DE1520897B2 - Process for the production of an epoxy ether - Google Patents

Description

Examples of the methylol-substituted phenols described above include:

2,2-bis (3-methylol-4-hydroxyphenyl) propane, 2-methylol-1,4-dihydroxybenzene, 2,6-dimethylol-1,4-dihydroxybenzene, ⁵

2- (3-methylol-4-hydroxyphenyl) -2- (4-hydroxyphenyl) propane,

2,2-bis- (3-methylol-4-hydroxyphenyl) pentane, 2- (3-methylol-4-hydroxyphenyl) -2- (3-tertiary-

butyl-4-hydroxyphenyl) butane, ¹⁰

2,2-bis (3-methylol-4-hydroxyphenyl) -

pentanoic acid,
1,1,2,2-tetrakis (3-methylol-4-hydroxyphenyl) -

ethane,
1- (3-methylol-4-hydroxyphenyl) -1,2,2-tris- ' ⁵

(4-hydroxyphenyl) ethane,
Bis (3-methylol-4-hydroxyphenyl) sulfide, bis (3-methylol-4-hydroxyphenyl) sulfone, bis (3-methylol-4-hydroxyphenyl) methane and methylol-substituted phenol-formaldehyde resins. ^20th

Other examples are those of the formula:

O _f2 ° ^H

OH

HOt

Cl

ei — c — ei

OH

CH ₂ OH

H
C ₃ H ₇ pa CH ₂ OH

HO

C ₃ H ₇ ^Cli ₃ C 3 H ₇

HO

CH ₂ OH

OCH ₃

^ X

CH ₇ OH

CH-

y ν

OH

3 °

35

40

45

OCH,

HO

CH

CH ₂ OH ⁵ ° <^ - 0H CHOH ⁵⁵

CH,

CH ₂ OH

6o

// V

HO

CH ₇ OH

-OH

CH ₇ OH

HO

/ V

-OH

CH ₂ OH

C-C = C CH, OH

SCH ₃

HO

CH ₇ OH

OH

The methylol-substituted phenols described above can be prepared by various suitable methods getting produced. They are preferably made by reacting the unsubstituted Phenol with formaldehyde or a substance called formaldehyde released in the presence of an alkaline catalyst. Formaldehyde is preferably in the form an aqueous solution such as the usual 37% formalin solution applied. The formaldehyde and Phenols are preferably combined in such amounts as about 1 mole up to a 5 to 10% excess Formaldehyde for each ring carbon atom to be converted. So are the monomethylol substituted Products obtained by using reactants on a mole per mole basis, while the dimethylol substituted products are obtained using 2 moles Formaldehyde per mole of phenol.

The alkaline catalysts used as reactants are preferably the alkali or Alkaline earth hydroxides and especially sodium hydroxide. These catalysts are generally used in amounts from about 0.1 to 10 percent by weight of the reactants.

Solvents can be used in the reaction if desired. Suitable solvents are those that are solvents for the phenols such as methanol, ethanol, water-alcohol mixtures and ketones. The amount of solvent used changes depending on the concentration and the reaction participants. Generally, the solvent makes up from 10 to 60 percent by weight of the Respondents off.

The temperatures used during the reaction can vary depending on the reaction rates desired. The reaction takes place slowly at room temperature or below. Faster speeds can be achieved by applying can be achieved by heat. Suitable reaction

Speeds (a few minutes to several hours) are obtained by using temperatures in the range of about 50 to 100 ^° C.

After the reaction, the alkaline catalyst can be neutralized by adding acidic substances, such as dilute sulfuric or hydrochloric acids, and the solvent can be removed by distillation.

Substituted methylol groups such as —CHOHR groups are also understood as methylol-substituted, where R is preferably a hydrocarbon or substituted hydrocarbons such as —CHOHCl ₃ , —CHOHCH = CH ₂ . These substituted phenols are obtained by replacing the formaldehyde in the above procedures with a suitable aldehyde such as acetaldehyde, acrolein and chloral and using more severe conditions such as higher temperatures.

According to the invention, the epoxy ethers are obtained by reacting the methylol-substituted ones described above Phenols with the epoxy-forming substances, such as halogen-epoxy-substituted alkanes and dihalo-hydroxy-substituted alkanes, preferably in the absence of water. The expression "Halogen-epoxy-substituted alkane" refers to those alkanes with a 1,2-epoxy group (otherwise known as a vicinal epoxy group) directly to a halogen-bearing one Carbon atom bonded, such as epichlorohydrin, epibromohydrin, 1,4-dichloro-2,3-epoxybutane or 1-chloro-2,3-epoxypentane. The term "dihalo-hydroxy-substituted Alkanes «refers to those alkanes with a number of 3 carbon atoms, one of which is attached to a halogen atom, the closest a hydroxyl group and the last a halogen atom, such as 1,3-dichloro-2-hydroxypropane, 2,4 - dibromo - 3 - hydroxypentane, 2,3 - dichloro - 3 - hydroxybutane, etc. Epichlorohydrin is given special attention because of its low cost and because of the superior properties of the epoxies obtained therewith.

As already stated, the reaction is preferably carried out in the presence of only small amounts of water carried out. This can be achieved by adding the epoxy forming material to the phenolic mixture adds, the mixture is allowed to stand to form an aqueous and organic phase and then the aqueous phase discarded.

The amount of polyhydric phenol and epoxy-forming substance in the reaction will vary depending on the the type of product desired. If simple monomeric types are desired, the phenol and the epoxy-forming material is preferably reacted in chemically equivalent ratios of 1: 2 to 1:10. If high molecular weight hydroxyl-containing products are desired, the epoxy-forming substances are used used in lesser amounts and the ratio varies from 1: 1.1 to 1: 2. "Chemical equivalent" refers here to the amount that is needed to provide an OH group for each epoxy group ', ·

Higher molecular weight products from the methylol-substituted dihydric phenols and epichlorohydrin by changing the proportions of the reactants as indicated above are preferred those of the formula

J Ό 'CH ₂ CH-CH ₂ -I-OR-OCh ₂ CHCH ₂ -) OROCH ₂ CH CH ₂

where R is a methylol-substituted divalent aromatic radical and η is an integer from 0 to 5.

The desired alkalinity is obtained by adding basic substances such as sodium or Potassium hydroxide. The alkali is used in at least chemically equivalent amounts, e.g. B. a Moles per phenolic OH group and preferably in a slight excess of up to 5%.

The above reaction is preferably the mixture to temperatures of approximately 50 60 carried out by heating to 150 ⁰ C and in particular of about 125 ° C. Atmospheric, super-atmospheric, or sub-atmospheric pressure can optionally be used.

The water formed during the reaction can be removed during or at the end of the reaction. When the reaction is complete, the water and excess reactants will be like the Excess of halogen-epoxy-substituted alkanes, preferably removed by distillation and the Residue that remains, then treated with an appropriate solvent, such as benzene, and used for Removal of the salt filtered. The remaining product can then be purified by suitable methods like extraction or distillation.

The epoxy ethers obtained according to the invention are liquid or viscous liquids to solids. They have more than one epoxy group per molecule and are essentially free of chlorine, ie contain less than 1 to 2% chlorine. In addition to the active epoxy groups, these ethers have at least one still reactive methylol group that is capable of further conversion. The Epoxyäther according to the invention are soluble and generally contractual in most solvents such as ketones, alcohols and liquid hydrocarbons, ¹ 'borrowed with many synthetic oils and resins.

The preferred epoxy ethers are the glycidyl ethers of phenol of the formula

HO

R ₁ R ₁

where X is a divalent radical with elements only from the group consisting of hydrogen, carbon, halogen, sulfur and oxygen, at least one R is a methylol or alcohol-containing group, with the other R and Ri as a member of the group consisting of hydrogen, hydrocarbon radicals, alkoxy radicals and Alkoxycarbonyl radicals with not more than 12 carbon atoms.
For certain applications it is sometimes desirable to have higher molecular weight epoxy resins. Such products can be obtained by changing the amount of methylol-substituted polyhydric phenol and halogen-epoxy-substituted alkane in the alkaline

Medium as described above, or by reacting the above-described epoxy resins with polyepoxides or polyvalent hydrogen-containing compounds. In this case they react polyvalent hydrogen-containing compounds with the epoxy group

—C-

-C-C

to a

OH

—C — C — C group.

In a preferred embodiment, the invention provides polyepoxides, the glycidyl ethers of methylol-substituted polyhydric phenols and especially those of the formula

CH ₂ - CH - CH ₂ --OR - OCH ₂ CHCH ₂ --OROCH ₂ - CH CH

where at least one R contains a methylol-substituted, divalent, aromatic radical and the other Rs are dissimilar aromatic radicals and χ is an integer from 0 to 10. Of particular importance are those of the formula described above, where R is a substituted or unsubstituted polynuclear aromatic radical.

Polyhydric phenols used for this purpose can be any of the polyhydric ones described above Phenols "which have been used to prepare the methylol-substituted phenols, for example Resorcinol, catechin, hydroquinone, methylfesorcinol, polynuclear phenols such as 2,2-bis (4-hydroxyphenyl) propane and l, l, 2,2-tetrakis (4-hydroxyphenyl) ethane.

The epoxy ethers prepared according to the invention and their higher molecular weight derivatives can via the Epoxy group can be polymerized into valuable products. You can use it alone or with other polyepoxides are polymerized in a variety of different proportions, for example in amounts of other epoxies between 5 and 59 percent by weight. The polyepoxides, which with the invention Epoxies produced can be copolymerized, include glycidyl polyethers of polyhydric phenols, which can be obtained by reacting polyhydric phenols such as bisphenol or resorcinol with an excess of chlorohydrin such as epichlorohydrin, polyepoxy polyethers, which are obtained by Reaction of an alkane polyol such as glycerol or sorbitol with epichlorohydrin and dehydrohalogenation of the product obtained, polymers made from ethylenically unsaturated polyepoxides have been, such as allyl glycidyl ether alone or with other ethylenically unsaturated monomers and Polyepoxy polyethers obtained by reacting a polyhydric alcohol or polyhydric phenol obtained with one of the polyepoxides described above. The glycidyl polyethers of polyhydric phenols, obtained by condensing polyethers of polyhydric phenols with epichlorohydrin, such as described above are also called "ethoxylin resins" designated.

A wide variety of hardening agents can be used in practicing the above homopolymerization and copolymerization described. Such agents include carboxylic acids or -Anhydrides such as oxalic acid, phthalic anhydride, Friedel-Crafts metal halides, such as aluminum chloride, zinc chloride, iron (III) chloride or boron trifluoride, as well as its complexes with ethers, acid anhydrides, ketones and diazonium salts, phosphoric acid and their partial esters including n-butyl orthophosphate, diethyl orthophosphate and Hexaäthyltetraphosphat, amino compounds such as triethylamine, ethylenediamine, diethylamine, dicyandiamide, Melamine and salts of inorganic acids such as zinc fluoroborate, potassium persulfate, nickel fluoroborate, Copper fluoroborate, selenium fluoroborate, magnesium fluoroborate, tin fluoroborate, potassium perchlorate, copper (II) sulfate, Copper (II) phosphate, copper (II) phthalate, magnesium arsenate, magnesium sulfate, cadmium arsenate, Cadmium silicate, aluminum fluoroborate, iron (II) sulfate, iron (II) silicate, manganese hypophosphite, Nickel phosphate and nickel chlorate, hydrazides, polymercaptans, urea-formaldehyde and phenol-formaldehyde condensates and their mixtures.

Examples of other hardening agents are the aromatic amines, for example ^ y diaminediphenylmethane, ρ, ρ'-aminodiphenylsulfone, triaminobenzene, ortho-, meta- and para-phenylenediamine, methylenedianiline, diaminotoluene, diaminodiphenyl, diaminostilbene, 1,3-diamino-4-isopropylbenzene and 1,3-diamino-4,5-diethylbenzene and mixtures thereof.

Examples of other hardeners are the amino hydrogen-containing polyamides, obtained from polymeric unsaturated Fatty acids such as dimerized or trimerized linoleic acid by reaction with aliphatic polyamines such as diethylenetriamine and triethylenetetramine: other examples are the N-aminoalkylpiperazines such as N-Aminoäthylpiperazine, the acetone-soluble adducts of monoepoxides and polyamines, the acetone-soluble adducts of polyepoxides and monoamines, the acetone-soluble adducts of polyamines and unsaturated nitriles, aliphatic polyamines of the formula

H ₂ N (RNH) _n H.

where R is an alkylene radical and η is an integer of at least 1, such as diethylenetriamine, triethylenetetramine after tetraethylenepentamine as well as other amines such as N, N'-diethyl-1,3-propanediamine and tetra (1,3-dimethylpropylene) pentamine.

Other examples are the anhydrides such as tetrahydrophthalic anhydride, Methylnadic anhydride, methylendomethylene tetrahydrophthalic anhydride, chlorenedic anhydride, (1,4,5,6,7,7-hexachlorobicyclo (2,2,2) 5 - hepten - 2,3 - dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, Phthalic anhydride, succinic anhydride, maleic anhydride, octadecenyl succinic anhydride and their mixtures.

Other examples are the boron trifluoride complexes with aliphatic or aromatic amines such as

309 582/409

BF ₃ ethylamine, BF ₃ diethylamine and BF ₃ aniline addition products.

The amount of hardener used can be over a considerable range depending on the one selected Means fluctuate. The catalytic type hardeners are preferably used in about 0.1 to 10 percent by weight, based on the material to be hardened. With hardener with replaceable hydrogen, like amine hardeners taking part in the reaction, the amount of hardener used will vary by approximately 0.6 to 1.5 equivalents, i.e. an equivalent amount represents sufficient hardener to produce a to provide replaceable hydrogen atom for each epoxy group to be reacted. Generally will obtaining satisfactory cures in amounts ranging from 1 to 25 percent by weight of that to be polymerized Materials fluctuate.

The epoxy ethers and their high molecular weight derivatives can also be hardened via the hydroxyl group by adding appropriate amounts, e.g. B. 1 to 25 weight percent polybasic acids or anhydrides or polyisocyanates.

The curing is preferably carried out by mixing the curing agent with the polyether Temperatures from about 0 to 200 ° C. Hardening can be accelerated by heat, and if so Rapid hardening is desirable at temperatures of around 50 to 200 ° C. However, as above mentioned, one of the great advantages of the epoxy compounds prepared according to the invention is their ability to cure at low temperature. In this case, hardening is preferably carried out at temperatures carried out from about 0 to 60 ° C and especially at 20 to 50 ° C.

In some cases, especially when making castings, those are made in accordance with the invention Epoxy ethers are soft to brittle solids and it can be beneficial to use a diluent during of use to use. These diluents are preferably of the reactive type, d. H. those who take part in the reaction. Examples of these diluents are the monoglycidyl compounds such as the alkyl glycidyl ethers, for example butyl glycidyl ethers or aryl glycidyl ethers such as Phenyl glycidyl ether. Other examples are the glycidyl ethers of dihydropyranalkanols, acetonitrile, Acrylonitrile, as well as liquid polyepoxides such as diglycidyl aniline. These substances are preferred used in amounts from about 0.1 up to or above 30 weight percent.

It has surprisingly been found that with many of the above-mentioned diluents Diluent in moderate amounts does not destroy one of the outstanding properties, but enables it these properties without obtaining any harmful effect. This is shown in the examples on Shown at the end of the description.

Are the epoxy ethers or their higher molecular weight derivatives in the production of castings or If investment materials are used, the hardening agents and the epoxy are generally mixed together and then poured into the desired shape containing the electrical wires or device and then heating the mixture to harden.

The epoxy ethers prepared according to the invention and their higher molecular weight derivatives are special suitable for the production of surface coatings because of their fast hardening speed at low temperatures Temperatures. When using the products for this purpose, it is generally desirable that Epoxy resin and the curing agent with the desired solvents or diluents and optionally other film-forming substances, extenders, fillers or dryers to apply and then the so to apply the resulting mixture to the surface to be coated. With the epoxies on this one Film-forming substances that can be used in the process are drying oils such as wood oil, linseed oil, and dehydrated oils Castor oil and soybean oil, cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, Ethyl cellulose and its mixtures, vinyl polymers, such as polymers of vinyl chloride, Vinylidene chloride, acrylonitrile, acrylates, diallyl phthalate, ethylene, propylene, butylene, rubber-like polymers of butadiene and isoprene, coal tar, pine oil and asphalt and other types of bituminous materials. The coatings produced in this way can be cured at room temperature, or it heat can be applied to accelerate the hardening process.

The higher molecular weight hydroxy-containing derivatives of the epoxy resins described above are particularly ■ ( suitable for use in the production of coating compounds because it has the hydroxyl group or groups can be reacted with drying oil fatty acids or via the hydroxyl groups can be cured with compounds such as urea or polyisocyanates.

The epoxy resins and higher molecular weight derivatives prepared according to the invention can also be mixed with corresponding Quantities of hardeners used in the production of valuable adhesives and laminates will. In using these products for these purposes, it is generally desirable to use the epoxy resin to combine with fillers and hardeners and then an applicable liquid as an adhesive to be used for materials such as wood, plastic or metal.

In addition, the epoxy ethers prepared according to the invention can be used as stabilizers for various halogen-containing polymers and especially the vinyl halide polymers can be used. These .,·

Products can be used alone or in '<■ (conjunction with other stabilizers such as urea and thiourea derivatives as stabilizers. In most cases, the products are effective as stabilizers in amounts of from 1 to 5 weight percent of the polymer to be stabilized. The epoxides can use the halogen-containing polymer can be blended by any suitable method such as by dissolving the products in a suitable solvent or rolling them together on a suitable roller.

The epoxy ethers prepared according to the invention are particularly attractive for use in aqueous Systems where the methylol group or groups dissolve or emulsify the resin in water facilitate. This makes the ether valuable in the production of water-based coatings, Adhesives, impregnation solutions, impregnation compounds for the treatment of fabrics, paper and leather Granting improved properties.

To illustrate the implementation of the invention, the following examples are given. Of course the examples serve only to illustrate and not to restrict the particular compounds or

conditions mentioned therein. Unless otherwise stated, parts in the examples are parts by weight.

example 1

This example illustrates the preparation and some properties of a monomethylol substituted diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane of structure

0x1-0-0.2 vJ

CH ₃
C—
CH ₃

CH ₂ OH

VO-CH ₇ -CH

46 parts (0.2 mol) of 2,2-bis (4-hydroxyphenyl) propane are dissolved in 25.4 parts of methanol and 18 parts (0.222 mol) of a 37% formalin solution and 21.5 parts (0 , 1 mol) of a 20% strength aqueous sodium hydroxide solution was added. This mixture is heated ^{at 82 °} C. for approximately 20 minutes. The reaction mixture is then neutralized with dilute sulfuric acid and the methanol is removed by distillation. A 10 molar excess of epichlorohydrin is then added to the reaction mixture and the mixture is stirred at room temperature. The combined mixture is then left to stand at room temperature until the water phase has separated off. The organic phase is then removed and combined with 25 weight percent methanol. This solution is heated to reflux and concentrated sodium hydroxide solution added to give a 5% excess over the phenol. After the reaction has ended, the excess epichlorohydrin and methanol are removed. The product obtained is then dissolved in methyl isobutyl ketone and filtered to remove the salt. The mixture is then distilled at 150 ° C. and 2 mm to remove the ketone solvent and to obtain the desired viscous, thick, substantially colorless resin having the above-mentioned structure. Analysis shows that the product has an epoxy value of 0.44 eq / 100 g, a hydroxyl value of 0.297 eq / 100 g, a chlorohydrin value of 0.118 eq / 100 g, a chlorine value of 1.1 percent by weight and a molecular weight of 428 ± 20 owns. Calculated values are epoxy 0.54 eq / 100 g, hydroxyl 0.27 eq / 100 g, molecular weight 370.

Example 2

This example illustrates the rapid cure rate one can get with the methylol substituted Epoxy ether achieved.

100 parts of the methylol-substituted glycidyl ether prepared according to the previous example are combined with 10.9 parts of diethylenetriamine. Disappearance of the epoxy group is determined versus time at 23.9 ° C by near infrared spectrography and the results are shown on a graph in FIG. 1 (line A) shown.

Similar results were obtained for a related mixture made from unsubstituted glycidyl ether and the diethylenetriamines. The results in the latter case are shown as line B. Examination of the graph clearly illustrates the rapid rate of cure (disappearance of the epoxy groups) obtained with the methylol-substituted glycidyl ethers.

Example 3

This example also illustrates the rapid rate of cure that can be achieved with the methylol substituted Epoxy ethers achieved.

The monomethylol-substituted glycidyl ethers according to Example 1 are 8.7 parts (per 100 parts of ether) Diethylenetriamine and 80 parts of dioxane are mixed and the mixture is cured at room temperature. the Gel time for this mixture is 1 hour. In a similar experiment using The gelation time is 11.4 parts of diethylenetriamine with the glycidyl ether of an unsubstituted bisphenol 8.4 hours.

The above experiment is repeated at 50 ° C.

The unsubstituted ether has a gel time of 25 minutes, while the methylol-substituted ether Ether has a gel time of only 3 minutes - a 50 to 50 mixture of the unsubstituted Glycidyl ether and methylol-substituted glycidyl ether According to Example 1, 10 parts of diethylenetriamine are cured in 7 minutes without a solvent.

Example 4

100 parts of the methylol-substituted glycidyl ether from Example 1 are mixed with 6 parts of diethylenetriamine united and the mix when. thin film applied and cured at room temperature. The results are compared to what you get from one Similar film made from diethylenetriamine and the unsubstituted glycidyl ether is obtained:

mono- U.N- methylol substituted substituted Drying time (dust 10 min. 45 min. dry) Dry - hard 2.5 hours 3.5 hours Solvent resistance no very soft 15 minutes in contact effect with methyl ethyl ketone 24 hours hardening

The above experiment is repeated except that the hardening is carried out at a low temperature 4.4 ° C was carried out. The film is dust-dry in 1.5 hours and dry and hard after 7.5 hours.

Curing at these lower temperatures also gives a product that has improved flexibility as well Has impact resistance.

Example 5

The monomethylol-substituted glycidyl ether prepared in Example 1 is mixed with 11.3 parts of metaphenylenediamine and the mixture is heated at 200 ° C. for about 4 hours. The resulting product is a hard, insoluble, infusible casting having a heat resistance of 26O ⁰ C. When the heating was continued 5 to 6 hours, so the heat resistance at about 300 ° C could be increased.

1,620

In a similar experiment, the diglycidyl ethers of unsubstituted 2,2-bis (4-hydroxyphenyl) propane are combined with 14 parts of metaphenylenediamine and heated at 200 ° C. for 4 hours. In this case, the casting has a heat resistance of 150 ⁰ C. In a further test is combined a glycidyl ether of a non-substituted phenol-formaldehyde resin with 16 parts of metaphenylene diamine and heated as above. The product in this case has a heat resistance of 190 ⁰ C.

A comparison of the above results clearly shows the unexpectedly superior improvement in heat resistance when using the epoxy ethers obtained according to the invention.

Example 6 ' ⁵

The monomethylol-substituted glycidyl ether prepared according to Example 1 is mixed with the following: 8 parts (per 100 of the resin) nadic acid methyl anhydride (methyl-endomethylenetetrahydrophthalic anhydride) and one part benzyldimethylamine and an equivalent amount of hexahydrophthalic anhydride and one part benzyldimethylamine. The mixtures are heated to 150 ⁰ C. The castings obtained are hard, insoluble, infusible products with high heat resistance.

B e i s ρ i e 1 7

This example illustrates the preparation and some properties of a dimethylol substituted diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane.

604 parts of 2,2-bis (4-hydroxyphenyl) propane are dissolved in 320 parts of methanol and 94 parts of water, and 460 parts of a 37% strength formalin solution and 57 parts of a 20% strength aqueous sodium hydroxide solution are added. This mixture is heated at 82 ° C for approximately 20 minutes. The product obtained is then neutralized with dilute sulfuric acid and the mixture is distilled to remove methanol. A 5 molar excess of epichlorohydrin is then added and the mixture is stirred at room temperature. The mixture is then left to stand until the water phase has separated •. The organic phase is removed and 25 percent by weight methanol is added. This mixture is then heated to reflux and a 5 mol percent excess of concentrated sodium hydroxide is added. After completion of the reaction, the excess epichlorohydrin and methanol at 125 to 13O ⁰ C and 25 mm distilled off. The product obtained, which is a mixture of salt and resin, is dissolved in methyl isobutyl ketone and filtered. The product is then distilled at 150 ⁰ C and 2 mm for the removal of the solvent and produces a soft solid resin having an epoxy value of 0,37äq / 100 g, a hydroxyl value of 0.05 eq / 100 g, a molecular weight of 515 ± 15 where the calculated values are epoxy 0.90, hydroxyl 0.50 and molecular weight 400.

CH ₂ -Ch-CH ₇ -O- / "\

CH ₃

Example 8

The monomethylol-substituted glycidyl ether prepared in Example 1 and that in the preceding Example, dimethylol-substituted glycidyl ethers prepared in various amounts are as follows Components combined and cured in the presence of equivalent amounts of diethylenetriamine: 10% refined Coal tar, 20% medium oil, 15% highly aromatic oil from petroleum, 25% pine oil. The products received are hard, tough castings.

Example 9

30 parts of the dimethylol-substituted diglycidyl ether, prepared according to Example 7, are mixed with 70 parts of unsubstituted diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane and the mixture is combined with 13 parts of metaphenylenediamine. The mixture is heated for 1 hour at 100 ° C and 24 hours at 180 ° C The product obtained has a heat resistance of 191 ⁰ C, compared to about 150 ° C for the unsubstituted ether alone.

B e i s ρ i e1 10

This example illustrates the preparation and properties of a tetramethylol-substituted-biglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane.

457 parts of "2,2-bis (4-hydroxyphenyl) propane are dissolved in 300 parts of methaifol and 400 parts of a 37% strength formalin solution, 47 parts of a 20% strength aqueous sodium hydroxide solution and 300 parts of water are added to this mixture. This mixture is added at room temperature, allowed to stand for 6 days and strength then 320 parts of a 37% formalin solution was added and the mixture ^additional! allowed to stand for 8 days. the mixture is neutralized with dilute sulfuric acid and then distilled to remove the methanol. a lOmolarer excess of epichlorohydrin is added and the mixture This mixture is left to stand until the water phase has separated off. The organic phase is removed and combined with 25 percent by weight of methanol, the solution is heated to reflux and concentrated caustic soda is added for a 5% excess, based on the phenolic hydroxyl content. When the reaction is complete, the excess epichlorohydrin and metha become nol distilled off at 125 to 130 ⁰ C and 25 mm. The product is dissolved in Methylisobutylkeion, filtered to remove the salt and mm distilled off at 13O ⁰ C 2 to obtain a soft solid resin having about four methylol groups to give per bisphenol group. The product has an epoxy value of 0.25 eq / 100 g and an OH value of 0.77 eq / 100 g.

Example 11

This example illustrates the preparation and some properties of a dimethylol substituted diglycidyl ether the following formula

OH

_CH CH ₂ H

O? O- ° -r ^c -r ° O-

CH,

HHH

O
CH ₂ CH-CH ₂

CHoOH

A polyhydric phenol containing two units of 2,2-bis (4-hydroxyphenyl) propane is produced by dissolving 228 parts of 2,2-bis (4-hydroxyphenyl) propane in 200 parts of methanol, and this The mixture is 46 parts of epichlorohydrin and 25 parts

20% strength aqueous sodium hydroxyl solution and 25 parts of water were added. The solution is held for 2 hours at 74 ° C under reflux, after which the temperature to 150 ⁰ C by removing the solvent is increased.

The product formed in this reaction has the formula

HO

CH,

CH,

OH

OH

85 parts of a 37% strength formalin solution, 25 parts of a 20% strength aqueous sodium hydroxide solution and 25 parts of water and 20 parts of methanol are added to the reaction mixture described above. This mixture is refluxed at 76 ° C. for ¹ _1/2 hours. The mixture is then neutralized with 15% sulfuric acid and methanol is distilled off. 840 parts of epichlorohydrin are used to dissolve the resin and the mixture is allowed to stand until it has separated into an aqueous and organic phase. The organic phase is removed and mixed with-150 parts and 40 parts of concentrated sodium hydroxide solution. This mixture is ^{refluxed for 1} _{l for 2} hours and the solvents are removed at 120 ° C. and 23 mm. The product obtained, which is a mixture of resin and salt, is dissolved in 500 parts of methyl ethyl ketone and filtered. The filtrate is distilled at a temperature of 140 ° C. to 2 mm Hg in order to remove the solvent. The product obtained is a hard, solid resin of the above structure and an epoxy value of 0.26eq / 100g, a hydroxyl value of 0.49eq / 100g and a molecular weight of 620. The calculated values are: epoxy value OriOaq / 100 g, hydroxyl value 0, 44 eq / 100 g and molecular weight 684.

example

This example illustrates the preparation and properties of a dimethylol substituted diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane of structure

J ■ - γ

CH2 CH "

/ VOC — C — C— CH- CH, - Ό— / Λ

QCC-CO-CH ₂

228 parts of 2,2 - bis (4 - hydroxyphenyl) propane, 170 parts of diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane and 175 parts of methanol are mixed together and 2 parts of potassium hydroxide Room temperature added. The mixture is heated to 140 ° C1 hour and the methanol by distillation removed. The product obtained is a polyhydric phenol of the above structure which is free from Is epoxy ether groups and free of methylol groups.

175 parts of methanol are added to the reaction mixture, along with 85 parts of 37% formalin, 30 parts of sodium hydroxide and 50 parts of water. This mixture is maintained ^l / ₂ hour at reflux. The mixture is neutralized with sulfuric acid and methanol is removed by distillation.

A 10 molar excess of epichlorohydrin is then added and the product at room temperature ditched. The mixture separates into an aqueous and an organic phase, and the organic Phase is removed and combined with 25 percent by weight methanol. This mixture is refluxed heated and a 5% excess of concentrated sodium hydroxide added. After the In reaction, the excess epichlorohydrin and methanol are removed by distillation at 125 bis 130 ° C and 25 mm, being the desired resin salt mixture remains. The product is dissolved in methyl ethyl ketone, filtered and then added to the desired Resin distilled. The product obtained has the structure described above and has an epoxy equivalent from 188eq / 100g.

309582/409

Example 13

This example illustrates the preparation and properties of the monomethylol-substituted tetraglycidyl ether of l, l, 2,2-tetrakis (4-hydroxyphenyl) ethane of the structure

HIGH-

O
CH ₂ ^X CHCH ₂ -O

O O

O-CH ₂ CH CH ₂ Q-CH ₂ CH CH ₂

0-CH ₂ CH

/ 398 parts of 1,1,2,2-tetrakis (4-hydroxyphenyl) -ethane are mixed with 250 parts of methanol, 85 parts of 37% strength formalin solution, 36 parts of sodium hydroxide in 65 parts of water. This mixture is _{refluxed for 2} hours and then neutralized with dilute sulfuric acid.

The methanol is removed by distillation and 2600 parts of epichlorohydrin are added and the Allow mixture to stand at room temperature. The separated organic phase is then removed and mixed with 200 parts of methanol and heated to reflux. 165 parts of sodium hydroxide will be then added over the course of 30 minutes and the mixture was refluxed for a further 30 minutes. The mixture is removed from excess epichlorohydrin and methanol by distilling at 130 ° C and 25 mm freed and the product obtained dissolved in methyl ethyl ketone, filtered and at 130 ° C at 2 mm distilled. The product obtained is a hard solid with the resin described above. That The product has an epoxy value of 0.464 eq / 100 g and a hydroxyl value of 0.36 eq / 100 g: molecular weight 610 ± 20.

Example 14

The previous example is repeated with the exception that 170 parts of the 37% formalin solution can be used in place of 85 parts. The product obtained is a dimethylol substituted one Tetraglycidyl ether of l, l, 2,2-tetrakis (4-hydroxyphenyl) ethane. The product has an epoxy value of 0.388 eq / 100 g and a hydroxyl value of 538 eq / 100 g; a molecular weight of 730 ± 25.

Example 15

The polyepoxy resins produced in Examples 1, 7 to 14 are used in equivalent amounts each of the following epoxy hardeners mixed: dicyandiamide, diethylenetriamine, boron trifluoride-ethylamine complex, Ethyl maleic anhydride, metadiphenylenediamine and a polyamide of dimerized Linoleic acid and ethylenediamine. Each of the mixtures obtained is kept at 100 ° C. for several hours hardened. In each case clear hard resins are obtained.

Example 16

The monomethylol-substituted diglycidyl ether-Ydn 2,2-bis (4-hydroxyphenyl) propane, prepared according to Example 1, is mixed with a large number of different proportions of bufyl glycidyl ether. The viscosities of the solutions obtained are shown in the drawing, FIG. 2 shown under line A. Each of these low-viscosity solutions is combined with an equivalent amount of metaphenylenediamine and cured at 100.degree. The products obtained are hard, tough, insoluble castings which have exceptional heat resistance.

Example 17

The monomethylol-substituted glycidyl ether of 2,2-bis (4-hydroxyphenyl) propane, prepared according to Example 1, is also mixed with various amounts of glycidyl ethers of dihydropyran-2-methanol. The viscosities of the solutions obtained are shown in the drawing F i g. 2 shown under line B. Each of these low viscosity solutions is mixed with an equivalent amount of metaphenylenediamine and cured at 10O ⁰ C. The products obtained are hard, tough resins with high heat resistance.

Example 18

The dimethylol-substituted diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane, prepared in Example 7, is mixed with 25% butyl glycidyl ether. The viscosity of the obtained solution at 25 ⁰ C is 82 poises. This solution is combined with an equivalent amount of metaphenylenediamine and cured at 100 ⁰ C. The product obtained is a hard, tough, heat-resistant resin.

Example 19

The dimethylol-substituted diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane, prepared according to Example 7, is mixed with various amounts of glycidyl ethers of dihydropyran-2-methanol. Each of the low-viscosity solution is mixed with an equivalent amount of metaphenylenediamine and cured at 100 ⁰ C. The products obtained are hard, tough resins with good heat resistance.

Example 20

OH

OH

105 parts of this resin are mixed with 42.5 parts of 37% strength formalin solution, 10 parts of sodium hydroxide and 500 parts of methanol. The mixture is heated to reflux and held for 30 minutes. 925 parts of epichlorohydrin are added, the mixture is heated to reflux and 74 parts of sodium hydroxide in 85 parts of water are added. The mixture is heated at reflux for ^l / ₂ hour and the volatiles at 135 ° C and 25 mm apart. The product obtained is dissolved in methyl ethyl ketone, nitrated and stabilized at 135 ° C. 2 mm. The solid resin obtained is identified as a glycidyl polyether of the dimethylol-substituted novolak resin described above. The resin cures easily with diethylenetriamine and with metaphenylenetriamine to form hard, insoluble, infusible, hardened products.

Example 23

This example illustrates the preparation and some properties of the diglycidyl ether of the monomethylol substituted one Resorcins.

110 parts of resorcinol are mixed with 85 parts of 37% strength formalin, 10 parts of sodium hydroxide and 500 parts of methanol. This mixture is heated to reflux and held for 30 minutes. 925 parts of epichlorohydrin are added and the mixture is heated to reflux. 74 parts of NaOH, dissolved in 85 parts of water, are added over ¹ l for ₂ hours. The mixture is kept ¹ I ₂ hour at reflux and then methanol, the excess epichlorohydrin and water are removed. The product obtained is dissolved in methyl ethyl ketone, filtered and the methyl ethyl ketone at 14O ⁰ C and 2 mm away. The product obtained is identified as the diglycidyl ether of monomethylol substituted resorcinol. This resin could easily be cured with metaphenylenediamine as mentioned above to a hard, cured resin having a high heat resistance.

Example 21

The previous example is repeated with the exception that resorcinol is replaced by hydroquinone will. The product obtained is the diglycidyl ether of monomethylol-substituted hydroquinone, the can also be cured with metaphenylenediamine to form a product with excellent heat resistance can.

Example 22.

This example illustrates the preparation and some properties of a glycidyl polyether of a dimethylol substituted one Novolak resin of the formula

A diglycidyl ether of monomethylol substituted diphenyl oxide is prepared by mixing of 100 parts of dihydroxydiphenyloxide with 50 parts of a 37% formalin solution, 10 parts of sodium hydroxide and 500 parts of methanol and reflux for 30 minutes. 850 parts of epichlorohydrin will be with 65 parts of sodium hydroxide dissolved in 70 parts of water are added. The mixture is 30 minutes held at reflux. The volatile constituents are removed at 130 ° C. and 25 mm. The received The product is dissolved in methyl ethyl ketone, filtered and distilled to remove the solvent. The product obtained is a solid resin identified as the above product which easily can be cured with diethylenetriamine and metaphenylenediamine.

Example 24

The dimethylol-substituted product could be obtained by repeating the foregoing Example with the exception that 100 parts of the 37% formalin solution were used.

Example 25 ^ - '

100 parts of the monomethylol-substituted diglycidyl ether, prepared according to Example 1, are with 50 parts of amine-containing polyamide of dimerized linoleic acid and diethylenetriamine mixed. the Mixture is discharged as a film and cured at 4 and 24 ° C. It will be the results shown below obtain.

Drying time

touch dry

kind of dry

Flexibility, core

Pencil hardness

Solvent resistance
Methyl isobutyl ketone

Xylene

Water (cold -
15 minutes) ...

4 ° C hardening

25 min.

7.5 hours

comes at

3.175 mm

by

HB

no

effect

the same

the same

24 ° C hardening

40 min.

2 hours.

comes at

3.175 mm

by

HB ""

no

effect

the same

the same

Example 26

100 parts of the dimethylol-substituted glycidyl ether of Example 8 with 50 parts of a amine group-containing polyamides of dimerized linoleic acid and diethylenetriamine mixed. the Mixture is hardened at 4 and 24 ° C. The results after 5 weeks are shown below.

Flexibility (core)
Pencil hardness

4 ⁰ C hardening

comes at

3.175 mm

by

B-F

24 ° C hardening

comes at

3.175 mm

by

HB

21
continuation 4 ° C hardening 24 ° C hardening no
effect
the same
the same
the same no
effect
the same
the same
the same Solvent resistance
age
Methyl isobutyl ketone,
1 H
Xylene, 1 hour
Water (cold -
24StA)
Sulfuric acid, 20%,
IStd

Example 27

The polyepoxy resin produced in Example 13 is dissolved in acetone to form a 60 percent by weight solution. Metaphenylenediamine is added at the rate of 12.6 parts per 100 parts of resin. A glass cloth is saturated with this solution, after which the acetone is removed under reduced pressure at room temperature. A 4-layer laminate produced from this fabric and ^{cured initially for 1 hour at 100 °} C. and then for 4 hours at 200 ^° C. shows excellent flexural strengths and modulus at elevated temperatures.

1 sheet of drawings

Claims (3)

1 2 at least one mole of alkali per phenolic OH claims: group at temperatures from 50 to 1500C, which is characterized in that one is a polyvalent 1. Process for the preparation of an epoxy ether phenol such a monomeric or polymeric phenol used by reacting a polyhydric phenol 5, which is mono- or polynuclear, at least with an epoxy-halogen-substituted alkane one bonded to a ring carbon atom, methyl or a dihalo-hydroxy-substituted ol group and optionally non-interfering substituted alkane in an amount ratio of 1: 1, contains 1 to tuen th. 1:10 in the presence of at least one mole It has been found that epoxy ethers of alkali per phenolic OH group at temperatures io epoxy-substituted alcohols and polyhydric alcohols from 50 to 150 ⁰ C, characterized by marked and preferably polynuclear, polyvalent that as polyhydric phenol, alcohols substituted on at least one such monomeric or polymeric phenol ring carbon atom with a methylol group, which is mononuclear or polynuclear, at least for example diglycidyl ether of 2,2-bis (3-methyloleine bonded to a ring carbon atom) 15 4-hydroxyphenyl) propane, of the unsubstituted thylol group and possibly non-interfering epoxy ethers contains quite different properties besit-substituents. zen and many of the current needs of epoxy 2. The method according to claim 1, thereby satisfying the identified resin industry. It has, for example draws that the alkali hydroxide is shown over- shown that this epoxy ether is a surprising shot up to 5%, based on the content of phenoli- 20 show rapid reaction at low temperatures, Shem hydroxyl is used. especially in combination with polyamines and -. 3. The method according to claim 1, characterized thereby cured with these substances at one speed draws that you can be more than methylol-substituted, 4- to 10-fold or more 'Valuable phenol is a methylol-substituted one faster than that of the usual epoxy resins. These powerful polyhydric phenol is used. 25 surprising properties allow the invented 4. The method as claimed in claim 1, characterized in that epoxy ethers are produced in one size draws that there is more than a methylol-substituted number of different applications, especially in valuable phenol to coat a methylolated phenol form and to treat the surface, aldehyde resin used. In addition, it has been found that the * .hardened 5. The method according to claim 1, characterized marked 30 products obtained by implementing the invention draws that the epoxy-forming material produced epoxy ether with hardener, in particular epichlorohydrin used. others obtained with the aromatic polyamine hardener have an unexpectedly high heat resistance Zen. The heat resistance is 50 to in many cases 35 150 ⁰ C higher than that which one under similar Epoxy ethers of unsubstituted polyvalent conditions with the unsubstituted glycidyl Phenols such as glycidyl ethers are obtained from 2,2-bis (4-hydroxy ethers. This surprising property permits phenyl) propane have been in tech for some time, the epoxy ethers produced according to the invention for niche use. They are widely used for important casting and pressing purposes and in the manufacture in the production of surface coatings, to use adhesive bonding of reinforced bodies, as in the materials, moldings and castings. These fabrics have thread spools and when laminating, however, there are also certain disadvantages that make their application. There is now a method of making these restrict. For example, it has been found that epoxy ethers are found using a that a considerable time is necessary to the resins methylol-substituted polyhydric phenol with a to harden at low temperatures. This prevents 45 epoxy-forming material from the group epoxy- their use for certain types of coatings, halogen-substituted alkanes and dihalo-hydroxy- as they are applied to roads, for example. substituted alkanes in the presence of an alkali Additionally, the hardened resins don't have the for sets. The formation of the epoxy ethers in this way the new application to projectiles and missiles is surprising as one could expect that the necessary heat resistance. 50 methylol group reacts with the epoxy-forming substance From British patent specification 743 647 is a yaw and would not be left behind as such. It is surprising that in this process a high conversion rate of epoxyhalogen-substituted alkanes can be obtained from the desired epoxyethers with the methylol group or groups which have not reacted with monohydric methylol-substituted phenols. These epoxy ethers can be made stronger with the help of 55.
Acids are hardened at elevated temperatures. The in the manufacture of the epoxy ether after It is an object of the present invention to provide a multi-value process used according to the invention Phenols to be used for the production of epoxy ethers are those which have at least one, pre-winding, which hardened in a simple manner in a short time, preferably two or more ring carbon atoms can be without high temperatures or associated with a methylol group contain. These aggressive reagents such as strong acids applied Phenols can be mononuclear or polynuclear, can with Need to become. non-interfering substituents such as halogen atoms, This object is achieved according to the invention by ether and ester residues. Alkyl residues, alkenyl residues, a process for the production of an epoxy ether by alkoxy radicals, sulfur, sulphonyl groups or mer- Implementation of a polyhydric phenol with a 65 capto groups. The phenols can epoxyhalogen-substituted alkane or a diha- also be those of the polymeric type, as they are logenhydroxy-substituted alkane in a quantity- by reacting phenols with formaldehyde- ratio of 1: 1, 1 to 1:10 in the presence of holds (novolak resins).