DE1912485C3 - Hardener for hardening polyepoxides - Google Patents

Description

characterized in that the hardening agent is of the following composition:

a) 35 to 55 percent by weight of an adduct of 2 moles of ethylenediamine, diethylenetriamine or hexamethylenediamine and 1 mole of bisphenol A glycidyl ether with one Epoxy equivalent of 190 or 250,

b) 43 to 30 percent by weight bis (aminomethyl) benzenes or bis (aminomethyl) cyclohexane !! or 2,2.4- (2,4,4-) trimethylhexamethylene diamines, and

c) 22 to 15 percent by weight phenol accelerator, where a), b) and c) together 100 percent by weight.

Implemented 2. A process for the preparation of the curing agent according to claim 1, characterized in that the adduct a) by stirring it is combined bisphenol-A-glycidyl ether in the polyamide or by shaking while avoiding local excesses, and then at temperatures between 50 and 15O ⁰ C where component b) can be present during adduct production or is subsequently stirred into the finished adduct and component c) is already present as a phenol or phenol mixture during adduct production or subsequently at normal or elevated temperature in the mixture of components a) and b) is added and dissolved.

3. Use of the hardening agent mentioned in claim 1 for the manufacture of elastic and chemical-resistant coatings and moldings.

It is known aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamines, such as z. B. diethylenetriamine or triethylenetetramine, for curing epoxy resins at room temperature use. However, the hardening products obtained in this way are relatively brittle, and Their water and acid resistance is only moderate, especially when using an excess of amine. For many purposes, the development of heat occurring during curing is a disadvantage, since z. B. in the production of larger castings due to poor heat dissipation, especially inside of the cast body maximum temperatures of over 200 ° C can be reached, with stress cracks, discoloration and additional shrinkage affect the properties of the hardening products. It is known to add phenols to polyamines, to accelerate the curing reaction, which occurs especially at low temperatures, e.g. B. to around the zero point, hardly runs at all and too hardened at high humidity Coatings and moldings with sticky and cloudy surfaces leads. The addition of phenols does accelerate the reaction and lower the curing temperature, however the chemical properties of the hardened products are adversely affected.

It is also known to use epoxy resins with adducts of epoxy compounds and certain polyamines to harden to the surface hardening of the amines, which in humidity lead to the so-called "Blue tarnish", d. H. the formation of a cloudy, sticky surface leads to improvement. This However, amine adducts also fail at lower temperatures, for example below 15 ° C., at which the Hardening is too slow. Also leave the chemical properties of the hardened products to be desired.

In the German Offenlegungsschrift 11 17 871 is a process for curing polyepoxides by adducts of epoxies and at least three amino hydrogen atoms containing polyvalent amino compounds, which is characterized is that an adduct of an epoxide with di- or tri - («- aminomethyl) benzene is used as an adduct used. According to the information in column 4, line 46, to column 5, line 56, phenol can be used as a hardening accelerator can also be used. A reworking of this known process has been done with phenol as a hardening accelerator show that the plastic layers obtained therewith in use with Water whiten and soften, so that this process is not suitable for high-quality plastic coatings to manufacture.

The object of the present invention was to find a curing agent in which the aforementioned Disadvantages do not occur.

The invention relates to a curing agent for curing polyepoxides based on

a) polyamine diepoxy adducts,

b) polyamines and

c) Phenol accelerators based on mono- and / or di-phenols that are mononuclear or are double-ringed and can be substituted,

which is characterized in that the hardening agent is of the following composition:

a) 35 to 55 percent by weight of an adduct of 2 moles of ethylenediamine, diethylenetriamine or hexamethylenediamine and 1 mole of bisphenol A glycidyl ether with an epoxy equivalent of 190 or 250,

b) 43 to 30 percent by weight of bis (aminomethyl) benzenes or bis-caminomethyl-cyclohexanes or 2,2,4- (2,4,4-) trimethylhexamethylene diamines, and

c) 22 to 15 percent by weight phenol accelerator, with a), b) and c) together 100 percent by weight result.

Another object of the invention is a method for producing the curing agent, which thereby

S 3 4

is characterized in that the adduct a) consists of another embodiment of the hardener Ren the bisphenol A glycidyl ether in the polyamine in that components a), b) and c) for Heroder Any excess is used by shaking while avoiding local deposition of the viscosity is combined and then at temperatures that can be inert, such as. B. the aromatics doors between 50 and 150 ° C is implemented, whereby 5 toluene or xylene, lower esters such as ethyl acetate, component b) in the production of adducts, ethylglycol acetate or ketones, such as methyl isobutylgen can be, or subsequently in the finished ketone or cyclohexanone, or the hardening Adduct is stirred in and component c) may be involved as a part, such as alcohols, eg. B. Phenol or phenol mixture even with the adduct benzyl alcohol, furfuryl alcohol or polyols, such as production is present or subsequently at norma- io Glycerin.

ler or elevated temperature in the mixture of the aforementioned hardening agent], which as combination components a) and b) added and to dissolve nation of components a) to c) are available is brought. for hardening a wide variety of epoxy resins

The invention also relates to the use, epoxy resins being such compounds

tion of the hardener for the preparation of 15 genes should be understood, which are more than one

elastic and chemical-resistant coating- have epoxy groups per molecule. Exemplary

genes and moldings. may be mentioned: polyglycidic ethers of polyvalent ones

The following phenols in phenols such as 4,4'-oxydpheny! Propane, 4,4'-dioxy-

Question: phenol, o-, m-, p-cresol, xylenols, resorcinol, diphenylmethane, phenol-formaldehyde resins, 4,4'-

Pyrocatechol, hydroquinone, phloroglucinol, pyro- 20 Dioxydiphenylsulfon, polyglycid ether of oxyacrylic

gallol, «- and / ^ - naphthol, p.-tert.-butylphenol, bis-carboxylic acids, as they are in the German Auslegeschrift

phenol A and 4,4'-dihydroxydiphenylmethane. 12 22 067 are described, and polyglycidyl ether from

In addition, there are the polyvalent thiols as novolaks or resols, such as bismercaptomethylbenzene,

known acidic or alkaline condensation basic polyepoxides, z. B. from bis- (4-monomethyl-

products of the phenols mentioned with aldehydes, 25 aminophenyl) methane. Aniline or 4,4'-diamino-di-

z. B. formaldehyde, in question. phenylmethane, polyepoxides based on s-triazine, poly-

The production of the adduct as component a) glycidyl ether from polyhydric alcohols, such as 1,4-from the epoxy compounds and polyamines butanediol, glycidyl ester of di- and polycarboxylic acid are carried out, by rening the epoxy compounds, such as diglycidyl phthalate, N, N-diepoxyin stir in the amine or mix it with propyl oxamide, triglycidyl cyanurate, epoxy by shaking, taking care not to use too large amounts of dation products of polyunsaturated unites admits so that local excesses avoided bonds, such as vegetable oils and their deterioration. Conversion products, epoxidation products of

You can also use both components in solution in di- and polyolefins, such as butadiene, vinylcyclohexene,

a neutral, inert organic liquid, 35 polybutadiene, epoxidation products of bicyclo-

turn, with dioxane in particular being suitable heptene derivatives or cyclohexene or cyclopentene

has proven. After the adducts have been prepared, condensed ring systems containing rings are produced. Further

the solvent removed again. Glycidyl polyether of polyhydric phenols such. B.

The excess of amine to be used in the case of the l, l-bis (4-oxyphenyi) methane, the hydrochi-

Production of the adduct should preferably be at least 40 nons, resorcinol, 1,3-bis- (4-oxyphenyl) -2-

be at least 90%, d. H. there are per equivalent of oxypropane and similar compounds. It is possible

Epoxy compound used two equivalents of amine borrowed, mixtures of the aforementioned polyepoxides and

det. In the case of diamines, they are preferably used one after the other.

1 mole of the amine per epoxy group in the molecule. In the inventive use of the hardening

Exceeding the excess amount is possible. The hardening of the polyepoxy resins can be used as a curing agent

The conversion to the adduct takes place expediently depending on the reactivity of the resins or the polyamines

Mostly at temperatures between 50 and 150 ° C, at room temperature or much higher

the mixing temperature being carried out at relative temperatures. Usually

Chosen low and then preferably something comes a temperature range from 0 to 150 ° C in

can be increased above 100 ° C, but also higher. 5 ° consideration. Appropriately, these new types of hardening

The selection of the components from which the ad- dant is used in such amounts that the

product has been formed is made so that the epoxy resin is equivalent, however, in many cases

Adducts have molecular weights below 1000. len an excess of up to 50% or a deficit of up to

The polyamine of component b), which is readily possible with 25% of the hardener combination Polyamine 55 used in adduct production. The curing reaction can optionally go through is different, can be added in the production of adducts, addition of alcohols, carboxylic acids, epichlorohydrate but can also be added subsequently to the finished product and hydrogen halide, as well as by delivered items Adduct are stirred in. The addition of polyamidoamines can also be accelerated or reduced the phenol which represents component c) or which flows.

It should be emphasized that with the new hardening countermeasures it should be emphasized that the phenol mixture is already being produced during the production of the adduct be or afterwards at normal or average even at low temperatures up to increased temperature in the mixture of the components zero point around and possibly at - 5 ° C tan a) and b) are added and brought to dissolve and hardening takes place. Even with high air, humidity and in some cases even under water

Components a), b) and c) will preferably be cured. By suitable choice of

selected so that the curing component a), b) and c) according to the invention can be the desired

medium a Höppler viscosity at 25 ° C of 100 reactivity, elasticity and chemical resistance

up to 5000 cP. match to the respective application.

When the novel hardeners are used to produce coatings, one can achieve good flow and good pigmentability.

The process according to the invention can be used to obtain cured epoxy resins which have excellent resistance to water, acids and chemicals, good surface gloss and, in some cases, very good elasticity. They are well suited for the production of large-volume castings, e.g. B. for toolmaking. But they can also be used as laminating resins, adhesives, putties, as synthetic resin cement and as coating, lining and repair material for concrete floors and concrete pipes. In contrast to many common amine hardeners, the novel combination hardeners described are compatible with bitumen, asphalt and similar tar products on their own and in combination with epoxy resins. Such combinations with tar products may be advantageously in _surface-ao Chen and corrosion protection, used in road construction and civil engineering. Examples include: casting and adhesive compounds, sealing and insulating material.

The epoxy resins to be hardened can be filled with fillers such as silicon dioxide, hydrated aluminum oxide, Titanium dioxide, glass fibers, wood flour, mica, graphite, calcium silicate and / or sand as well the usual pigments with grain sizes from 0.5 to 5 mm can be mixed.

The following examples explain the preparation of the hardeners according to the invention and their use.

Adduct A

To 1200 g of ethylene diamine were added with stirring at 30 to 6O ⁰ C in portions in 2 hours 1900 g of a polyglycidyl ether of bisphenol-A-based optionally with an epoxy equivalent of 190th After the addition was complete, 605 g of ethylenediamine were distilled off again at 55 to 100 ° C. under reduced pressure. The residue had an amine number of 446 and an HAV of 62.5.

example 1

400 g of adduct A were mixed with 425 g of 2,2,4- (2,4,4-) trimethylhexamethylenediamine and 175 g of phenol mixed at 50 ° C. The hardener has a HAV of 64.3, a viscosity, measured in the Höppler viscometer, at 25 ° C., of 1805 cP and a pot life (i.e. the time it takes for a mixture of 100 g of a bisphenol-A-based polyglycidyl ether to gel with an epoxy equivalent of 190 and 34 g of the curing agent at room temperature elapsing time) of 19 min.

Hardening: 190 g of a bisphenol A-based polyglycidyl ether with an epoxy equivalent of 190 are mixed with 64.3 g of the hardening agent and poured into 4 mm thick sheets without bubbles. After 24 hours of curing at room temperature, the plates are annealed for 2 hours at 120 ⁰ C. In addition, coatings are applied to glass and metal plates in the appropriate mixing ratio. Testing of mechanical properties and chemical resistance gave excellent results. A layer on a glass plate was dust-dry after 65 minutes and after 6 hours it was tack-free and completely dried to a high gloss.

35

45

Example 2

450 g of adduct A were mixed with 425 g of a mixture of 7% 1.3 and 30% 1,4-bis (aminomethyl) benzene and 175 g of phenol mixed at 50 ° C. The hardener has an HAV of 57.5. a viscosity in the Höppler viscometer, measured at 25 "C, of 135OcP, a top time (100 g of a polyglycidyl ether based on bisphenol A mixed with an epoxy equivalent of 190 and 30 g of the curing agent) for 20 minutes and one amine number! \ on 550

Hardening: 190 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 are mixed with 57.5 g of the hardening agent and poured bubble-free to form 4 mm thick plates. To After curing for 24 hours at room temperature, the plates are tempered at 120.degree. C. after 2 hours. Besides that are in the appropriate mixing ratio Coatings made on glass and metal plates. Testing of mechanical properties and chemical resistance gave excellent results. One layer on a glass plate was dust-dry after 155 min and after 5 h sticky and high-gloss dried through.

Example 3

500 g of adduct A were mixed with 325 g of 2.2.4- (2,4,4-) trimethylhexamethylenediamine and 175 g of phenol mixed at 50 ° C. The hardener has a HAV of 70.5, a viscosity in the Höppler viscometer, measured at 25 C, of 835OcP, a pot life (100 g of a bisphenol A-based polyglycidyl ether with an epoxy equivalent of 190 and 37 a of the curing agent mixed) of 17 min and an amine number of 425.

Hardening: 190 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 are mixed with 70.7 g of the hardening agent and poured bubble-free to form 4 mm thick plates. To After curing for 24 hours at room temperature, the plates are tempered at 120 ° C. for a further 2 hours. Besides that coatings are applied to glass and metal plates in the appropriate mixing ratio. The test of the mechanical properties and chemical resistance gave excellent results Results. A layer on a glass plate was dust-dry after 160 minutes and tack-free after 4 1/2 hours and dried to a high gloss.

Example 4

500 g of the Addukls A were mixed with 325 g of a mixture of 70% 1.3 and 30 ° / ol, 4-bis (aminomethyl) benzene and mixed 175 g of phenol at 5O ⁰ C. The curing agent has an HAV of 64.3, a viscosity in the Höppler viscosimeler, measured at 25 ° C., of 6970 cP, a pot life (100 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 and 34 g of the curing agent mixed) of 34 min and an amine number of 469.

Hardening: 190 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 are mixed with 64.3 g of the hardening agent and poured bubble-free to form 4 mm thick plates. To After curing for 24 hours at room temperature, the plates are tempered at 120 ° C. for a further 2 hours. Except-

] ■

For this purpose, coatings are made on glass and metal plates in the appropriate mixing ratio. The tests of the mechanical properties and chemical resistance showed excellent Results. A layer on a glass plate was dust-dry after 150 minutes and after 3 hours non-sticky and dry to a high gloss.

Adduct B

10

618 g of diethylenetriamine were heated to 70 ° C. and 750 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 250 were added at this temperature for 1 hour. After 30 min further thorough Verrührens 300 g of diethylene triamine were distilled again at 120 to 150 ⁰ C under vacuum. The adduct then had a HAV of 96.5.

20th

Example 5

510 g of adduct B were at 50 ° C with 332 g 2,2,4 - (2,4,4 -) trimethylhexamethylenediamine and 177 g of phenol mixed. The hardener has a HAV of 69.7, a viscosity in the Höppler viscometer, measured at 25 ° C., of 10,720 cP, a pot life (100 g of a bisphenol A-based polyglycidyl ether with an epoxy equivalent of 190 and 36.5 g of the hardening agent mixed) of 34 min, measured at 20 ° C., and an amine number of 447.

Hardening: 190 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 are mixed with 69 g of the curing agent and Potted bubble-free to form 4 mm thick plates. After curing for 24 hours at room temperature the plates were tempered for a further 2 hours at 120.degree. In addition, in the appropriate mixing ratio Coatings made on glass and metal plates. Tests of mechanical properties and chemical resistance gave excellent results. One layer on a glass plate was dust-dry after 225 min, after 5 '/' 2 h Non-tacky and high-gloss when dried through and was characterized by a high level of water resistance out.

Adduct C

928 g of hexamethylenediamine were heated to 70 ° C. and at this temperature in portions over the course of 2 h with a total of 760 g of a polyglycidyl ether based on bisphenol A with one epoxy equivalent of 190 added. After 30 minutes of further thorough stirring, 460 g of hexamethylenediamine were added at 80 to 150.degree distilled off again. The adduct then had a HAV of 101.

Example 6

614 g of adduct C were mixed with 399 g of 2,2,4 - (2,4,4 - yrrimethylhexamethylenediamine and 115 g of phenol at 50 ° C. The curing agent has an HAV of 76.0, a viscosity in the Höppler viscometer, at 25 ° C measured, of 2305 cP, and a pot life (100 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 ⁶ S and 40 g of the curing agent mixed) of 34 min, measured at 20 ° C, and an amine number of 421 .

Hardening: 190 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 are mixed with 76 g of the hardening agent and poured into 4 mm thick sheets without bubbles. After curing for 24 hours at room temperature, the plates are heated at 120 ° C. for a further 2 hours. In addition, coatings are applied to glass and metal plates in the appropriate mixing ratio. The tests of the mechanical properties and chemical resistance gave excellent results. A layer on a glass plate was dust-dry after 180 min, after 6 h ₂ ¹ Z tack-free and high-gloss by dried, and was characterized by a large water resistance.

Example 7

450 g of adduct A were mixed with 425 g of a mixture of 70% 1.3- and 30% 1,4-bis (aminomethy!) - cyclohexane and 175 g of phenol mixed at 50 "C. The curing agent has an HAV of 58, one Viscosity in the Höppler viscometer, measured at 25 ° C, from 1300 cP. a pot life (100 g of a polyglycidyl ether bisphenol A based with an epoxy equivalent of 190 and 30 g of the curing agent mixed) of 15 min and an amine number of 550.

Hardening: 190 g of a polyglycidyl ether based on bisphenol Α with an epoxy equivalent of 190 are mixed with 58 g of the hardening agent and poured into 4 mm thick sheets without bubbles. After 24 hours of curing at room temperature, the plates are annealed for 2 hours at 120 ⁰ C. In addition, coatings are made on glass and metal plates in the appropriate mixing ratio. Testing of mechanical properties and chemical resistance gave excellent results. A layer on a glass plate was dust-dry after 140 minutes and after 4 hours it was tack-free and completely dried to a high gloss.

Example 8

500 g of adduct A were mixed with 325 g of a mixture of 70% 1.3 and 30% 1,4-bis (aminomethylkyclohexane and 175 g of phenol mixed at 50 ° C. The hardener has an HAV of 65, a viscosity in the Höppler viscometer, measured at 25 ° C., of 5850 cP, a pot life (100 g of a Polyglycidyl ethers based on bisphenol A with an epoxy equivalent of 190 and. 34 g of the hardener mixed) of 31 min and an amine number of 460.

Hardening: 190 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 190 are mixed with 65 g of the hardening agent and poured bubble-free to form 4 mm thick plates. To After curing for 24 hours at room temperature, the plates are tempered at 120 ° C. for a further 2 hours. In addition, in the appropriate mixing ratio Coatings made on glass and metal plates. Tests of mechanical properties and chemical resistance gave excellent results. One layer on a glass plate was dust-dry after 140 min and dried out to a high gloss and tack-free after 3 h.

Claims (1)

Patent claims: 1. Hardening agent for hardening polyepoxides on the basis of a) polyamine diepoxy adducts, b) polyamines and c) Phenol accelerators based on mono- and / or di-phenols, which are mononuclear or binuclear, and can be substituted,