DE1283840B - Process for the preparation of meltable and grindable, crosslinkable resins containing free epoxy groups - Google Patents

Description

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It is part of the known state of the art that, by their nature, they can be aromatic, aliphatic or cyclo-polyepoxy resins with organic, active hydrogen aliphatic, saturated or unsaturated and monomeric containing compounds which are a plurality of or be oligomeric. Such epoxy resins are epoxidized have active hydrogen atoms, to highly crosslinked diolefins, ζ. B. butadiene dioxide, hexadiene dioxide, vitamins, tough, infusible, and insoluble resinous 5-nylcyclohexenedioxide and dipentenedioxide and glycidic compounds Compositions react. dyl esters of polycarboxylic acids such as adipic azelaic

For example, the sebacic acid, dimeric and trimeric products described in the U.S. patent are unsaturated-2 506 486 described, thermosetting compounds of fatty acids, phthalic, isophthalic, terephthalic or Settlements by reacting 1 mole of a diglycidyl hexahydrophthalic acid.

ethers of a dihydric phenol with 0.2 to 1 mol io. Further epoxy compounds are glycidyl ethers alieines dihydric phenol produced. The obtained, phatic, polyhydric alcohols, such as ethylene glycol, highly cross-linked products have high tensile strength - propylene glycol, hexylene glycol, diethylene glycol, di-glycol and good resistance to alkalis and other propylene glycol, polyethylene glycols, polypropylene bases. These thermosetting resins are called glycols, polybutylene glycols, dihydroxyalkyl ethers by described horn-like and tough. They should be shockproof 15 dihydric phenols, glycerine or trimethylol and can propane without breaking, tearing or flaking off.

cut, turned, sawn or in any other way are particularly preferred epoxy compounds

will be working. Polyglycidyl ethers of polyhydric phenols, which by

It has now been found that fusible and conversion of an epihalohydrin with a grindable, crosslinkable, free epoxy groups containing ao polyhydric phenol is formed. Polyglycidyl ethers can be produced with tend resins if they are produced at a tem- low molecular weight if the temperature is below 175 ° C, preferably at 75 to a dihydric phenol with an epihalohydrin 175 ⁰ C, a polyepoxy compound that has more than one in excess of epihalohydrin under Ver-Epoxygruppe per molecule contains, with an organic twist of an alkali as a condensation and de-compound, which is converted at least two active hydrogen hydrohalogenating agents. The Veratome contains per molecule that react with the epoxy group ratio of the reactants is 1 mol of dihydric polyepoxy compound, in the ratio of total phenol to 2 to about 10 mol of epihalohydrin 1 epoxy equivalent to about 0.3 to 0.8 active water and about 2 equivalents Alkali. Polyglycidyl substance equivalents of the active hydrogen-containing ethers with a slightly higher molecular weight are converted to organic compounds up to the gel point using less than 2 mol of epihalogen and then the reaction mixture to at least hydrin (1.2 to 2 mol) to 1 mol of dihydric phenol 25 ⁰ C below the reaction temperature and an amount of alkali that cools that of the EpiTemperature used. halohydrins is approximately equivalent.

As in "Principles of Polymer Chemistry" by These polyglycidyl ethers contain dihydric phenols-P. J. F1 or y, Cornell University Press (1953), pp. 47, 35 th more than one to about two 1,2-epoxy groups shown, the gel point occurs at a nonlinear per molecule.

For this invention, polyglycidyl ethers can have a second stage in the course of the polymerization. The valuable phenol with a wide range of mole condensate suddenly changes from a viscous liquid weight and melting point to an elastic gel. Before the gel point is 40 den. The molecular weights can range from 222 to approx. Beyond the gel point temperature range up to approximately 125 ^° C. However, the polyglycidyl ethers, which are no longer absorbed into a liquid, have molecular melts and are completely soluble, even in solvents, no longer weighing from about 340 to about 1000. The gel point of the Inventions 45 have melting points of about 0 to about 75 ⁰ C. contemporary products is as the one reaction point The dihydric phenols from which the poly-

defined that the reactants, when derived from a glycidyl ether, are bivalent Plate are no longer converted to liquid phenols, the two phenolic hydroxyl groups are fusible and contained in hot dimethylformamide and are free from other groups that are not are more completely soluble. React 50 times with epoxy groups. Examples

As soon as the gel point is reached, the reaction of such reactive groups are amine and tongue by cooling the reactants to a min-carboxylic acid groups. Suitable dihydric phenols least about 25 ⁰ C lower than the implementation, for example, ρ, ρ'-dihydroxydiphenylpropane, getemperatur lying temperature canceled. Mentioned in the general residential bisphenol A, resorcinol, 1,4-Dihygemeinen the reactants to below 5O ⁰ C 55 droxynaphthalin, ρ, ρ'-dihydroxydiphenylmethane, di-, and preferably cooled to 25 ⁰ C or lower. hydroxydiphenyl, dihydroxydiphenyl sulfone and chloro-

The resinous compositions obtained entranted and brominated derivatives such as tetrabromo and retain unreacted tetrachloro-bis-phenol-A, although they are cross-linked.

Epoxy groups and can be made into finely divided powders The organic, active hydrogen-containing

be pulverized. These powders have 60 compounds that are necessary for the process according to the invention Small particle sizes and the existing ren used have substituents that are not min converted epoxy groups as reactive fillers, at least two active hydrogen atoms per molecule, Keep reactive thickeners or thixotropic agents. The active hydrogen containing substances or molding powder found use. tuents are phenolic hydroxyl groups, carbon

Those for use in this invention in acid, sulfonamide or amino groups. The organitracht Coming epoxy compounds are any compounds containing active hydrogen low molecular weight polyepoxy compounds that are more polyhydric phenols, aliphatic and aromatials have one 1,2-epoxy group per molecule. You see polycarboxylic acids, arylsulfonamides, aliphatic

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and aromatic primary and secondary polyamines, heating above the gel point can lead to hard,

Aminophenols, amino acids and phenolic acids. lead horn-like, crosslinked resins.

The polyhydric phenols which are reacted in the organic The preferred reactants are diepoxy resins and processes according to the invention with the polyepoxy compounds containing 2 moles of active hydrogen comprise the 5 compounds listed above. When these reactants are in proportions dihydric phenols, from which the polyglynes are derived from 1 epoxy equivalent to about 0.3 to cidyl ethers of dihydric phenols. Other polyhydric phenols suitable for use with approximately 0.8 active hydrogen equivalents are, for example, Novas, practically all of the active hydrogen lacquers have the reaction products of phenol and substituents reacting when the gel point is reached. Represent formaldehyde, as well as pyrogallil, phloro- io. Another crosslinking (between the epoxy groups glucine or trihydroxynaphthalene. When used and the hydroxyl groups that have arisen in the course of various combinations of epoxy compounds) takes place slowly and polyvalent phenols can the function- can easily be checked,
Small, crosslinked products of this invention can be produced with a reaction between a polyepoxy compound of a wide range of physical and chemical formation and a multiply active hydrogen. holding organic compound runs at increased

Polycarboxylic acids used according to the invention are crosslinked to a temperature without a catalyst

for example oxalic, malonic, amber, glutaric, product. Reaction temperatures above 150 ° C

However, adipic, pimelic, corkic, azelaic acid, dimerized acids are sometimes used to initiate the reaction.

and trimerized, unsaturated fatty acids, phthalic, 20 required. After the reaction has started, can

Isophthalic, terephthalic, trimellitic or trimesic acid. they become exothermic and fairly rapid, so it does

Arylsulfonamides, which is very difficult in the invention, the reaction at the beginning

Processes can be implemented, Ben-Gelpunkt are to be aborted. It is then more beneficial to do this

zolsulfonamid, p-toluenesulfonamid or naphthalene conversion between epoxy groups and active ones

sulfonamide. 25 hydrogen atoms with a basic catalyst

Aliphatic and aromatic primary and secondary to catalyze, so that the reaction rate

där amines which can be controlled in the process according to the invention.

Can be used as reactants are Me catalysts that can be used for this reaction

thylamine, propylamine, butylamine, 2-ethylhexylamine, are basic catalysts, such as the so-called

Decylamine, dodecylamine, hexadecylamine, octadecyl- 30 Bronsted bases, which represent proton acceptors,

amine, aniline, benzylamine, N, N, -Dimethyläthylen- Such catalysts are amines, quaternary ammo

diamine, Ν, Ν'-diethylethylenediamine, piperazine, N-Me- niumverbindungen ^ N-AlkylcarbonsäureamidejN, N-Di-

thyl - N '- butyloctylenediamine or N, N' - dimethylalkylcarboxamides, dialkyl and tetraalkylsubsti-

phenylenediamine. Other suitable amines are ethylene-tuierte ureas and thioureas or alkyl

diamine, propylenediamine, diethylenetriamine, tetra-substituted guanidines. Depending on the specially

ethylene pentamine or m-phenylenediamine. The catalyst used can vary the amount of catalyst

preferred amines are aliphatic or aromatic 0.001 to 0.2 moles per mole of that initially used

primary amines ranging from 1 to about 20 carbon epoxies. Preferably, however,

atoms and contain only one amino group, as well as about 0.002 to about 0.05 mol of catalyst

disecondary amines containing 1 to about 20 carbon 40 det. The preferred catalysts are the N ₅ N di-

atoms and contain only two amino groups. alkylcarboxamides and the tertiary amines, from

Also compounds that use mixed active water- which use approximately 0.02 moles per mole of diepoxide

Have substance substituents are to be invented.

proper procedures useful. Such compounds include the reaction is carried out at a temperature o, m, and p-aminophenyl, phenol, salicylic, 45/2 of 175 ° C, preferably at about 75 to m-hydroxybenzoic, p-hydroxybenzoic acid, Glycine, about 175 ⁰ C carried out. The lowest Tempe-alanine, phenylalanine hydroxyphenylalanine, aspartic, raturbereich is between 100 and about 125 ⁰ C. or glutamic acid. When polyfunctional, aliphatic amines, such as

In the production of friable, epoxy compounds, diethylenetriamine, triethylenetetramine or tetra-containing Gels must have the upper limit of the reac- 5 ° ethylene pentamine for the process according to the invention ratio - about 0.8 active water - used as Η-active organic compounds atoms per epoxy equivalent - are adhered to, the reaction can be carried out without the use of heat so that the formation of tough, hard, can be carried out in the heat from the outside at room temperature, curable compositions that are not too fine This is especially true when about 0.6 to Powders can be ground up is prevented. 55 approximately 0.8 active hydrogen equivalents of the amine Care must also be taken that the reaction with 1 epoxy equivalent of the polyepoxy compound is reversed Gel point is canceled, especially then, are set. However, as soon as the gel point is reached when one or both of the reactants is more than two functional, it is generally more advantageous to use the reactants contain nelle groups per molecule. As indicated above, cool below about 5 ° C to allow the reaction can give epoxy resins, which more than two epoxy 60 is canceled, and the products at the low groups per molecule contain, and compounds that store temperature so that a further reaction contain more than two active hydrogen atoms, with- is prevented.

to each other to friable, functional gels under The inventive reaction between Epoxyder The prerequisite is that the rearrangements and active hydrogen can be carried out in the solution setting at the beginning of the gel point. Such solvents will. When these are more functional reactants: aromatic hydrocarbons, ketones, ethers are used, the gel point has already been reached, esters and mixtures of such solvents. In the before all active hydrogen atoms have reacted. in most cases, however, it is desirable that the

The functional gels can be intimately networked, functional compositions of this distributed form detection of solvents are free. Since it is difficult to mix with epoxy resin curing agents, is to solvent from a crosslinked product. If these mixtures are heated and removed under pressure, If the implementation of the polyepoxy compounds will be used, shaped structures will be created, dung with the repeatedly active hydrogen containing 5 The finely divided, prepared according to the invention, Tending, organic compound therefore preferably functional gels have proven to be reactive fillers carried out in the absence of solvents. and especially as reactive thickeners for

Epoxy resins found useful in practicing the inventive method. Be known Epoxy resins fillers can be added to the handsator put together in the reaction vessel io habung properties of the resins before curing and the two reactants can be used prior to adding the physical properties of the cured resins of the catalyst can be dissolved together, or modified. The fine die obtained according to the invention active hydrogen-containing compound can form dispersed compounds when they are epoxy resins the epoxy resin and the catalyst are partially added, colloidal dispersions that are clear are set. The reactants should be stirred, 15 and only slightly hazy. These dispersions until the exothermic reaction has ended; thereby have excellent thickening properties that to ensure that the temperature in the their usability in protective coatings and for is kept within the limits defined above. Increase after loading binder. Except the functional ones The end of the exothermic reaction is stirring gels thixotropic or thickening the dispersions no longer necessary, and the implementation up to 20 properties compare, they also take part in the Gel point can take part in the curing reaction itself at the same temperature as the epoxy groups in was used initially, with a lower or the gels in the same way with the added at a higher temperature. Curing agents react like the epoxy groups in In general, after the exotherm has ceased, the resins. The hardening reaction is caused by the Implementation of the stirrer preferably from the presence of these functional gels is not made difficult, Action vessel taken out, and this is in and in some cases, especially in the case of foil aneinen When the oven is heated to the desired temperature, the hardening reaction is even postponed. Resin samples are then periodically corrected for this. As the functional gels attached to the hardening container taken and react to their infusibility and not just as inert substances are present on a hot plate and their solubility in the mixtures, the mechanical tested in hot dimethylformamide. If the properties of the cured product are not spoiled the infusibility and insolubility worsens.

is sufficient, the container is removed from the oven. The invention is illustrated by means of the following

taken, and the reactants are explained on examples below. Parts mean 50 ^° C. by ^{weight, preferably cooled to 25 °} C. or below. 35 parts.

After cooling, the reaction products can be The epoxy equivalent weights of the starting epoxy

using known methods to form a fine powder and functional gel products be ground up. were after that of Jung and Kleebert,

The method according to the invention can also be described in Kunststoffe, Vol. 51, p. 714 (1961) Presence of a wide variety of fillers that determines 40 functioning. Before the epoxy analysis of the To modify the crosslinked, functional gel products obtained, they were powdered nellen product are carried out. Such gels in neutralized methyl ethyl ketone overnight Fillers include finely divided metals, metal oxides, soaked to swell them. The swollen fabrics Metal salts, clays, silicates, organic and inorganic were then analyzed Ganic pigments, thermoplastic and by heat 45 τ »· · 1 1

curable resins, etc. B e 1 s ρ 1 e I I

Thermosetting compositions are placed in a suitable container equipped with a thermo

expediently in the shape or form of a meter, a stirrer and an external heat source, which they occupy in the crosslinked state. Example- was equipped, 393.4 parts of a diglycidyl manner, as long as they are 50 ethers of the ρ, ρ'-dihydroxydiphenylpropane with a still thermoplastic, crosslinkable compounds can be molded into various structures by epoxy equivalent weight of 196.7 and 114.2 parts poured them into molds, filled with ρ, ρ'-dihydroxydiphenylpropane. Extruded through heating sheets or applied as coatings, the temperature was raised to 120 ⁰ C. After being. The compounds are then cured by heat as the diphenol had dissolved in the epoxy resin, and as a cast article, foil or coating, 1.7418 parts of N, N-dimethyl were added to the reactants. The potting can be given for veracetamid. The mixture was heated to 125 ⁰ C various applications advertising carried out by machine heated and held for 3 hours at this temperature, the. In general, heat curable The container was then changed with the reactants, but according to compositions only by physical methods that the stirrer and thermometer removed and not by being subjected to chemical reactions in a heated oven (125 ° C) by having them turned 60 will. represents. Samples were taken periodically from the container and tested for infusibility for functional, heat-curable compounds in a hot plate and for insolubility in and can be tested in the thermosetting state chemically hot dimethylformamide. After 20 hours, react as it corresponds more reactive epoxy groups 65 hot in 125 ⁰ C oven was keeping the reaction product. The produced according to the invention functions. It was then removed from the oven; gels can be whole and cooled with ice water by known methods. The obtained functional can easily be divided into fine powder. In this fine gel had an epoxy equivalent weight of 836 and

10

20th

a softening point of 55 to 65 ⁰ C determined on a Fisher melt block.

The functional gel product was broken into small pieces in a mortar and then pestle Milled in a ball mill for 50 hours. A finely ground powder was obtained from which one a larger part passed a No. 325 sieve.

Example 2

Following the same procedure as in Example 1, 394.3 parts of the diglycidyl ether used in Example 1 were reacted with 137 parts of ρ, ρ'-dihydroxydiphenylpropane using 1.7439 parts of Ν, Ν-dimethylacetamide as a catalyst. After 3 hours heating at 125 ° C with stirring and after 17 hours, heating in an oven at 125 ⁰ C, the reactants were gelled. After cooling, the functional gel product showed an epoxy equivalent weight of 1159 and a softening point of 70 to 80 ⁰ C. This product, as described in Example 1 pulverized. The powder obtained was so fine that a major portion passed through a No. 325 sieve.

Example 3

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Following the procedure of Example 1, 393.4 parts of the diglycidyl ether described in Example 1 and 159.8 parts of p, p'-dihydroxydiphenylpropane were reacted using 1.7460 parts of Ν, Ν-dimethylacetamide as a catalyst. After the reactants 2.35 hours long long hot in a 125 ⁰ C with stirring to 125 ° C and 16 hours the oven had been heated, the mixture was gelled. After cooling in ice water to room temperature, the gelled product was broken into small particles in a mortar with a pestle. The product showed an epoxy equivalent weight of 1504 and a softening point of 70 to 8O ⁰ C. This product was prepared as described in Example 1 ground to a fine powder; the results were comparable to those obtained in Example 1.

Example 4

Following the same procedure as in Example 1, 393.4 parts of the diglycidyl ether described in Example 1 were reacted with 182.6 parts of p, p'-dihydroxydiphenylpropane using 1.7428 parts of NN-dimsthylacstamide as a catalyst. After the mixture hot 2.23 hours with stirring to 125 ° C and 14.5 hours einsm 125 ⁰ C furnace had been heated, it gelled. The gelled product was then cooled to room temperature with ice water and ground in a mortar with a pestle. The product had an epoxy equivalent weight of 2382 and a softening point of 80 to 90 ° C. As described in Example 1, it was ground to a very fine powder.

Example 5

According to the same working white as in Example 1, 393.4 parts of the diglycidyl ether described in Example 1 were reacted with 91.32 Tsilsn of p, p'-dihydroxydiphenylpropane using 1.7453 parts of Ν, Ν-dimethylacetamide as a catalyst. After 3 hours heating under stirring at 125 ° C for 24 hours and heating in an oven at 125 ⁰ C, the product had gelled. It was cooled to room temperature in ice water and broken into small particles in a mortar with a pestle. The gelled product had an epoxy equivalent weight of 696.7 and a softening point of 60 to 70 ° C. The product was then ground to a very fine powder using the procedure described in Example 1.

In order to demonstrate the suitability of the comminuted, functional gels of this invention as thickeners for epoxy resins, the products of the preceding examples were mixed with a diglycidyl ether of ρ, ρ'-dihydroxydiphenyl propane (epoxy equivalent weight: 197) and cured with tetraethylene pentamine (TÄPA) according to the following procedure : The functional gel and the diglycidyl ether were ^{mixed on a hot plate (plate temperature: 200 °} C.) with stirring for 4 minutes. The hardener was stirred in and the mixture was spread in a 5.08 cm long strip across one end of a glass plate. The glass plate was then placed vertically so that the strip with the mixture was on top. The amount of mixture that ran off before the mixture became tack free and cured was observed. The proportions of reactants used and the observations were as follows:

mixture Functional gel Diglycidyl ether TÄPA Maximum expiration Non-sticky after A.
B.
C.
D.
E. 1-2 parts
2 - 2 parts
3-2 parts
4-2 parts
5-2 parts 8 parts
8 parts
8 parts
8 parts
8 parts ITeil
ITeil
ITeil
ITeil
ITeil 12.7 cm
2.54 cm
12.7 cm
17.8 cm
10.2 cm 5.6 hours
4 hours
7 hours
7 hours
7 hours

All of the above films were fully cured after 5 days at room temperature.

Example 6

Following the procedure of Example 1, 1.899 parts of a diglycidyl ether of p, p'-dihydroxydiphenylpropane with an epoxy equivalent weight of 189.9 with 570.7 parts of p, p'-dihydroxydiphenylpropane using 8.71 parts of Ν, Ν-dimethylacetamide as a catalyst implemented. After the mixture had been heated for 2.5 hours with stirring to 125 ⁰ C and for 26 hours in an oven at 125 ° C, it gelled. The gelled product was taken out of the oven and cooled to room temperature in ice water. As described in Example 1, it was ground to a fine powder. The product had an epoxy equivalent weight of 932. The finely divided gel was mixed with various epoxy resin curing agents listed below. The mixtures were divided into three

809 639/1956

Claims (1)

9 10 passed through a mineral grinder thoroughly chilled with ice water. After cooling down that had mixed and then filled into a mold that is functionally gel product of an epoxy equivalent weight 150 ⁰ C had been preheated. The shape was then of 727.5. placed in a hydraulic press where the mixture was The functional gel ^{product was broken into small particles and in a mine at 150 0} C for 1 minute under a pressure of 5 ralienmahlwerk 70 kg / cm ^{2 was} set. The resulting molded shapes were then ground in a ball mill for 50 hours. Discs were hardened and had good strength. A finely ground powder was obtained from which speed. a larger portion passed through a No. 325 sieve. ■ The mixtures of functional B e "s η i 18 The gel and hardening agents were as follows put together: According to the same procedure as in example 7 389.4 parts of that described in Example 7 were obtained Mixture A diglycidyl ether of p, p'-dihydroxydiphenylpropane Functional gel 93.2 parts ^ 3 _{657 parts n} _Butylamine implemented. After 114- 2,4-Diammotoluene 1.5 parts _{15 hour} heating to 125 ° C were the reactants Mixture B gelled. The networked, functional product had a Functional gel 93.2 parts epoxy equivalent weight of 369 and an extension Tris (hydroxymethyl) aminomethane .. 3.0 parts chung point from 30 to 40 ° C. The product was, Mix C lightly after cooling to 0-5 ° C Functional gel crush 93.2 parts a ° to a fine powder. m-phenylenediamine; 1.4 parts of the patent claims: Funkkmelles Gel 93.2 parts ^L Method of making meltable and BFs monoethylamine 2.0 parts of grindable, crosslinkable, free epoxy groups -p, ρ 95 containing resins, thereby marked- lsc ung _., net that one can at a temperature below Functional gel 93.2 parts _γοη ' _{preferably at} 75 to 175 ⁰ Ω one Benzophenontetracarbonsaure- polyepoxy compound that has more than one epoxy ni7u -l'i '"" · « 'TS: contains group per molecule, with an organic BF ₃ -Monoathylamm 0.5 parts _{3o Ver} f _{ηαυη% the} ^^^ _{two active (} f water contains ο- · 1 7 substance atoms per molecule, which ^{react with the epoxy e} * ^s P ^{J e} groups of the polyepoxy compound, in a suitable container with a thermal ratio of 1 epoxy equivalent of the polyepoxymeter, a stirrer and an external heating source was equipped with about 0.3 to 0.8 activated water, 778.8 parts of a diglycidyl 35 substance equivalents of the active hydrogen enthalether of ρ, ρ'-dihydroxydiphenylpropane with a tendency organic compound to the gel point epoxy equivalent weight of 194.7 and 171.2 Parts reacted and then filled the reaction mixture on a Paratoluenesulfonamid. The temperature was increased at least 25 ⁰ C below the Umsetzungsauf 125 ° C. After the p-toluenesulfone temperature cools down, the amide had dissolved in the epoxy resin, the 4 ° 2. Process according to claim 1, characterized by reacting 3.48 parts of N, N-dimethylacetamide, was drawn as active hydrogen shocked. The organic compounds containing reactants were heated to 125 ° C. for 3 hours with constant stirring. The container turns the at least one phenolic hydroxyl, which was mixed with the mixture after the stirrer and a carboxylic acid, a sulfonamide or a thermometer had been removed, into an amino group. placed oven heated to 125 ° C. From the container 3. The method according to claim 1, characterized in samples were taken periodically and recorded on the that diglyci- Infusibility on a hot plate and on dyläther des ρ, ρ'-dihydroxydiphenylpropane and the insolubility in hot dimethylformamide as organic, active hydrogen containing checked. After 3 hours of heating in the 125 ⁰ C 5 ° compound ρ, ρ'-dihydroxydiphenylpropane or the mixture was gelled in a hot oven. The gelled adipic acid or p-toluenesulfonamide or butyl Product was taken out of the oven and used amine.