DE1165030B - Process for the preparation of curable compounds containing epoxy groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 07 d

Number:
File number:
Registration day:
Display day:

German class: 12 ο - 27

H 35729 IVb / 12 ο
February 25, 1959
March 12, 1964

It is known that hardenable compounds containing epoxy groups made from di- or polycarboxylic acids can thereby be produced produce that one alkali salts of these acids, for. B. disodium phthalate, at elevated temperature with an excess of a haloepoxyalkane, e.g. B. epichlorohydrin, reacts from the excreted Inorganic salt is filtered off and the excess haloepoxyalkane is distilled off. the technical implementation of this process is not very easy, among other things because the educated inorganic salt is present in finely divided form and causes certain difficulties during filtration.

It has now been found that curable compounds containing epoxy groups can be obtained in a simple manner and using easily accessible starting materials can be produced by organic Compounds that contain more than one carboxyl group in the molecule, at elevated temperature with a haloepoxyalkane, which contains a halogen atom adjacent to the epoxy group, for Reaction brings. The haloepoxyalkane is used in an amount of more than 2 moles per carboxyl group used. Organic high molecular weight compounds which are insoluble in the reaction mixture are used as catalysts admitted that either

a) salt-like groups or

b) groups which change into salt-like groups under the reaction conditions, or

c) acid amide groups

contain. To isolate the epoxy compounds formed, the catalyst is separated off from the reaction mixture. Then remove the excess Halogenepoxyalkane and volatile reaction products formed are distilled off.

Organic compounds which contain more than one carboxyl group in the molecule and which can be used as starting materials for the process according to the invention are, for. B. aliphatic di- and polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dichlorosuccinic acid, citric acid, aconitic acid, dimerized fatty acids or carboxylic acids, which can be obtained by adding maleic anhydride to unsaturated fatty acids. Aromatic carboxylic acids are also suitable, e.g. B. o-phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimesic acid, pyromellitic acid, naphthalene-2,6-dicarboxylic acid, naphthalic acid, diphenyl-0,0'-dicarboxylic acid, diphenyl-ρ, ρ'-ρ, ρ ' -dicarboxylic acid, etc. Also cycloaliphatic carboxylic acids, processes for the production of epoxy groups
containing curable compounds

Applicant:

Henkel & Cie. G. m. B. H.,

Düsseldorf-Holthausen, Henkelstr. 67

Named as inventor:

Dr. Manfred Budnowski, Düsseldorf-Holthausen, Dr. Manfred Dohr, Düsseldorf

ζ. B. tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid or hexahydrophthalic acid, are suitable, as are a number of heterocyclic carboxylic acids, though the latter are generally out of the question because of their price.

The carboxylic acids used as starting materials can, in addition to carboxyl groups or halogen atoms also contain other substituents in the molecule, provided that this disrupts the reaction will, e.g. B. hydrocarbon residues, ether groups, ester groups and others. m. For example, as Starting materials ether carboxylic acids in question, z. B. ethylene glycol-bis-jp-carboxyphenyl ether] and corresponding Ethers of other polyhydric alcohols or diphenyl ether p ^ '- dicarboxylic acid or such Ether carboxylic acids, which are derived from polyhydric phenols such as resorcinol, diphenylolpropane or p, p'-diphenol, by reaction with halocarboxylic acids, ζ. Β. Chloroacetic acid, can be obtained.

Suitable starting materials are also ester carboxylic acids, such as those used, for. B. by esterification of a polyvalent Alcohol, such as glycol, glycerol, pentaerythritol or mannitol, with a corresponding excess a di- or polycarboxylic acid or polybasic by reaction of the alcohols mentioned with anhydrides Acids can be obtained in a suitable molar ratio. Such products are e.g. B. Partial esters from a glycol, for example ethylene glycol and 2 moles of a dicarboxylic acid, such as adipic acid or Terephthalic acid, also partial esters, which are obtained from a glycol by reaction with 2 moles of a dicarboxylic acid anhydride, such as maleic anhydride, phthalic anhydride or endomethylenetetrahydrophthalic anhydride, can be obtained.

If you want to manufacture higher molecular weight products, you can use polyester as a starting material, for example

409 538/540

3 4

with terminal carboxyl groups and corresponding form of their salts, eg. B. in the form of chlorides or the size of the molecule. These can be z. B. sulfates to use.

Prepared in a known manner by ~ Another group of suitable catalysts are polybasic carboxylic acids with polyvalent Aiko- those high molecular weight compounds that get reactive converts and thereby contain the carboxylic acids in Ent- 5 capable groups, which are among the appealing Used excess. On the same nimble terms in salty groups over-purpose you can also go from polymers or. Such compounds are, for example, highly copolymers unsaturated carboxylic acids such as molecular organic bases, e.g. B. Anions from acrylic acid, Maleic acid, fumaric acid and others, exchangers in the form of the free bases. Others too walk. io resins containing tertiary nitrogen, the

In some cases it is advantageous to use mixtures of known quaternary epihalohydrins different carboxylic acids as starting materials to compounds are suitable, for. B. use melamine. So it is z. B. possible by adding a resin, or hardened with organic amines certain amount of dicarboxylic acids with longer epoxy compounds. They are also high molecular weight Carbon chains, such as adipic acid, sebacic acid, 15 compounds suitable, the divalent sulfur brassylic acid, or to contain atoms of dimerized fatty acids which are capable of interacting with halogen Starting materials, such as B. phthalic acid, an epoxyalkane in ternary sulfonium compounds over certain Plasticization of the invented by hardening.

Epoxy compounds obtained according to the invention- Furthermore, such high-

to achieve. For the same purpose it is suitable in 2 ° molecular organic compounds, In some cases advantageous, the reaction mixture which acidic and basic groups side by side in the Contain smaller amounts of monocarboxylic acids, especially a molecule. Such products are e.g. B. as of longer-chain fatty acids. Ion exchangers under the name hermaphrodite

Haloepoxyalkanes, which contain a halogen atom in ionic resins, are commercially available. Of course you can too Contain adjacent position to the epoxy group and the 25 so-called mixed bed ion exchangers, d. H. Mixed not in accordance with the invention with the above-described gene consisting of anion exchangers and cation exchangers than exchange a carboxyl group-containing compounds can be used.

are implemented, for example, epichlorohydrin, Finally, such processes come as catalysts

Epibromohydrin, 1,2-epoxy-3-chlorobutane, 1-chlorine bonds in question, which acid amide groups ent-2,3-epoxybutane, l-chlorine ^ S-epoxy-S-methoxy-pentane 30 hold, z. B. polyamides, also the well-known Harnu. a. The preferred starting material is epichloride resins.

hydrin used. The amount of haloepoxy mentioned catalysts are for the

alkane is more than 2 moles per carboxyl group. Process according to the invention expediently in granular It is advantageous to use the haloepoxyalkane in substantial form. Fine powdery fractions are advantageous larger excess, e.g. B. 10 to 40 mol and 35 adhered beforehand by sieving and / or washing out more per carboxyl group to be used. That not separated. In this way one achieves that the converted haloepoxyalkane will not separate the catalyst from the reaction during the reaction changed and can be easily recovered and blended, e.g. B. by centrifugation, decanting can be used again. or filtering, runs extremely smoothly. For the

Coarse filters are primarily sufficient as catalysts. Used to advantage Substances in question, which are in the reaction mixture one close-meshed wire screens for this purpose, do not dissolve and therefore after the reaction has ended. The catalysts can generally be used as desired

can easily be separated mechanically. Used on often as they differ, from a minor one this way it is avoided that the reaction mechanical abrasion is not consumed apart from, product in a cumbersome manner by washing out 45 Should their activity after repeated use must free from the catalyst or that by slacking off, so they can be regenerated in a simple manner Catalyst residues when the cursed are distilled off. The type of regeneration is of that term constituents of the reaction mixture chemical constitution of the catalyst in question Side reactions are triggered. It depends on sators. In many cases it is washed out and organic sources with water are therefore preferably sufficient as catalysts. In other cases see high molecular weight compounds that are used in the catalysts by treating them with are insoluble in the reaction mixture. Salt solutions or with dilute acids or

First, such Ver bases are regenerated as catalysts.

The amount of the catalyst can be varied within wide limits

hold, e.g. B. the salts of high molecular weight organic 55 fluctuate. The optimal amount depends on the Acids, such as alkali, ammonium or amine salts, the constitution of the catalyst depends on the case of polyacrylic acid. It is particularly useful if it can be easily determined by preliminary tests. Catalysts to form so-called ion exchange resins. The process according to the invention is carried out in the manner

use. Cation exchange resins, which carried out acidic, that said starting compound groups, z. B. sulfonic acid groups, carboxyl groups, fertilize 60 and the catalyst heated for a few hours Phosphonic acid groups and others. In some cases it is useful to use the an inert organic solvent is used for the process according to the invention in the form of a reaction mixture Salts, e.g. B. to be added in the form of alkali, ammonium solvents. If you use something or amine salts. It is furthermore possible, which is expedient, to use epichlorohydrin as halogen Catalysts anion exchange resins, d. H. 65 epoxyalkane, in a larger excess, see above Ion exchangers with basic groups, e.g. B. Amino- it is recommended to use the reaction mixture on the back groups, to boil quaternary ammonium or phosphorous flux. Then the catalyst nium groups and ternary sulfonium groups, separated in by z. B. the mixture through a

5 6

fine sieve made of V4A wire. The separation will usually be a product with a high content of the catalyst goes in this way extraordinarily use of epoxy oxygen. On the other hand, it becomes smooth and quick. Subsequently, the excessively long processing time of the resin-hardener mixture schüssige haloepoxyalkane and volatile reac- desired, so you choose compounds with low tion products such. B. dichlorohydrin, distilled off, and 5 content of epoxy oxygen. Even the elasticity of the, although preferably at reduced pressure. The cured product can be varied by the content of haloepoxyalkane distilled off, optionally epoxy oxygen. Further possibilities of variation after appropriate cleaning, for further approaches, result from the choice of the starting point. Dihalohydrin formed can be easily converted into epihalohydrin with the addition of plasticizing compounds in a known manner by means of that already described above. It was known from French patent specification 1,066,037 and the German patent application K 10079 IVb / 39c produced by the process according to the invention containing curable epoxy groups Sodium phthalate and epichlorohydrin, 15 temperatures of about 100 to 150 ° C to polymerize, epoxy compounds produced are not identical. It was pointed out that even with you differ from these, as a rule, hardening occurs due to lower temperatures. As a content of several percent of organic ion exchanger in this known bonded halogen, z. B. chlorine. Among other things, they are distinguished by anion exchangers with amine removers in comparison to the products obtained by the known method of using or quaternary ammonium groups or melamine using low vis-formaldehyde resins. It was therefore over-viscosity and bright in color. surprising that the same resins as catalysts according to the invention can be produced products may be suitable for a process for the preparation of curable overall with all as curing agents for epoxy compounds epoxy compounds, wherein Tempe suitable materials, for example with organic bases 25 temperatures above 100 ⁰ C can be applied. On or with di- or polycarboxylic acids or the basis of the above-mentioned prior publications was anhydrides to be cured. Their usefulness under the conditions used according to the invention is versatile. You can e.g. B. in combination with rapid polymerisation of the epoxy compounds to form suitable hardeners as adhesives, casting resins, paints - expect.

resins or for the production of glass fiber reinforced 30 It was also known to produce glycidate esters

Plastics are used. In general, make that carboxylic acids with at least the

The new products can be used for all those twice the stoichiometrically required amount

Use purposes for which you have previously used epichlorohydrin in the presence of a tertiary

of epoxy compounds. With amine or a quaternary ammonium salt

their advantageous properties, in particular their increased temperature. In this procedure

low viscosity and their light color, they are exclusively low-molecular

in many cases the previous epoxy compounds used in the amounts used

think. are soluble in the reaction mixture. This well-known

Surprisingly, it has been shown that the process is suitable for the preparation of low-boiling paints of the glycidic esters of monobasic carboxylic acids prepared by the process according to the invention, and that the viscosity can be reduced by vacuum distillation if the batch is used . However, if small amounts of water of up to about 3%, based on the dicarboxylic acids, are used as starting compounds in these processes, the amount of haloepoxyalkane is added. When removing mixtures which already tend to polymerize when the excess haloepoxyalkane 45 epichlorohydrin is distilled off, the water is essentially removed so that the reaction product has lower epoxy values than is water-free. In this way, reaction products according to the invention and often strongly discolored products are obtained which are only slightly yellow in color and in color. The following comparative tests A to D are almost as clear as water in many cases. Additions serve to explain this fact. For the small amounts of up to 1% ^ar * organic 50 experiments A and B, the known peroxides, z. B. Methyläthylketonperoxid or Cyclo process a low molecular weight catalyst (benzylhexanone peroxide, water trimethylammonium chloride are used without difficulty). Receive products for the Verhelle. Seek C and D, an ion exchange resin served as

An increase in the content of the catalyst according to the invention. Otherwise it was under the same BeProdukte On epoxy oxygen one can work on conditions. For experiments A and C Achieve different ways, for example by, on the one hand, and B and D on the other hand, became the same that with a particularly large excess of the amount of the starting compounds (adipic acid relevant haloepoxyalkane works or that and epichlorohydrin) used, one made by the present process

Product treated again with epichlorohydrin and catalyst.

It is a particular advantage of the 73 g (V ₂ mol) of adipic acid according to the invention, 740 g (8 mol) of epichloro

Process that with its help epoxy groups hydrin and 1 g of benzyltrimethylammonium chloride

curable compounds containing very ver were ^{heated to 115 °} C. for 6 hours with stirring,

with a different content of epoxy oxygen 65 Then at a pressure of 45 mm Hg

can. In this way, the properties of the bulk of the excess epichlorohydrin can be reduced

of products vary widely. One sets distilled off. Then an attempt was made at one

z. B. Value on particularly short curing times, so pressure of 2 mm Hg the remaining volatile components

7 8

to remove from the mixture. However, this succeeded 3700 g of epichlorohydrin heated under reflux for 5 hours,

not, since the mixture was already after cooling down, the reaction mixture

Bottom temperature of 98 ° C gelled. Then filtered off from the catalyst. Then the

the experiment was carried out using a vacuum of excess epichlorohydrin at a pressure of

0.1 mm repeated. However, it was not possible here either, 5 40 mm Hg distilled off. Eventually it was at one

all volatile components from the mixture to a pressure of 0.5 mm Hg residual epichlorohydrin and

remove as gelation occurred again. The epichlorohydrin formed during the reaction up to

Epoxydsauerstoff content of the gelled product to a pot temperature of 12O ⁰ C distilled off. Of the

was less than 1% in each case · The residue consisted of 310 g of a very light-colored

ίο liquid epoxy compound with the following characteristics

Attempt B pay:

Epoxy oxygen 6.5%

73 g adipic acid (V ₂ mol), 1850 g epichlorohydrin, - ,,, _{7 5} ",

(20 mol) and 1 g of benzyltrimethylammonium chloride ° '°

were heated to 115 ° C. for 6 hours with stirring. 15 not nitrogen

Subsequently, it was again initially detectable in one

Pressure of 45 mm Hg the main ^{amount of the over- viscosity at 50 0} C *) 45OcP

Schüssigen epichlorohydrins distilled off. Then color according to L ο ν i b ο nd (1 "cuvette) 9.0 yellow

was tried at a pressure of 2 mm Hg the j 7 R ₀ ^

remaining volatile components from the mixture to 20

remove. Here, the resin gelled at a swamp ". *) ^B fi ^to ü ** ™ ^{and in de} ? following examples, the specified temperature of 115 ⁰ C. At this temperature, V ^ tatswerte wuzden with the Hoppler Viskosuneter gewaren only about 60% of the theoretically expected

Part of dichlorohydrin passed over. For comparison, the corresponding values are used

The stand still contained 1.0% epoxy oxygen. 25 one of disodium phthalate and epichlorohydrin

the method of the German patent specification 944 995 Experiment C indicated epoxy compound prepared:

73 g adipic acid (V ₂ mol), 740 g epichlorohydrin, epoxy oxygen 6.5%

(8 mol) and 100 g of the commercially available anion constituent 30 ^{Chior υ} ' ^{5 / o}

tauschers-Lewatit MN (registered trademark) nitrogen

in the form of the hydrochloric acid salt (by viscosity three times at 50 ° C 1100 cP

Washing with acetone freed from adhering water) _{Lovibond color} (i "cuvette) 27.9 yellow

were heated to 115 C for 6 hours with stirring. 25 6 red

The catalyst was then filtered off, and 35 '

it became the main anion exchanger used at a pressure of 45 mm Hg

the amount of excess epichlorohydrin is distilled off - it is the commercial product »Dowex 1 X 10« lates. Thereafter, the remaining volatile (registered trademark). This represents after the If the sump temperature rises up to 130 ° C, share a strongly alkaline mixture according to the supplier removed. In contrast to the tests A 40 represents an ion exchanger based on polystyrene, which and B the mixture did not gel. Rather, it was made to contain quaternary benzylammonium groups. This a light-colored, thin-bodied epoxy compound with an ion exchanger was shaped with equal success Obtained epoxy oxygen content of 6.1%. the free base and in the form of the hydrochloric acid salt

used. Experiment D 45 Example 2

73 g of adipic acid (V ₂ mol), 1850 g of epichlorohydrin, 166 g of o-phthalic acid, 3700 g of epichlorohydrin and 80 g

(20 mol) and 100 g of the commercially available anion from a water-containing commercially available strongly acidic

tauschers-Lewatit MN (registered trademark) cation exchanger, which by treatment with

in the form of the hydrochloric acid salt (loaded with ammonium ions _{by three 50% aqueous NH 4 C1 solution}

Washing with acetone from adhering water was, were refluxed for 5 hours. Subsequent

freed) were ßend with stirring for 6 hours at 115 ° C ßend the reaction mixture in the same

heated. The catalyst was then worked up as described in Example 1,

filtered, and the main amount of the over- There were 310 g of an epoxy compound with the following

Schüssigen epichlorhydrins at a pressure of 55 get the key figures:

mm Hg distilled off. Finally, the remaining epoxy oxygen 6 9 ° /

borrowed volatile components at a pressure of 2 mm Hg: \ 71 0 /

and with a sump rising to 130 ° C tempera- chlorine 7.1 / "

door distilled off. There were 144 g of a light thin nitrogen not

liquid epoxy compound with an epoxy 60 detectable

oxygen content of 7.6% obtained. Viscosity at 50 ^° C. 350 cP

To further explain the invention, the _{color Qach L 0 v} i _bond (! "- cuvette) 7,0 yellow,

the following examples. 15 red

Example ⁶ 5 in the case of the cation exchanger used

it is the commercial product »Lewatit KSN«

166 g of o-phthalic acid were mixed with 80 g of a commercial (registered trademark). This product represents conventional water-containing anion exchanger and, according to the supplier's information, a phenolic resin

with - SO ₃ H groups on the core or in the side chain.

With the same approach, in which instead of the cation exchanger as a catalyst, 10 g of ammonium chloride 312 g of an epoxy compound having the following properties were obtained:

Epoxy oxygen 4.8%

Nitrogen 0.8%

Viscosity at 50 ⁰ C 500 ocP

Color dark brown

Example 3

IO

10

Tabel

° / o H ₂ O based on the end Epoxy VjI HUI Viscose
cito + used epichlorine
hydrin prey oxygen Ve oil LdL
50 ⁰ C G 0 /
/O 7.5 cP 0 310 6.5 6.6 450 0.5 300 7.1 6.0 390 1.0 300 7.3 6.7 300 *) 1.5 320 7.2 11.39 300 2.7 310 4.3 11.72 13th 340 3.6

Example 1 was repeated, with varying amounts of water being added to the batch became. The results are shown in Table 1 below.

*) Color according to Lovibond (1 "cuvette): 1.4 yellow, 0.5 red.

e ι s ρ ι e

The same approach as in Example 1 was repeated with the addition of various catalysts. the (Note: the results obtained in the ion exchanger are shown in the following Water is not taken into account in the table.) Table 2 reproduced:

Tabel

Type of catalyst

Amount of catalyst

Yield g

Epoxy
oxygen chlorine 5.1 9.1 5.3 "11.3 6.9 6.9 6.8 7.2 6.9 7.1 5.5 12.0 6.7 9.3 4.0 15.3 3.15 14.63 5.5 8.17 6.3 - 4.5

viscosity

50 ° C

cP

Resin according to Example 1 hardened with diethylenetriamine ..

Modified melamine resin according to British patent 877 670, example 4, ^{cured at 120 °} C. for 5 hours.

Anion exchanger »Dowex 1 X 8« *) in the form of the free base

Anion exchanger »Dowex 1 X 10« *) in the form of chloride

Anion exchanger »Dowex 1 X 10« *) used for the eighteenth time in the form of chloride

Anion exchanger "Lewatit MN" *) in the form of the free base

Anion exchanger »Lewatit MN« *) in the form of chloride

Cation exchanger »Lewatit S 100« *) in the form of the sodium salt

Wool

Powdered casein

Gelatin in sheet form, crushed

Polyamide (nylon) in the form of small cubes with an edge length of about 2 mm

80 80 80 160 80 20 80

120 350 310 310 300 320 400 320

310 310 320 320

340

618 460 465 455

1910 2110 1090

860

*) Registered trademark.

Annotation:

According to the supplier's information, the »Lewatit MN ®« anion exchanger used is a strongly basic polycondensate which contains —NR ₃ H groups. The »Lewatit S100®« cation exchanger is a styrene resin which contains - SO ₃ H - groups on the core and is strongly acidic.

The anion exchangers listed in Table 2 were all used in a water-containing state.

B e i s ρ i e 1 5

Example 1 was repeated with varying amounts of epichlorohydrin. The results obtained are entered in Table 3 below:

Tabel

Epichlorine the end Epoxy \ -JliUr viscosity hydrin prey oxygen % 50 ⁰ C G G % 8.0 cP 1850 320 6.2 7.5 3700 310 6.5 5.3 450 7400 310 8.2 380 409 538/540

Example 6

Example 1 was repeated, but instead of 1 mol of phthalic acid per 1 mol of the following acidic Connections were used. The results are summarized in Table 4:

Table 4

acid the end
prey
G Epoxy
oxygen chlorine viscosity
50 ⁰ C
cP Isophthalic acid. 290 6.8 5.2 - Terephthalic acid 300 6.6 7.5 crystallized Endomethylene
tetrahydro
phthalic acid .... 350 6.2 5.8

The product made from terephthalic acid was converted into a by recrystallization from ethyl acetate dry powder with a melting point of 100 to 103 ° C. This product had 10.8% epoxy oxygen and 1.2% chlorine.

Example 7

202 g of sebacic acid were mixed with 200 g of a commercially available water-containing anion exchanger (»Lewatit MN «[registered trademark] in the form of the free base) and 3700 g epichlorohydrin 7 hours heated to reflux. The reaction mixture was worked up in the manner described in Example 1. 330 g of a light-colored, thin-bodied product were obtained, some of which after standing for a while crystallized and had the following key figures:

Epoxy oxygen 6.7%

Chlorine 5.3%

Color according to L ο ν i b ο η d (1 "cuvette) 0.1 yellow,

0.0 red (diluted 1: 1 with acetone)

As far as this has been ascertained so far, this product dissolves in all others using this process Resins produced and lowers their viscosity while improving the elastic Properties. It is also used as a diluent for others than after the process of the invention produced epoxy compounds suitable.

Example 8

536 g of a half ester, which by reaction of phthalic anhydride with the complete Hydrogenation of diphenylolpropane produced dihydric alcohol in a molar ratio of 2: 1 15.5 kg of epichlorohydrin and 700 g of a commercially available water-containing anion exchanger were used ("Lewatit MN" [registered trademark] in the form of the free base) 8 hours under reflux heated. The reaction mixture was worked up in the manner described in Example 1. It 650 g of an epoxy compound were obtained, which had the following key figures:

Epoxy oxygen 4.1%

Chlorine 4.4%

Viscosity at 50 ^° C. 3400 cP

Color according to L ο ν i b ο η d

(1 "cell) 3.0 yellow,

0.5 red (diluted with acetone in a ratio of 1: 1)

Example 9

536 g of a partial ester, which by reaction of pentaerythritol and succinic anhydride in Molar ratio 1: 4 had been prepared, were with 11.0 kg of epichlorohydrin and 300 g of a commercially available aqueous anion exchanger ("Dowex 1 X 10" [registered trademark]) 8 hours heated to reflux. The reaction mixture was worked up in the manner described in Example 1, ίο 740 kg of an epoxy compound were obtained, which had the following key figures:

Epoxy oxygen 3.7%

Chlorine 7.0%

Viscosity at 50 ° C 1400 cP

Color according to L ο ν i b ο η d

(Ι '' cell) 0.7 yellow,

0.1 red (diluted 1: 1 with acetone)

Example 10

304 g of tetrachlorophthalic acid were mixed with 7.5 kg of epichlorohydrin and 150 g of a commercially available one water-containing anion exchanger ("Dowex 1 χ 10" [registered trademark]) 11 hours at reflux heated. The reaction mixture was worked up in the manner described in Example 1. It 306 g of a thin epoxy compound were obtained, some of which after standing for a while crystallized. The following key figures were obtained:

Epoxy oxygen 4.25%

Chlorine 35.60%

Viscosity at 5O ⁰ C 12 30OcP

Example 11

The example below shows the use of epibromohydrin in place of epichlorohydrin.

9.5 g of o-phthalic acid were mixed with 11.0 g of a commercially available water-containing anion exchanger (»Lewatit MN« [registered trademark] in the form of the sulfuric acid salt) and 300 g of epibromohydrin heated under reflux for 7 hours. The reaction mixture was worked up in the manner described in Example 1. There were 20 g of a light-colored epoxy compound with the following parameters obtain:

Epoxy oxygen 5.0%

Bromine 15.8%

Example 12

25.4 g of pyromellitic acid were mixed with 100 g of a commercially available water-containing anion exchanger ("Dowex 1x10" [registered trademark] in the form of the free base) and 740 g epichlorohydrin 9 hours heated to reflux. The reaction mixture was worked up in the manner described in Example 1. 6u 54 g of an epoxy compound were obtained which had an epoxy oxygen of 6.2%.

Example 13

150 g of dimerized abietic acid (commercial product “Dpolymerx” [registered trademark] from the company Hercules Powder) were mixed with 100 g of a commercially available water-containing anion exchanger (»Lewatit MN «[registered trademark] in the form of the

hydrochloric acid salt) and 1850 g epichlorohydrin 7 hours heated to reflux. The reaction mixture was worked up in the manner described in Example 1. There were 170 g of an epoxy compound with 2.11% Obtain epoxy oxygen.

Example 14

By reacting diphenylolpropane (bisphenol A) with monochloroacetic acid in a molar ratio 1: 2 an ether carboxylic acid with two carboxyl groups in the molecule was produced. 52 g of this Product were mixed with 100 g of a commercially available water-containing anion exchanger ("Lewatit MN" [registered trademark] in the form of the hydrobromic acid salt) and 1700g epichlorohydrin 7 hours heated to reflux. The reaction mixture was worked up in the manner described in Example 1. 60 g of an epoxy compound were obtained which contained 2.5% epoxy oxygen.

Example 15

From 1 mole of octadecanediol-1,12 and 2 moles of phthalic anhydride a half ester was produced. 100 g of this ester together with 1800 g of epichlorohydrin and 100 g of the anion exchanger "Lewatit MN" (registered trademark containing water) in Heated form of the free base at reflux for 7 hours. The reaction mixture was in the example 1 described way worked up. 130 g of an epoxy compound were obtained which contained 2.4% Has epoxy oxygen. This product is particularly elastic after hardening and is suitable for Elastification of other epoxy compounds.

Example 16

A partial ester was prepared from 1 mole of castor oil and 3 moles of phthalic anhydride. 100 g of this product were converted into an epoxy compound in the same manner as described in the previous example. The yield was 125 g. The product had a Epoxydsauerstoffgehalt of 2.7% and a viscosity of 460 cP (at 5O ⁰ C).

Example 17

To 200 g of molten phthalic anhydride 150 g powdered oxyethylated methylcellulose was added (commercial product "Culminal" [registered trademark] C 3003/300 the patentee) in a nitrogen atmosphere at 14O ⁰ C with stirring. After a reaction time of 30 minutes at 140 ^° C., the mixture was slowly cooled. After cooling, the product, which had solidified in the meantime, had an acid number of 315 and an OH number of 34.

100 g of the product described above with 1800 g of epichlorohydrin and 100 g of des Anion exchanger »Lewatit MN« (registered trademark containing water) in the form of the free base Heated under reflux for 7 hours. The reaction mixture was that described in Example 1 Way worked up. It became an epoxy compound with a content of 4.7% of epoxy oxygen obtain. The yield was 110 g.

Example 18

100 g of a dimerized fatty acid (commercial product "Emery" [registered trademark] 3065-S) were with 1800 g epichlorohydrin and 100 g of the anion exchanger "Lewatit MN" (registered trademark water-containing) in the form of the hydrochloric acid salt heated under reflux for 7 hours. The reaction mixture was Worked up in the manner described in Example 1. There were 120 g of an epoxy compound with 3.9% Obtain epoxy oxygen.

Example 19

100 g of citric acid were mixed with 1800 g of epichlorohydrin and 100 g of the anion exchanger »Lewatit MN «(registered trademark containing water) in the form of the sulfuric acid salt for 12 hours under reflux heated. The reaction mixture was worked up in the manner described in Example 1. It 150 g of an epoxy compound with 5.8% epoxy oxygen were obtained.

B e i s ρ i e 1 20

100 g of aconitic acid were mixed with 1800 g of epichlorohydrin and 100 g of the anion exchanger "Lewatit MN" (registered trademark containing water) in the form of the hydrochloric acid salt heated under reflux for 10 hours. The reaction mixture was in the example 1 described way worked up. 130 g of an epoxy compound were obtained which contained 6.7% Has epoxy oxygen.

Example 21

The following example shows that the ion exchanger even without the simultaneous presence of Water is catalytically effective. At the same time, this example shows that without the addition of water, the color of the Product is a little less bright. 2000 g epichlorohydrin and 150 g of the anion exchanger »Lewatit MN «(registered trademark containing water) were stirred in a distillation apparatus for Boiling heated. The heating was continued until there was no water in the distillate which had passed over more was to be proven. At this point in time the bottom temperature was 117 ° C. There were a total of 150 g of distillate passed over.

82 g of o-phthalic acid were added to the dehydrated mixture and refluxed for 6 hours heated. The reaction mixture was then in the manner described in Example 1 worked up. 110 g of an epoxy compound were obtained which had the following key figures:

Epoxy oxygen 6.5%

Color according to Lovibond (1 "cuvette) .. 11.0 yellow,

1.8 red

Example 22

17 g (Vio ^M ° l) thiophenedicarboxylic acid-2.5, 370 g (4 mol) technical-grade epichlorohydrin with a water content of 0.1% and 30 g of a water-containing commercially available anion exchanger ("Lewatit MN" [registered trademark]) in the form of the hydrochloric acid salt were refluxed for 7 hours. The reaction mixture was then worked up in the same way as described in Example 1. 28 g of an epoxy compound with the following key figures were obtained:

Epoxy oxygen 5.5%

Chlorine 7.9%

Example 23

16 g (Vio mol) furandicarboxylic acid-2.5, 370 g (4 mol) technical epichlorohydrin with a water content of 0.1% ^and 30 g of a water-containing, commercially available anion exchanger (»Lewatit MN [registered trademark]) in the form of the hydrochloric acid salt were refluxed for 7 hours. The reaction mixture was then worked up in the same manner as described in Example 1. 30 g of an epoxy compound were obtained which had an epoxy oxygen of 6.1% ^and a chlorine content of 7.0%.

B e i s ρ i e 1 24

98 g (V2 mol) methyl-endomethylene-tetrahydrophthalic acid (so-called methylnadic acid), 1850 g (20 mol) technical epichlorohydrin with a water content of 0.1% ^{and <} i 150 g water-containing commercially available anion exchanger ("Leatit MN" [registered trademark]) in the form of the free base were refluxed for 7 hours. After the usual work-up, 125 g of an epoxy compound with the following key figures were obtained:

Epoxy Oxygen 5.3%

Chlorine 6.6%

Example 25

172 g of hexahydrophthalic acid, 3700 g of technical grade epichlorohydrin and 150 g of a commercially available one water-containing anion exchanger (»Lewatit MN« [registered trademark]) in the form of the free base were refluxed for 7 hours. The work-up resulted in 305 g of an epoxy compound the following key figures:

Epoxy oxygen 6.9%

Chlorine 6.85%

Viscosity at 50 ° C 390 cP 4 <>

The work-up resulted in 368 g of an epoxy compound with the following key figures:

Epoxy oxygen 5.5%

Chlorine 4.9%

Viscosity at 50 ^° C. 5100 cP

Claims (3)

Patent claims: 1. Process for the preparation of curable compounds containing epoxy groups by reacting compounds containing more than one carboxyl group in the molecule with haloepoxyalkanes, which contain the halogen adjacent to the epoxy group and which are used in an amount of more than 2 mol per carboxyl group, with increased Temperature and in the presence of organic catalysts, characterized that the catalysts are high molecular weight organic insoluble in the reaction mixture Compounds used that a) salt-like groups, or b) Groups which are converted into salt-like groups under the reaction conditions can, or c) acid amide groups contain, and that the reaction is optionally carried out in the presence of small amounts of water performs. 2. The method according to claim 1, characterized in that the reaction mixture is water up to about 3%, based on the haloepoxyalkane, added. 3. The method according to claim 1 and 2, characterized in that the haloepoxyalkane is used in a larger excess, preferably 10 to 40 mol per carboxyl group and more. Example 26 216 g of naphthalenedicarboxylic acid-2,6, 3700 g of technical Epichlorohydrin and 200 g of a commercially available water-containing anion exchanger (»Lewatit MN «[registered trademark]) in the form of the free base were refluxed for 10 hours. Considered publications: German Patent No. 944 995; German patent application: K 10079 IVb / 39c (published on July 1, 1954); French Patent No. 1,066,037; German Auslegeschrift No. 1 033 204; P a q u i η, epoxy compounds and epoxy resins, 1958, pp. 173 to 175; Chemische Technik, Vol. 10, 1958, pp. 193 to 196. 409 538/540 3.64 © Bundesdruckerei Berlin