KR810001048B1 - Method of forming curable epoxy resin composition - Google Patents

Abstract

A poly(oxypropylene) diamine (I) was treated with urea, PhNCO, HCO2H, or BzOH to prep. poly(oxypropylene)diureides or diamides which were used as additives to improve the thermal shock resistance of epoxy resins hardened with methyl-5-norbornene-2,3-dicarboxylic anhydride. Thus, 1980g I (mol. wt. 2000, 1.01 mequiv. HN2/g) and 180g urea were heated at 130oC-134≰C for 2 hr, treated with 990 g I during 3hr at 132oC, and heated at 134oC for 70min to prep. a diurea.

Description

Curable Epoxy Resin Composition

The present invention relates to a curable epoxy resin with increased thermal shock resistance. In particular, it is related with the anhydrous epoxy resin containing polyether diurade and diamide.

Epoxy resins form a variety of polymeric materials with a wide range of physical properties. The resin contains an epoxide group which is cured by reaction with a catalyst or a curing agent to obtain a cured epoxy resin composition having desired properties. One such hardener is generally anhydride. The most commonly used anhydrides are bifunctional compounds such as maleic anhydride and phthalic anhydride and tetrafunctional compounds such as pyromellitic anhydride.

It is known to use polyamides as epoxy curing agents. Simpleamides such as acetamide, benzamide and adiamide have been used but the use of basic catalysts has been required due to their low activity or solubility. The advantages and disadvantages of polyamide as a curing agent are Henry. Lee and K. Although discussed in the Epoxy Resin Handbook by Neville, hydrogen in primary and secondary amides is generally less reactive with epoxy groups.

It is known that various ureas and substituted ureas useful as homocuring agents or curing accelerators are effective as co-curing agents.

Aliphatic and aromatic compounds having one terminal uraid group are known. It is known that each terminal amino group can be reacted with an aliphatic diamine having at least one unstable hydrogen atom and urea to produce a diurade whose terminal is an aliphatic compound.

Epoxy resins must withstand high and low temperature repeated cycles without degradation in order to mold, seal or encapsulate. However, lowering the temperature increases the stress due to shrinkage and reduces the ability of the resin to flow, thereby relieving stress.

Anhydrous curable resins are useful when applied where high thermal flexibility is required, but such materials are brittle and have low thermal shock resistance. Diluents and modifiers improve the thermal shock resistance, but unfortunately affect the thermal flexibility of May and Tanaga's epoxy resins. As such, most plasticizers are incomparable with cured resins and thus are not widely accepted in the epoxy industry.

It has been found that special diureides or diamides terminated in polyoxyalkylene materials, with molecular weights of 2000 to 3000, provide cured epoxy resin compositions that exhibit distinct thermal shock resistance when used as epoxy additives. In particular, when the epoxy resin to which the additive is added is cured with a special bicyclic anhydrous hardener, a material having high thermal flexibility and high thermal shock resistance is obtained.

The results of imparting additives according to the present invention are particularly surprising in that similar ureides with lesser molecular weights of compounds do not result in the same improvement in the curable resin. The cured epoxy resin composition of the present invention is useful for coating, casting and sealing.

The present invention has (i) the amount of hardening of a bicyclic polyepoxide having a epoxide of at least 1.8 equivalents, (ii) a substituted bicyclic bicyclic anhydride, and (iii) having a ureide group or an amido group at the end. It provides a cured epoxy resin composition composed of an effective amount of an additive composed of polyether diurade or diamide having a molecular weight of 2000 to 3000.

The present invention also provides an epoxy resin composition obtained by curing the resin described above.

On the other hand, the curable epoxy resin composition having a high thermal shock resistance is bisineal poly epoxide; A cured amount of a bicyclic bisine anhydride comprising a substituted cyclopentadiene and a Diels-Alder adduct of maleic anhydride; And an effective amount of a polyether diurade or diamide additive.

In preparing the resin of the present invention, a diglycidyl ether of 4,4'-isopropylidene bisphenol, a cured amount of methyl-bicyclo [2,2,1] heptene-2,3-dicarboxylic anhydride, Dimethylaminomethyl substituted phenol accelerators and effective amounts of polyether diurades or diamides having a ureido or amido group at the ends and a molecular weight of about 2000 are used.

According to the present invention, polyepoxide, anhydrous hardening agent and polyether-containing compound having diurade or diamide at the end and optionally a promoter are thoroughly mixed and cured according to a conventional method while maintaining thermal flexibility and having a very high thermal shock resistance. A hardened epoxy resin is obtained.

Bisinal polyepoxide containing compositions cured with amines are generally organics having at least 1.8 reactive 1.2-epoxy groups per mole on average. The polyepoxide material may be monomers or polymers, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic, or heterocyclic, and may be substituted with other cyclic moieties other than epoxy groups such as hydroxyl groups, ether groups or aromatic halogen atoms. It may be substituted.

Poly of glycidyl ether prepared by epoxidation of the corresponding allyl ether or by reaction of at least one mole of epichlorohydrin with an aromatic polyhydroxyl compound, i.e., isopropylreddene bisphenol, novolak or resorcinol. Epoxides are preferred, and epoxy derivatives of methylene and isopropylidene bisphenol are particularly preferred.

Widely used types of polyepoxides useful in the present invention include resin type epoxy polyethers obtained by reacting epihalohydrin such as epichlorohydrin with polyhydric phenol or polyhydric alcohol. Examples of suitable dihydric phenols include 4,4'-isopropylidene bisphenol, 2,4'-dihydroxydiphenylethylmethane 3,3'-dihydroxydiphenyl-diethylmethane, 3,4'-dihydro Oxydiphenyl-methylpropylmethane, 2,3'-dihydroxy diphenylethylphenylmethane, 4,4'-dihydroxydiphenylpropylphenylmethane, 4,4'-dihydroxydiphenylbutylphenylmethane, 2,2'-dihydroxydiphenylditolalmethane and 4,4'-dihydroxydiphenyltolylmethylmethane. Other polyhydric phenols that co-react with epihaltohydrin to provide such epoxypolyethers include compounds such as substituted hydroquinones such as resorcinol, hydroquinone and methylhydroquinone.

Examples of the polyhydric alcohol which co-react with epihalohydrin to provide a resinous epoxy polyether include ethylene glycol, propylene glycol, butylene glycol, pentanediol, bis (4-hydroxycyclohexyl) dimethylmethane, 1,4-dimeth Tyrolbenzene, glycerol, 1,2,6-hexanetriol, trimetholpropane, mannitol, sorbitol, erythritol, pentaerythritol, dimers, trimers and higher polymers thereof, for example polyethylene glycol, poly Propylene glycol, triglycerol, dipentaerythritol, polyallyl alcohol, polyhydric thioethers, i.e. 2,2'-3,3'-tetrahydroxydipropylsulfide, merhapto alcohols ie monothioglycerol or dithio Glycerol, polyhydric alcohol partial esters, ie monostearin or pentaerythritol monoacetate and halogenated polyhydric alcohols such as glycerol, sorbitol or pentaerythritol Monochlorohydrin and the like.

Another polyepoxide polymer that can be used in the present invention and that can be cured with anhydrides includes epihalohydrins such as epichlorohydrin, preferably formaldehyde, in the presence of a basic catalyst, ie sodium or potassium. Epoxy novolak resins obtained by reacting with a resin such as aldehyde and phenol per se and a resin-like condensate polymerized with polyhydric phenol are included. Further details on the properties and preparation of this epoxy novolak resin can be found in the Epoxy Resin Handbook by Lee and Neville.

It is contemplated that the polyepoxide compositions useful for the practice of the present invention are not limited to those containing polyepoxides, but merely used on behalf of polyepoxides.

Anhydrous hardeners that can be used in the present invention are generally alkylsubstituted bicyclic bisine anhydrides, such as cyclopentadiene substituted with DL-Altihydrate of maleic anhydride. Preferred compounds generally have the following structural formula.

Wherein R is alkyl and more preferably alkyl of 1 to 4 carbon atoms. Preferred alkyl groups are methyl, ethyl, propyl and n-butyl. Most preferred alkyl is methyl. Most preferred anhydride is methyl-bicyclo [2,2,1] heptene-2,3-dicarboxylic anhydride.

Polyether diurade and diamide additives can generally be described as polyoxyalkylene-containing materials having ureido or amido groups at the ends and having a molecular weight of 2000-3000. In particular, this compound is a polyoxyalkylene compound which has a ureido or amido group at the terminal and has the following general formula.

Wherein X is hydrogen, methyl or ethyl; Z is alkylene of 2 to 5 carbon atoms and n is the number of molecules of the general formula of 2000 to 3000 molecular weight. Preferred diurades and diamides are compounds in which Z is a 1,2-propylene group and n is 16-19.

The polyether diureide compound is a ureido-forming compound at a molar ratio of about 2 mole of ureido-forming compound per mole of dioxyamine at 120-150 ° C. with a polyoxyalkylene diamine having such a molecular weight of ureido-containing product of 2000-3000. Can be formed by reacting.

Similarly, polyether diamide compounds can be obtained by reacting amido-forming compounds with polyoxyalkylene diamines at a dolby ratio of about 2 moles of amido-forming compounds per mole of diamine at 25-150 ° C. Many methods are known for acylating amine reactants to obtain such compounds.

Diamines useful for forming the additives are polyoxy alkylene diamines of the general formula:

Wherein X is hydrogen, methyl or ethyl, Z is alkylene of 2 to 5 carbon atoms; And n is 15-25. Preferred polyoxypropylene diamines are those compounds wherein X is methyl, n is 16-19 and Z is 1,2-propylene group. Such polyoxyalkylene polyamines can be produced by a known method. What is shown here as n is an average, not an integer.

A ureido forming compound is generally a compound which supplies O = C-NH group, and urea is preferable. When urea is used as the reactant, the reaction proceeds with ammonia. The first amino group at the end of the polyoxyalkylenepolyamine soon converts to a ureido group.

Urea is a preferred ureido forming compound, but other ureido forming compounds may also be used. Polyoxyalkylene-polyamine reaction product is already contained in the first group at the end, so NCO M ⁺ an alkali metal such as potassium or sodium in general M ^{+ -} it is possible to use the isocyanate of the general formula: Preferred isocyanates that can be used in the present invention are particularly useful sodium and potassium isocyanates.

Amide forming compounds are generally compounds that supply a formyl (H. CO ⁻ ) group. Suitable such compounds include formic acid, acid chlorides and esters thereof. Acylation reactions that can be used are known and will not be discussed further here.

According to the invention, the reactants are simply mixed in the correct molar ratio in the correct molar ratio and heated until the reaction takes place.

The function of the polyoxy alkylene polyamine depends on the number of the first amino group at the end, which is 2 in the present invention. It will be appreciated that one mole of ureido forming compound or amido forming compound will react with the first amino group at one end of the polyoxyalkylenepolyamine. It is particularly important to maintain a special molar ratio of reactants in forming the additive compound used according to the invention. In particular, about 1 mole of ureido-forming compound or amido-forming compound is required per mole of amino group of polyoxyalkylene polyamine. As such, diamine and about 2 moles of ureido-forming compound or amido-forming compound are used. Preferably, the reaction proceeds in the presence of a slight excess of ureido-forming compound or amido-forming compound so that the amido group can be completely converted.

Optionally, the epoxy resin formulations of the present invention may include a "promoter" to speed up the anhydrous cure of the epoxy resin, in particular at ambient temperature. In many applications, such accelerating action is particularly advantageous when epoxy resins are used as adhesives in flammable environments, such high temperature curing is unnecessary and even dangerous. The use of amine containing compounds as epoxy hardener-promoter is known from the epoxy resin manual of Li and Neville.

Accelerators that can be used in the present invention are known; For example, there are known tertiary amines. Preferred promoters according to the invention are dialkylamine substituted aromatic compounds and preferably dimethylaminomethyl substituted phenols.

According to the method of the present invention, the thermal shock resistance of the non-curable epoxy resin of the prior art is effective by adding an effective amount of polyether diurade or diamide having a terminal ureido or amido group as described above and having a molecular weight of 2000 to 3000. It is improved by soaking. An effective amount of adhesive to improve adhesion is by the use of resins and accelerators. In general, the additive may be used as much as 5 to 35 parts by weight based on 100 parts by weight of the resin component, preferably 10 to 20 parts by weight.

The exact amount of additive effective to increase the thermal shock resistance can be easily determined without much experimentation since the resin mixture containing the additive effective amount shows a change that can be easily seen as the curing proceeds. In particular, cured resins are opaque and milky when cured, resulting in a glossy milky product. Advantageously, it should be noted that this arbitrary absorption movement enhances the beauty of the mold and precludes the need for the use of white pigments or layering agents.

Preferably, the thermal shock resistance of the prior art resin adds an effective amount of polyoxypropylene diuraide or diamide additive based on condensation of 2 moles of urea or formic acid with 1 mole of polyoxypropylene diamine having a molecular weight of 2000. This is improved. Preferred resins are polyglycidyl ethers of polyhydricphenols cured by incorporating a cured amount of methyl bicyclo [2,2,1] -heptene-2,3-dicarboxylic anhydride with a dimethyl-aminomethyl substituted phenolic accelerator. It is composed.

The curable epoxy resin composition of the present invention is generally composed of a bisinal polyepoxide, a cured amount of alkyl-substituted acyclic bicyclic anhydride curing agent, and an effective amount of a polyether diurade or diamide additive and optionally may add an accelerator.

Anhydrous curable resins having excellent thermal shock resistance according to the present invention and no actual thermal alteration are prepared according to conventional methods. The polyepoxide composition is mixed with the anhydrous curing agent using the equivalent of the functional carboxyl groups of the curing agent used. In general, the equivalent number of carboxyl groups is 0.8 to 1.2 times the number of epoxide equivalents present in the curable epoxy resin composition. Preferred stoichiometric amount is 0.9. 1-5 parts by weight based on 100 parts by weight of resin is generally and satisfactory when using an accelerator. The exact amount of components according to the above general requirements is mainly determined by the purpose of applying the cured resin.

The additive is combined by mixing with the uncured resin. Preferably, the additive is first mixed with a curing agent or accelerator before the additive is added to the resin. The components forming the curable material are well mixed by standard methods and degassed in the presence of commercial antifoams and small amounts of silicone oil to prevent pores and bubbles. All epoxy resins known herein are generally useful for the present invention, but it is preferred not to use only those based on aliphatic compounds. At least 50% by weight of the resin component, preferably 80% by weight, most preferred is the presence of a resin containing 100% by weight of polyglycidyl ether of polyhydric phenol, which greatly improves the desired properties of the cured material.

Preferably the curable resin is 4,4'-isopropylidene bisphenol diglycidyl ether; An effective amount of polyether diurade having a molecular weight of about 2000 having a ureido group or an amido group at the terminal and a curing amount of methyl bicyclo [2,2,1] heptene 2,3-dicarboxylic acid anhydride, a dimethylaminomethyl substituted phenolic accelerator, and a terminal It consists of diamide. More preferably, 80 to 90 parts by weight of a curing agent is used per 100 parts by weight of the resin.

Preferred proportions of the component are 1 to 5 parts by weight of accelerator; 80 to 90 parts by weight of anhydrous hardener; And 5 to 35 parts by weight of an additive, wherein all of the above amounts are based on 100 parts by weight of the resin. Generally, the mixture of epoxy resins, additives, anhydrous hardeners and accelerators is self-cured at high temperatures of 200 ° C, more preferably 100-190 ° C, most preferably 135-170 ° C.

Even more preferably, the resin of the polyhydric phenol type polyglycidyl ether is 80-90 parts by weight of methyl bicyclo [2,2,1] heptene-2,3-dicarboxylic anhydride; A polyether diureido or diamido, wherein the terminal having a molecular weight of 5-40 parts by weight of about 2000 is a polyoxyalkylene-polyamine; is cured by binding 1 to 5 parts by weight of a dimethylaminomethyl substituted phenol accelerator. The composition is cured at 100-190 ° C. to produce a product having excellent thermal shock resistance according to the invention.

It will be appreciated that various commonly used additives may be mixed with the polyepoxide containing compositions of the present invention prior to final curing. For example, in some cases it may be desirable to add small amounts of other anhydrous cocatalysts. It may also add competing conventional dyes, dyes, fillers, flash retardants or natural or synthetic resins.

Moreover, although not preferred, it is also possible to use known solvents for polyepoxide materials such as toluene, benzene, xylbene, dioxane and ethylene glycol monomethylether. The polyepoxide resin containing the additive of the present invention can be used in any of the above where polyepoxides are commonly used.

An outstanding aspect of the compositions of the present invention is that they provide an opaque, smooth, white glossy surface upon curing, which is particularly advantageous for mold or mold operations. The compositions of the present invention can be used as injectables, surface coatings, pottings, capsule compositions and reddening agents.

Examples 1 to 42 below describe the formulation and use of additives whose ureido is terminal, and Examples 43 to 58 describe the formulation of additives whose terminal is amido.

Example 1

Agitators were equipped with 1980 g (1 mol) of polyoxypropylene polyamine and 180 g of urea (3.0 mol) having a molecular weight of about 2000 and a trademark of Zephamine D-2000, with 1.1 millieq. (Meq) of primary amine per gram. Into a suitable reaction vessel. The mixture was flushed with nitrogen and stirred at 130-134 ° C. under a nitrogen pad for 2 hours.

A second portion of 990 g (0.5 mole) of Jeffamine D-2000 was added at about 132 ° C. over 3 hours. The reaction mixture was held at 134 ° C. for 70 minutes, during which the mixture was vigorously stirred to wash the sublimate from the upper surface of the reaction vessel. The crude reaction product was stripped at 130 ° C./1.4 mmHg to obtain a viscose residue, which was 2.54% N and 0.01 meq total amine / g.

Example 2

Materials with bis (N-substituted ureido) termini were generally prepared according to the process of Example 1. 891 g of "Jepamine D-2000" was charged to the apparatus described in Example 1. 109 g of phenylisocyanate were added to the stirred polyoxypropylenediamine at about 55 ° C. over 45 minutes under a nitrogen atmosphere. The temperature was raised to 60 ° C. and the mixture was further stirred for 2 hours. The compound with the corresponding bis (N-phenylureido) terminal was recovered and analyzed as 2.2% N, 0.009 meq total amine / g. Various epoxy formulations using diglycidyl ethers of 4,4'-isopropylidene bisphenol were cured with various known polyamine curing agents to describe the benefits of the polyether ureide additive of the present invention. Where indicated, commercially available accelerators were used. Three drops of silicone liquid were added to each formulation to prevent pore and bubble formation. The gas was removed under vacuum and the formulation cured under the indicated conditions. In the examples the cured product was subjected to the Izod impact strength (ASTM nomenclature D-256), bending strength and flexural modulus (ASTM nomenclature D-790-66), tensile strength and the like of the American Society for Testing Material ASTM. Break point elongation (ASTM nomenclature D-638-64T), flexible temperature (ASTM nomenclature D-648-56) and strength (ASTM nomenclature 2240-64T) or strength Shore D tests were performed. The abbreviations pbw, psi and g in the table refer to parts by weight, pounds per inch ² and grams, respectively.

[Examples 3-5]

In this example, the epoxy resin was prepared by curing diglycidyl ether of 4,4'-isopropylidene bisphenol with methyl-bicyclo [2,2,1] heptene-2,3-dicarboxylic anhydride. The indicated amount of diurade prepared in 1 was added to a dimethyl aminomethyl substituted phenol accelerator to prepare. The resulting resin was poured into a 1/8 "panel and tested by ASTM described herein. The data are listed in Table 1 below for comparison purposes only.

TABLE I

1) “Nadic methyl anhydride” is available from Allied Chemical Corporation Morristown, N.J. Sells in 07960

2) DMP-10 is shown in Rohm and Haas, Philadelphia, Pa. Sold in 19105.

3) the product of Example 1

4) 2 hours at 100 ℃, 1 hour at 130 ℃, 3 hours curing at 150 ℃

[Examples 6-15]

The following examples show that resins containing additives according to the invention have unexpected thermal shock resistance.

Resins for the following examples were prepared according to the formulations shown in Table 2. Approximately 50 g of sample was washed with a 1 / 4-ring filter paper cut from Whatham 19 × 19 mm cellulose extraction thimble (outer diameter 1 (, inner diameter 3/8 ＂, thickness 1 / 6 ＂) was used to envelop.

The cane was formed on an aluminum milk test evaporator (5 cm in diameter x 1 cm in depth). The results are in Table 3 below.

TABLE 2

TABLE 3

Number of samples decomposed during the cycle

1) Nadic methyl anhydride

2) ＂DMP-10＂

3) the product of Example 1

4) Inferior: The oven is 160C (30 minutes), the bath is -40C (15 minutes), room temperature (15 minutes) and the decomposition is examined and if not constant, recycle to the oven.

5) All 10 samples were degraded after the cycle.

[Examples 16-18]

In this example, the epoxy resin was prepared by substituting 'Jepamine D-2000' with a diuraide additive in the same manner as in Examples 4 and 5. This example shows that the thermal temperature is considerably lower when using the “Jepamine D-2000” additive for the polyetherdiureide end additive of the present invention. Table 4 shows the formulations of Examples 16-18 with the corresponding thermoplastic temperatures.

TABLE 4

1) Nadic methyl anhydride

2) ＂DMP-10＂

3) Zephamine D-2000

4) Curing as in Examples 3-5

The alkyl-bicyclo [2,2,1] heptene dicarboxylic acid anhydride of the present invention and other commercially available anhydrides were used to exhibit the superior properties expected of the resins prepared according to the invention.

[Examples 19-21]

In this example, hexahydro phthalic anhydride was used with the benzyldimethylamine promoter as the curing agent. The amount of polyether diurade that has to be used to protect the thermal shock, prepared according to Example 1, is such that it would deteriorate other physical properties. Table 5 shows the formulations and properties of cured resins prepared with other curing agents.

TABLE 5

1) Prepared according to Example 1

2) Curing cycle: 2 hours at 125 ℃, 3 hours at 150 ℃

[Examples 22-31]

The following examples using the cured resins of Examples 19-21 are indicative of the reduced thermal shock resistance of resins prepared by another method compared to the resins prepared according to the invention. About 50 g of sample was used to wrap the scrubber as in Examples 6-15. The results of the test where 10 samples were used for each formulation are shown in Table 6 ¹⁾ .

TABLE 6

[Number of Samples Decomposed During Circulation]

1) Thermocycling: Check the oven at 160 ° C (30 minutes), bath at -40 ° C (15 minutes), room temperature (15 minutes), and disintegrate.

[Examples 32-41]

In the following examples, epoxy resins were prepared using phthalic anhydride as a curing agent and benzyldimethylamine as an accelerator. The formulations of these resins are shown in Table 7. The cured resin is subjected to a thermal shock test in accordance with the process of Examples 22-31. The results of this test using 10 samples per formulation are shown in Table 8. This example shows that the epoxy resin cured in accordance with the present invention provides improved thermal shock resistance over resins cured with phthalic anhydride.

TABLE 7

TABLE 8

[Number of samples decomposed during circulation ³⁾ ]

1) Curing cycle: 2 hours at 125 ℃, 3 hours at 150 ℃

2) Prepared according to Example 1.

3) Thermocycling: The oven is examined for decomposition at 160 ° C (30 minutes), for bath at -40 ° C (15 minutes) and at room temperature (15 minutes).

4) All 10 samples were decomposed after circulation.

Example 42

In this example, the unexpected selectivity of the additives of the present invention appeared. Anhydrous hardener was prepared as shown in Table 9 using the bis (phenyl urea) compound prepared in Example 2 as an additive.

TABLE 9

1) Nadic methyl anhydride

2) product of Example 18

3) ＂DMP-10＂

4) 3 hours curing at 125 ℃

The clear appearance of the mold after curing indicates that there are no improved properties obtained by quadranting the bis (phenyl urea) additive according to the invention.

Example 43

In this example a polyether diamido terminal additive for use according to the invention was prepared. 971 g (0.5 mole) of Zephamine D-2000®, 76.5 g (1.5 mole) of 90% by weight of water-soluble formic acid and 200 ml of toluene were added to a suitable reaction vessel equipped with a stirrer, a thermometer reflux cooler and a Dean-Strap trap. The mixture was poured into nitrogen, flashed and stirred at reflux under a nitrogen pad for 2 hours. The aqueous phase was separated on Dean-Starktrap. The crude reaction residue was stripped at 97 ° C./0.4 mmHg of a rotary evaporator to obtain a viscose residue. The result was 1.64% N and 0.07 meq total amine / g. In order to describe the advantages of the polyetherdiamide additive of the present invention, various epoxy formulations using diglycidyl ethers of 4,4'-isopropylidenebisphenol are cured with various known polyamine curing agents and described in Examples 3 to 5. Took the test.

[Examples 44-46]

In this example the epoxy resin cured the diglycidyl ether of 4,4'-isopropylidene bisphenol with methyl-bicyclo [2,2,1] -heptene-2,3-dicarboxylic anhydride and Example 43 The indicated amount of amide prepared in was added to the dimethylamino methyl substituted phenol accelerator to prepare. The resulting resin was imparted to a 1/8 "panel and subjected to the ASTM test indicated here.

The data are shown in Table 10 below for comparison purposes only.

TABLE 10

1) Nadic methyl anhydride

2) ＂DMP-10＂

3) product of Example 43

4) 2 hours at 100 ℃, 1 hour at 130 ℃, 3 hours curing at 150 ℃

[Examples 47-56]

The following examples show that resins containing additives according to the invention have unexpected thermal shock resistance. The resins prepared in Examples 44 to 46 were subjected to thermal shock resistance tests. About 50 g of sample was used to wrap the scrubber as in Examples 6-15. The results are in Table 11 below.

TABLE 11

[Number of samples destroyed during circulation ¹⁾ ]

1) Thermocycling: The oven is examined for decomposition at 160 ° C (30 minutes), for bath at -40 ° C (15 minutes) and at room temperature (15 minutes).

2) All 10 samples were decomposed in 3 cycles.

Example 57

In this example a polyether bis (benzamide) additive was prepared. Using the apparatus and process of Example 43, 1330 g (0.696 mole) of Zepazamine D-2000 Mk, 170 g of benzoic acid (1.393 mole) and 5 ml of benzene were charged to a suitable reaction vessel. The resulting mixture was flashed with nitrogen and stirred at reflux (156-240 ° C.) under nitrogen pad continuously with water (85% theory). Vacuum was slowly applied over 1 hour to facilitate removal of residual water. The mixture was stirred under vacuum (185 ° C./30 mm Hg) for another 1 hour. On cooling, a light brown viscose liquid phase reaction product consisting mainly of bis (benziamido) material was shown.

Example 58

In this example the unexpected selectivity of the additives of the present invention is shown. Anhydrous curing agent was prepared as shown in Table 12 using bis (benzamide) prepared in Example 57 as an additive.

TABLE 12

1) Nadic methyl anhydride

2) product of Example 57

3) ＂DMP-10＂

4) 3 hours curing at 125 ℃

The clear appearance of the mold after curing indicates that there are no improved properties obtained with the bis (formamide) additive according to the invention.

Claims (1)

An effective amount of additive consisting of a bisinal polyepoxide having an epoxide equivalent of 1.8 or more, a cured substituted bicyclic bisinal anhydride, and a polyether diurade or diamide having a terminal ureido or amido group and having a molecular weight of 2000 to 3000 Curable epoxy resin composition obtained by mixing.