US 3892684 A
A composition for producing clear, cured epoxy resins, said resins containing specified glycidyl ethers of propoxylated glycerine as flexibilizers, and being cured at room temperature.
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Description (OCR text may contain errors)
"United States Patent [1 1 Logan Related US. Application Data Division of Ser. No. 299,491, Oct. 20, 1972, Pat. No. 3,792,018, which is a continuation-in-part of Ser. No. 195,455, Nov. 3, 1971, abandoned.
US. Cl. 260/2 N; 260/2 EP; 260/18 PF; 260/47 EN; 260/59; 260/78.4 EP; 260/79; 260/268 R; 260/309; 260/561 A; 260/584 B Int. Cl. C08g 30/10 Field of Search 260/2 EP, 2 N, 2 EC July 1, 1975  References Cited UNITED STATES PATENTS 3,029,286 4/1962 Bressler et a1. 260/584 3,240,376 3/1966 Smith et a1 260/2 EP Primary ExaminerMorris Liebman Assistant Examine'r-T. Pertilla Attorney, Agent, or Firm-Ronald L. Hemingway; Richard C. Wine; Julis P. Filcik  ABSTRACT A composition for producing clear, cured epoxy resins, said resins containing specified glycidyl ethers of propoxylated glycerine as flexibilizers, and being cured at room temperature.
3 Claims, No Drawings CLEAR FLEXIBILIZED EPOXY RESINS' This is a division of application Ser. No. 299,491, filed Oct. 20, 1972, now US. Pat. No. 3,792,018, which application is a continuation-in-part of application U.S. Ser. No. 195,455, filed Nov, 3, 1971, and now abandoned.
BACKGROUND OF THE INVENTION It is common practice in the epoxy resin industry to incorporate flexibilizers into epoxy resin compositions to improve the physical properties of the cured'resin. The function of the flexibilizer is to impart some degree of resiliency and toughness to a normally rather rigid system and thereby to improve thermal shock and impact resistance of castings, improve peel strength of ad hesives and increase the flexibility of films made from the resins. The conventional procedure for preparing flexibilized epoxy resins is to mix the base resin (c.g., the diglycidyl ether of bisphenol A)'with the flexibilizer (e.g., the diglycidyl ether of polypropylene glycol) then to add a curing agent (e.g., diethylenetriamine) in sufficient amount to react withall, or nearly all of the oxirane oxygen groups in the mixture( Belgian Pat. No. 756,055, issued Mar. 11, 1971 describes a particularly desirable flexibilizer which is a glycidyl ether of propoxylated glycerine. The flexibilizer is prepared by reacting glycerine and propylene oxide (or a polymer of propylene oxide) to form an intermediate reaction product and then reacting the intermediate with from about 2 to about 3.3 moles of epihalohydrin per mole of intermediate and effecting ring closure by dehydrohalogenation. These flexibilizers have between 2 and 3 oxirane oxygen linkages per mole of flexibilizer and. for purposes of convenience herein;
2 adhesives for laminating layers of clear glass, etc.) where a clear cured resin is required. The principal object of the present invention is to provide epoxy resin will be called triepoxide flexibilizers. The above triepoxide flexibilizers wherein the molecular weight is between 1,500 and 2,500 are particularly useful since they impart outstanding toughness, structural integrity at elevated temperature. and chemical resistance to the cured resins containing them. It has been found, how- ClH -O CH --O Gil -O ever, that this preferred triepoxide flexbilizer, when incompositions containing triepoxide flexibilizers having a molecular weight of from about 1,500 to 2,500 wherein the cured resin obtained in room temperature curing is clear rather than opaque.
DESCRIPTION OF THE INVENTION According to the present invention it has been surprisingly found that when'a precondensate isformed between the 1,500 to 2,500 molecular weight triepoxide flexibilizer and a curing agent capable of curing an epoxy resin at room temperature, and this preconden sate is then mixed with the base resin, and the-mixture is allowed to cure at room temperaturena clear cured resin results. When using the conventional procedure of mixing the base resin and'flexibilizer, followed by addition of curing agent and curing atroom temperature, an opaque cured resin is formed. Likewise an opaque resin results when the base resin is mixed with the curing agent, followed by addition of the flexibilizer and curing at room temperature. Accordingly, the present invention provides 1) a novel process for preparing clear-cure flexibilized epoxy resins wherein a 1,500 to 2,500 molecular weight triepoxide is used as the flexibilizer and curing is accomplished at room temperature, (2) a novel composition of matter which consists essentially of the condensation product of said triepoxide flexibilizer and a room temperature curing agent and (3) a novel clear cured epoxy resin composition which is produced by the process herein. The clear cured resin composition prepared according to the present invention has substantial parity in physical and chemical properties to the corresponding opaque compositions prepared in the conventional manner (i.e., without precondensing' the triepoxide flexibilizer and the curing agent). The triepoxide flexibilizers which are used in the present invention are described by the following general formula l O. CH CH CH X crrcn 0 1.301 1 Cl T011 m ta,
corporated into an epoxy resin composition and cured 1 to 3, the sum ofn is equal to from 2 to 3. r is equal at room temperature. (i.e.. between about 5C and 35C) with the common room temperature, curing agents (e.g., diethylenetriamine) generally gives an opaque cured resin. On the other hand, when high temperature curing agents. (e.g.. hexahydrophthalic anhydride) are used in these systems and ,curing isperformed at high temperature (e.g., 120C or higher),,a clear cure is obtained.
For reasons of convenience and economyit is preferred that curing be accomplished at room tempera; ture. Although the opaque flexibilized resins obtained by room temperature curing of-tesin compositions containing the 1.500 to 2.500 molecular weight triepoxide flexibilizer are useful and even desirable for many purposes. there are other instances (e.g., clear coatings.
to from 0 to l. the sum of M +1; r is 3, and m, n, p and r are selected so as to give a molecular weight of from about 1,500 to about 2.500, and c] is an number from 0 to 1.3. The correspondingcompounds wherein J I -cn cs is replaced-by I on -cn cit x wherein X is a chlorineor bromine can also be present in small amounts. At least two oxirane oxygens, and preferably three, arepresentpen molecule of the flexibilizer (i.e., preferably )1 3).'The flexibilizers of the invention are prepared by (l) reacting glycerine with propylene oxide (or propylene oxide polymer) to form an intermediate propoxylated glycerine (2) reacting the propoxylated glycerine with from about 2 to 3.3 moles of either epichlorohydrin or epibrornohydrin per mole of propoxylated glycerine and (3) effecting ring closure by dehydrohalogenation in any conventional manner such as by reacting with sodium hydroxide. The degree of propoxylation of the glycerine is chosen so as to provide a reaction product of from L500 to 2,500 afterreaction with the epihalohydrin and subsequent dehydro-halogenation. Although the flexibilizers of the invention can contain from two to three epoxide groups per mole, for purposes of simplicity and convenience they will be referred to herein as triepoxides. Any of the epoxy base resins having more than one l,2-epoxy group which are useful in the formulation of epoxy resin compositions are useful in the present invention. Typical examples of the most widely used types o f b ase resins are as follows: diglycidyl ether of bisphenol A, glycidyl ethers of novolac resins, glycidyl ethers of mononuclear diand trihydric phenols, glycidyl ethers of polynuclear phenols, glycidyl ethers of aliphatic polyols. glycidyl esters, glycidyl epoxies containing nitrogen, thioglycidyl resins, silicon-glycidyl resins, fluorine-glycidyl resins, etc. Other suitable epoxy base resins include epoxy compounds derived from olefins, animal or vegetable oils, synthetic polyesters, unsaturated polyethers. etc.
The curing agents which are suitable for use in the invention are those of the stoichiometric type (as opposed to the catalytic type) which are capable of curing an epoxy resin at room temperature or lower, i.e., at a temperature of from about 35C. to about 5C. or lower. stoichiometric curing agents contain active hydrogens and actually react with the epoxy compounds to form crosslinks. the reaction taking place on the basis of one active hydrogen of the curing agent per epoxide group of the epoxy compound. Catalytic curing agents, on the other hand, act by catalyzing direct reactions between the epoxide groups, and are not part of the present invention.. Examples of stoichiometric. room temperature curing agents are as follows:
1. aliphatic polyamines, for example, diethylene triamine, bis(hexamethylene) triamine and triethylene tetramine 2. N-aminoethyl piperazine 3. Amidopolyamines which are formed from the re action of carboxylic acids with aliphatic polyamines, e.g., 1
ill I which is the product of the reaction of stearic acid with diethylene triamine.
4. substituted imidazoles, e.g., 2-ethyl-4-methyl imidazole. 7
Many other stoichiometric room temperature curing agents are known to those skilled in the art and are suitable for use in the invention herein.
The precondensate of triepoxide flexibilizer and room temperature curing agent which is essential to the practice of the invention-herein is prepared by reacting the flexibilizer with the curing agent. The proportions of the two components are selected such that the amount of curing agent is sufficient to stoichiometrically react with the flexibilizer and to react with from about 75% to 125% (preferably from about 90% to about I 10%) of the amount of epoxy base resin which accomplished is not critical. The reaction can be accomplished at room temperature in which case from about 2 to about 24 hours is required. If desired the reaction time can be reduced to about 30 minutes or less by heating the reaction mixture. If the reaction mixture is heated to about 1 15C it has been found that the reaction can be completed in about l5 minutes. Completion of the reaction can be determined by a negative result in a test for oxirane oxygen. e.g. the test described in an article by 'A. J. Durbetaki entitled Direct Titration of Oxirane Oxygen with Hydrogen Bromide in Acetic Acid. Analytical Chemistry, Vol. 28, pages- To form a clear, cured, flexibilized epoxy resin composition the precondensate is mixed with an epoxy base resin and the mixture is allowed to cure at room temperature. Room temperature curing normally takes from about 3 hours to about 7 days. Time needed for curing is not significantly affected by using the process of the invention rather than the conventional method of mixing the components of the resin. The proportions of precondensate and epoxy base resin are generally selected such that the triepoxide flexibilizer is present in the final cured resin composition at a level of from about 5 parts to 50 parts by weight per 100 parts by weight of the epoxy base resin. Preferably the flexibilizer is present at a level of about 5 parts to about 15 parts per 100 parts of base resin.
In a typical manner of practicing the invention,one first establishes the ratio of flexibilizer to base resin which he desires in the finished resin. He then calcuresin. He reacts this amount of curin g'agent with all of the flexibilizer toform the precondensate, thenj mixes the precondensate with the base resin and allows the 7 mixture to cure at room temperature.
As hereinbefore described, the present invention provides a process for preparing clear, cured; flexibilized epoxy resins, said process comprising the steps of:
A. reacting a triepoxide flexibilizer of the type hereinbefore described. and having a molecular weight of from about l,500 to 2,500, with a room temperature curing agent, as hereinbefore described, to form a precondensate, the proportions of the reactants being such that the curing agent is present in sufficient amount to stoichiometrically react with the flexibilizer and with from about to about 125% of the epoxy resin with which said precondensate is to be mixed in Step B.
B. mixing the precondensate of Step A with an epoxy base resin in proportions such that the resulting mixture contains from=about 5 parts to about 50 parts by weight of triepoxide flexibilizer per parts by weight of epoxy base resin, and
C. curing the mixture of Step B at a temperature of 35C or less to form a clear epoxy resin.
Although the obtaining of a clear cured resin is the primary benefit obtained by way of thepresent invention, certain other benefits are also obtained. For example. many of the curing agents arevolatile liquids invention, their volatility is greatly reduced. Accordin gly, the precondensates can be prepared and shipped by chemical manufactures to the resin formulator who can then formulate the finished resin with less exposure to the hazards normally associated with handling of the volatile curing agents. Those curing agents which are solids, are converted to liquid form when precondensed with the flexibilizer thus providing easier handling and measuring. Further, when, the formulator uses a precondensate thefle'xibilizer and curing agent, he has only two components to mix to form the final epoxy resins, instead of three. v
The cured epoxy resin compositions of the invention can also contain additives which are conventional in epoxy resin technology, e.g., dyes, and diluents such as xylene; dibutyl phthalate, etc. Other-.flexibilizers and plasticizers including flexible epoxy resins, epoxy resins derivedfrom. aliphatic acids, hydroxyl-termin a ted flexibilizlers, natural and synthetic rubbers, and resinous l of glycerin and stannic chloride over a period of 45 minutes. The reaction flask was cooled with cold water to keep the maximum temperature reached during addition below 55C. The reaction mixture was stirred for 45 minutes after completion of the addition step.
120 grams of sodium hydroxide. as a aqueous solution, was added to the product of the addition step. The mixture was heated to 90C and stirred for 2 hours. The mixture was allowed to separate into two layers and the water layer was drained off. This procedure Oxirane Oxygen 2.4% Organic Chloride 0.6% Hydrolyzable Chloride 0.2% 7 Moisture 0.08% Average Molecular weight 1800 Epoxide equivalent weight 668 EXAMPLE II The following epoxy resin compositions were prepared, the amounts of the components being expressed in parts by weight. 7
DETA Flexibilizcr Base resin dicthylcnetriamine the triepoxidc flexibilizer of Examplc Epon 828 (diglycidyl ether of hisphcnol A having an cpoxidc equivalent weight of about 185492) purchased from Shell Chemical Co. New York. N.Y.
EXAMPLE I This example will illustrate the preparation of a triepoxide flexibilizer suitable for use in the invention.
REACTANTS I530 gm. 1 mole) Propylene oxide adduct of glycerin (Hydroxyl value 1 10 mg KOH/gm matcrial)* 277.5 gm. (3 moles) l-chloro-2.3 cpoxypropanc 7.6 gm. Stannic Chloride 240 gm. (6 moles) Sodium Hydroxide (as a 30% solution) A commercial male of romulatcd uhccrine urchased from Jefferson t L T Chemical (o. ol Houston. 1 cxas. contamm a roxlmatch 1'5 pro oxlLlc unlts or L l mole.
PROCEDURE The ,1-chloro-2.3 cpoxypropane was added dropwise to a stirred flaskcontaining the propylene oxide adduct Compositions A, B and C were prepared by mixing the base resin and flexibilizer together, then adding the DETA curing agent. Composition D does not contain a flexibilizer and was prepared by mixing the curing agent with the base resin. Formulas E, Fand G. were made according to-the invention by first reacting the DETA and flexibilizer at l 15C. for 15min. to form a precondensate, then mixing the precondensate with the base resin at room temperature. All of the epoxy resin compositions were allowed to cure at room temperature and were tested, 7 days after they were prepared. Compositions A, B and C were opaque after curing, whereas Compositions D, E, F andG were clear. The cured compositions were milled tostandard dimensions and all testing was according to the procedures specified in ASTM Standards, Plastics-Methods of Testing, Part 27, except for the light transmittance test which was performed in the following manner.
A cured sample of Composition D having a thickness of 0.25 inches was placed against the aperture of a photographic light meter. A monochromatic source of light was directed onto the sample and adjusted to a distance which gave a reading of foot candles on the meter. Keeping the light at this fixed distance, 0.25 inch thick samples of the other cured compositions were placed over the aperture and transmittance readings in foot candles were taken.
Results obtained on the cured resin samples are shown in the following table.
7 8 x A B C D 1 E I F' G Tensile Strength (PS1) R911 10.494 7908 3713 y 7444 9591 7259 Elongation 3.7 '60 -'5.5 3.0 2.6 6.6 t .2 Izod Impact Strength (ftJbs/in.) 0.48 0.70 0.63 0.18 0.55 1 0.48 0.82 Heat Deflection Temperature (C) 67 88 74 57 I04 59 56 Light Transmittanee (ft. candles) 7 i 33 '15 I00 100. 100 100 Chemical Stability (7( weight gain in l'week) v 30% H 50. 0.89 0.99 I584 0.74 1.1 0.88 0.86 H 0 0.18 0.33 0.74 r 0.40 0,30 0.43 0.65 a 3071 NaOH 41.18 "0.28 .'().04 ().l '-0.07 0.()2 -0.04 T: Acetone 29.3 30.6 35; 28.0 29,9 35 35 Appearance opaque opaque opaque clear clear clear clear EXAMPLE 111 An experiment similar to that in Example 11 was performed, substituting TETA (triethylene tetramine) on an equal active hydrogen basis for DETA. The compoabove experiment and substantially similar results are obtained ii -that clear cures are obtained when flexibilsitions prepared were as follows, the amounts of the 7 components being expressed in parts by weight.
in and curing agent are precondensed before mixing with the epoxy base resin and opaque cures are obtained when said precondensation is not done'z'bis (hexainethylcne) triam'ine. N-aminoethyl piperazine,
the amide formed by the reaction of one mole of stearic acid with l mole of diethylene trianiine. and 2-ethyl-4- methyl imidazole. i
The following 'epoxy base resins are. substituted for the Epon 828 in the above experiment on an equal epoxide equivalent weight basis and substantially similar results are obtained in that clear cures a're obtained when flexibilizer and curing agent'are precondensed before mixing with the epoxy base resin and opaque H .l K L M N O TETA 13.1 13.3 13.7 12.9 13.1 13.3 13.7 Flexibilizer" 5.0 10.0 20.0 5.0 10.0 200 Base resin 100.0 100.0 100.0 100.0 100.0 100.0 100.0
The triepoxidc flexibilizer of Example 1 Epon X28 (diglycidyl ether of bisphcnol A having an epoxide equivalent weight of about 185-192) purchased from Shell Chemical Co.
of New York. N.Yv
Compositions H, .l and K were prepared by mixing the base resin and flexibilizer together, then adding the TETA curing agent. Composition L does not contain a flexibilizer andwas prepared by mixing the curing agent with the base resin. Formulas M, N and 0 were made according to the invention by first reacting the TETA and flexibilizer at 115C for- 15 minutes to form a'precondensate} then mixing the precondensate with the base resin at room'temperature. All of the epoxy resin compositions were allowed to cure at room temperature and we'retested 7v days after they were prepared. Compositions H, J and K were opaque after curing, whereas Compositions L, M, N and 0 were clear. The cured compositions were tested in the same manner as those of Example 11, except tests for light transmittance and'chemical stability were not run. Results are shown in the following table.
cures are obtained when said precondensation is not done: polyglycidyl ether of phenolformaldehyde novalac resin having an epoxide equivalent weight of 176 to 181, diglycidyl ether of resorcinol having an epoxide 0 equivalent weight of about] 10, triglycidyl ether of trihydroxy biph'enyl having an epoxide equivalent weight of 144, triglycidyl ether of trimethylol-propane. having an epoxide equivalent weight of 100. diglycidyl ester of linoleic dimer acid having an epoxide equivalent weight 5 of 390 to' 470, the diglycidyl ether of tetrafluorobis- [(2,3 epoxy propoxy) dime thyl silyl] benzene having an epoxide equivalent weight of about 170.
What is claimed is:
H .l K L M N o Tensile Strength 9588 X665 7825 9055 9470 9719 6776 (PS1) /r Elongation ("/r) 5.3 7.2 5.5 5.3 4.4 5.8 9.5 Izod Impact 0.30 0.47 0.61 0.24 0.24 0.45 0.48
Strength (ft. lbs/in.) Heat Deflection 1 61.5 (v0.5 62 5? 59 -18 Temp. (5C) l k Appearance opaque opaque opaque clear clear clear clear The following curing agents are substituted onan equivalent active hydrogen basis for TETA in the l. A precondensate for use in preparing clear flexibilized epoxy resin compositions. consisting essentially of A. triepoxide flexibilizer having the formula 0. ll Cll wherein X is chlorine or bromine. n is a number from I to 3. the sum of n p is equal to from 2 to 3, r
is equal to from t) to l. the sum of :1 +1; r is 3, and m. n, p and rare selected so as to give a molecular weight of from about L500 to about 2.500. and q is a number from O to L3, and
B. a stoichiometric type curing agent capable of curing epoxy resins at temperatures of 35C or lower, the proportions of A and B being such that B is present in sufficient quantity to react stoichiometrically with all of A and with from about 75% to about l% of an epoxy base resin when said epoxy base resin is mixed with said precondensate in such proportion that from about 5 to about 50 parts by weight of flexibilizer are present per parts by weight of epoxy base resin.
2. The precondensate of claim 1, wherein the curing agent is selected from the group consisting of aliphatic polyamines, N-aminoethyl piperazine. amidopolyamines which are formed by the reaction of carboxylic acids with aliphatic polyamines and substituted imidazoles.
3. The precondensate of claim 2, wherein the curing agent is selected from the group consisting of diethylene triamine. bis (hexamethylene) triamine and triethylene tetramine.