percent of Vinyl resin-6, 1.5 phr of Trigonox 29-B-75, and 0.5 phr of Zelec UN mold release.

28.

13,117 A time to peak exotherm of about 52 seconds was observed.
The cured composite was removed from the mold after 70 seconds and tested as described in Control A.
The results are shown in Table II.
Example 11 The procedure of Control A was repeated except that th~ resin contained the following ingre-dients:
80 wt. percent of Vinyl resin-6, 20 wt. percent of 2-hydroxyethyl acrylate, 1.5 phr of Trigonox 29-B-75, and 0.5 phr of ~elec UN mold release.
A time to peak exotherm of about 52 seconds was observed.
The cured composite was removed from the mold af~er 72 seconds and tested as described in Control A.
The results are shown in Table II.

~ple 12 The procedure o$ Control A was repeated ~xcept that the resin contained the following ingre-dients:
80 wt. percen~ of Vinyl resin-6, 20 wt. percent of 2-hydroxyethyl methacrylate, 1.5 phr of Trigonox 29-B-75, and 0.5 phr of Zelec t~ mold release.
A time to peak exotherm of about 63 seconds 2g .

13,117 was o;bserved.
The cured composite was removed from the mold after 78 seconds and ~ested as described in Control A.
The results are shown in Table II.

30.

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e ~4 r-l 41 rl O
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O O O O O O O O
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O 1:~ ~1 ~) ~ ~ ~ ~ ~ ~) ~) ~q ~n U~

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~:
.,1 O ~ 00 1-- 0 o C~l 00 E~r~ O O~ C~ C;~ /30 ~ 1_ 1_ 1_ 'O
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~ x E~ ~

~1 o o o ~ o o o o o o o o o ,d ~21 r-l O 00 c~l 00 ~ r ~1 5 .. t~i~
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rl r-l R R ~ CJ
0 ~ ~rl rl rl rl rl rl rl rl rl ~ ~ U~ r 1:~ ~ a~ a.) o ,_,-rl ~I h ~ ~ h ~ 1 1-1 r-l r-l ~1 ~I r-l r~ l ~I r-h h h h ~ h h ~ c~ h ~ h~
~3 ~ ~ ~ ~r ~ rl rl.r ~ ~3 r ~ rl O ~1 I ~
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Claims (28)

13,117 WHAT IS CLAIMED IS:

1. A curable molding composition comprising a mixture of:
(a) a vinyl ester produced from the addition of an unsaturated monocarboxylic acid to a polyepoxide, and having a molecular weight greater than 300, (b) a functionalized derivative of acrylic or methacrylic acid having a molecular weight of less than 300 characterized by the following formula:

(III) wherein R2 is independently hydrogen or methyl; X
and Y are independently -O- or , wherein R5 is hydrogen or lower alkyl; R3 is an aliphatic or aromatic radical containing from 2 to about 10 carbon atoms, optionally containing -O- or ; R4 is hydrogen or an aliphatic or aromatic radical containing from 1 to 10 carbon atoms; and b and c are integers of or greater than 1; and (c) an ethylenically unsaturated monomer which is soluble in and copolymerizable with (a) and (b) and which is different from (b).

32.

13,117

2. A curable composition as defined in claim 1 wherein the unsaturated monocarboxylic acid is selected from acrylic acid, methacrylic acid, crotonic acid, and acids prepared from the reaction of hydroxyalkyl acrylates or methacrylates with maleic or phthalic anhydride.

3. A curable composition as defined in claim 1 wherein the polyepoxide is saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic which may be substituted with halogen atoms, hydroxyl groups and ether radicals.

4. A curable composition as defined in claim 1 wherein the polyepoxide is an epoxidized ester of an unsaturated monohydric alcohol and unsaturated monocarboxylic acid.

5. A curable composition as defined in claim 1 wherein the polyepoxide is a epoxidized ester of unsaturated monohydric alcohol and polycarboxylic acid.

6. A curable composition as defined in claim 1 wherein the polyepoxide is an epoxidized ester of a polyethylenically unsaturated monocarboxylic acid.

7. A curable composition as defined in claim 1 wherein the polyepoxide is an epoxidized derivative of a polyethylenically unsaturated polycarboxylic acid.

33.

13,117

8. A curable composition as defined in claim 1 wherein the polyepoxide is a epoxidized polyethylenically unsaturated hydrocarbon.

9. A curable composition as defined in claim 1 wherein the polyepoxide is an epoxidized polyester obtained by reacting a polyhydric alcohol and an unsaturated polycarboxylic acid and/or anhydride.

10. A curable composition as defined in claim 1 wherein the polyepoxide is the glycidyl polyether of a polyhydric phenol and/or a polyhydric alcohol.

11. A curable composition as defined in claim 1 wherein the polyepoxide is of the following formula:

wherein R1 is hydrogen or an alkyl radical and (a) has a value of from 0.1 to about 5.

12. A curable composition as defined in claim 1 wherein the polyepoxide has the following formula:

34.

13, 117 wherein d has values so that the average molecular weight of the saturated polyepoxide is from about 340 to about 2000.

13. A curable composition as defined in claim 1 wherein the vinyl ester resin is present in amounts of from about 10 to about 75 weight percent.

14. A curable composition as defined in claim 1 wherein the component (b) is selected from one or more of the following: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-methylaminoethyl acrylate, 2-methylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, 2-aminoethyl acrylamide, 2-aminoethyl methacrylamide, diethylene glycol monoacrylate, diethylane glycol monomethacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, 35.

13,117 pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, glycerol monoacrylate, glycerol monomethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, glycidyl methacrylate, glycidyl acrylate, and hydroxymethyl acrylamide.

15. A curable composition as defined in claim 1 wherein component (b) comprises 2-hydroxyethyl acrylate.

16. A curable composition as defined in claim 1 wherein component (b) comprises 2-hydroxyethyl methacrylate.

17. A curable composition as defined in claim 1 wherein the functionalized derivative of acrylic or methacrylic acid is present in amounts of from about 2 to about 75 weight percent.

18. A curable composition as defined in claim 1 wherein the ethylenically unsaturated monomer comprises styrene.

19. A curable composition as defined in claims 1 or 18 wherein the ethylenically unsaturated monomer is present in amounts of from about 10 to about 75 weight percent.

20. A curable composition as defined in claim 1 which contains a curing initiator.

36.

13,117

21. A curable composition as defined in claim 20 wherein the curing initiator is a perester and/or perketal, or a mixture of peresters and/or perketals.

22. A curable composition as defined in claim 20 wherein the curable initiator is an azo and/or peroxide containing compound.

23. A curable composition as defined in claim 20 wherein the curing initiator is a mixture of an azo cmpound and a perester and/or perketal.

24. A curable composition as defined in claim 20 which contains an acidic cure accelerator.

25. A curable composition as defined in claim 19 which contains an accelerator comprising a cobalt containing compound.

26. A molded article prepared from the composition of claim 1.

27. A molded article as defined in claim 26 which contains from about 10 to about 75 weight percent of one or more fibers having a melting point or a glass transition temperature above about 130°C.

28. A molded article as defined in claim 27 wherein the fiber is selected from fiberglass, carbon fibers, aromatic polyamide fibers, and mixtures thereof.

37.