DE1191107B - Process for the production of soluble reaction products from glycidyl polyethers and phenol-aldehyde condensation products which result in pore-free coatings on curing - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number:
File number:
Registration date:
Display day:

C08g

German class: 39 c-30

1191107
N10216IVd / 39c
17th February 1955
April 15, 1965

By heating with phenol-aldehyde condensation products, glycidyl polyethers can become reactive Containing hydroxyl groups are hardened. Depending on the reaction conditions in the condensation of a phenol with an aldehyde, products can be obtained which exclusively phenolic hydroxyl groups or both phenolic and etherified or non-etherified contain alcoholic hydroxyl groups, the latter being known as resoles are.

It has been found, however, that glycidyl polyethers hardened in this manner having an average molecular weight of at least 1,600 when used as coating masses do not result in a satisfactory uniform surface, but rather in a larger one or smaller dimensions have craters and / or pores. As a result of these flaws, these Coatings do not provide the desired protection against chemical and mechanical effects.

These disadvantages can be eliminated according to the invention by using special soluble reaction products from glycidyl polyethers and phenol-aldehyde condensation products.

The invention relates to a process for the production of soluble reaction products of glycidyl polyethers and phenol-aldehyde condensation products, which result in pore-free coatings on curing, which is characterized in that a glycidyl polyether of a polyhydric phenol with an average molecular weight of 1200 to 4000 ^{1 1} to 4 hours at a temperature between 110 and 150 ° C with a resol, preferably in solution, to react, the resol containing an average number of more than two reactive groups per molecule in the form of phenolic and etherified or non-etherified alcoholic hydroxyl groups and the glycidyl polyether and the resole are present in weight ratios between 70:30 and 80:20.

It is already known to use resoles and low molecular weight and therefore liquid glycidyl polyethers To harden novolaks, however, the problem arises with such low molecular weight polyepoxides the formation of pores or craters does not appear at all, and therefore there are no special ones Measures for the preparation of a soluble reaction product described in the context of the invention, which is only converted into the insoluble and infusible state through heat hardening will. In addition, only resols and no novolaks can be used in the context of the invention.

Method of producing when hardening
pore-free coatings resulting in soluble
Reaction products from glycidyl polyethers
and phenol-aldehyde condensation products

Applicant:

Bataafse Petroleum Maatschappij N.V.,

The hague

Representative:

Dipl.-Chem. Dr. phil. E. Jung, patent attorney,

Munich 19, Romanplatz 10

Named as inventor:

Pieter Bruin,

Nantko Kloos, Amsterdam (Netherlands)

Claimed priority:

Netherlands of February 19, 1954 (185 265)

In addition, practical experience has shown that with glycidyl polyethers with an average molecular weight of at least 1600, the majority represent solid substances, pore formation can only be avoided if the above special procedural conditions described are observed.

From the inventively produced soluble reaction products Coatings made be prepared by heating to a temperature between 230 ° C, in particular between 170 and 200 ⁰ C, to cure, wherein the heating time depending on the temperature used is between 5 minutes and 3 hours, preferably between 10 and 60 minutes, can fluctuate.

The glycidyl polyethers used as the starting material of a polyhydric phenol with a average molecular weight of 1200 to 4000, for example by reaction of a divalent Phenoles, such as 2,2-bis- (4-oxyphenyl) -propane, with epichlorohydrin or dichlorohydrin in alkaline Medium are generally com-

509 539/416

3 4

Pricked mixtures, which in particular contain molecules of the following structural formula:

O O

CH ₁ -CH-CH ₁ - (ORO-CH ₈ -CHOH-CHu) _n -ORO-CH ₈ -CH - CH ₈

Here , R denotes a divalent, substituting gel and then no longer can be used

th or unsubstituted phenylene radical, and η is can.

an integer. Those to be used according to the invention The leading to the soluble reaction product

Ending glycidyl polyethers should have an average number of conversion can advantageously have in the presence of epoxy groups per molecule, the io catalysts, preferably acidic catalysts,

is greater than one. be carried out, for example H ₃ PO ₄ , p-toluene

The resols to be used can be derived from sulfonic acid, benzene disulfonic acid and oxalic acid,

Monohydric as well as polyhydric phenols The invention is illustrated by the following examples

be derived, for example from phenol, cresol, explained in more detail:

p-octylphenol, resorcinol, alkylresorcinol or the glycidyl polyether mentioned in the examples

2,2-bis (4-oxyphenyl) propane. The used Re- was from 2,2-bis- (4-oxyphenyl) -propane and epichlor-

brines should be miscible with the glycidyl polyethers hydrin was produced in an alkaline medium.

or during the course of the reaction, the parts given are parts by weight, and the

and remain miscible even while cooling. Percentages are percentages by weight.

Although the reaction between the glycidyl poly- so

ether and the resol also in the melt

can be performed, it is preferred to use the same in 60 g of a glycidyl polyether with a mean

Presence of solvents, for example number of 1.45 epoxy groups per molecule, one

Mixtures of the ethyl ether of ethylene glycol acetate, softening point of 131 ° C and a diameter of

and toluene or from diacetone alcohol and xylene, 35 average molecular weight of 2900 were at a

perform. After the reaction has ended, a temperature of 120 ° C is added to a mixture of the same

practically always a completely dissolved part of diacetone alcohol and xylene, even in the cold.

homogeneous and clear solution was obtained, even if 86 g of a 30% strength were then added to this

The resols used were originally given with the Gly-butanol solution of a resol, which is made from phenol

cidyl polyethers were not miscible . 30 and formaldehyde had been produced. These

When the reaction is carried out in solution, the mixture has been mixed for IV2 hours at a temperature such that the glycidyl polyether is generally heated in between 116 and 120 ° C. At the beginning and in the form of an approximately 40 to 60% solution, use ⁸ A or IVs hours after the start of heating , and the resole can be added to this in dissolved or undissolved form to the samples of the reaction product formed . When the resol is solid and only took 35. These were made with a mixture of equal parts of the ethyl ether of ethylene glycol acetate solution of the glycidyl polyether can be dissolved in the holes with difficulty or not at all, and toluene on a viscosity suitable for spraying is advisable, the resole diluted as a solution in such a viscosity . Add the diluted solution obtained, solvent which is then degreased with the resin and can be mixed with the sandblasting solution. 40 fan-treated iron sheets sprayed on. To

The soluble reaction product can, if desired, evaporate the solvents at room temperature

thinned and can then be applied as a coating, the coatings for 30 minutes at a

wear, for example by spraying, brushing, hardened at a temperature of 200 ° C.

or immersion, and then this can be.

Coating are hardened. As a diluent 45 that the formed from the sample taken first

for the soluble reaction product , both craters and pores in the deten coating mass can be used

Paint industry known solvents used. The coatings used by the after one

be, for example, the ethyl ether of ethylene reaction time of ³ A hours taken sample

glycol acetate, the monoethyl ether derived from ethylene glycol, showed only a limited amount

Benzyl alcohol or mixtures thereof with aromatic 50 such defects, while the coatings of the

see hydrocarbons like xylene or toluene. last sample completely smooth and free of craters

The most favorable reaction time for the reaction between and pores were.

see the Glycidylpolyäther and the resole was off the flexibility of the cured coatings, the so hängjg of the other conditions used, for example, probably by bending over a mandrel of 1.562 the temperature, the type of verwen- mm 55 diameter as determined by folding It was found that the polyether and the resol, as well as the ver, were very good, and it was found that the ratio in which these components to the reaction increased with increasing reaction time.
to be brought. For this reason, the impact resistance was also excellent, the fastest reaction time was determined for each individual case, the latter was determined by means of a weight of 910 g in which, after various reaction times, samples 60 were taken, which were hemispherical at the lower end and the coatings produced from them (diameter 9 mm) and hardened from one. These hardened test surfaces of a height of 105 cm on the back of the specimen are dropped for the presence of craters and pore plates, and are tested for them. The formation of such defects takes care that the coating is not damaged. generally with increasing reaction time from up to 65 The resistance to water and it completely or almost completely ceases. The solvents were also good. The coating reaction, however, should not remain in contact for so long during more than 6 hours of contact that the product which is formed begins to react with boiling water and is unchanged

no softening when exposed to methyl ethyl ketone for 5 minutes at room temperature were exposed. When the coatings were treated with a boiling, 20% alkaline solution no noticeable changes after one hour.

Example 2

The reaction described in Example 1 was repeated with a phenol-formaldehyde resole resin, which was made from 2,2-bis (4-oxyphenyl) propane and formaldehyde in the following way:

334 g of 2,2-bis (4-oxyphenyl) propane were dissolved in 584 g of an aqueous 30% solution of formaldehyde suspended and then 354 g of a 33% sodium hydroxide solution into the mixture stirred in. The temperature was kept below 40 ° C. during this process. The solution was cloudy at the beginning clear after a few hours, and it stood for 6 days at a temperature of about 23 ° C- ao calmly. Then 260 g of a 53% sulfuric acid were added with careful stirring, whereupon the clear solution separated into two layers, namely an upper water layer and one lower resin layer. The resin layer was separated »5 and washed with 500 ecm of water each time, up to about 3 ecm of a 0.5 sodium hydroxide solution to neutralize 100 ecm of the wash water sufficient. The resin layer was then in a vacuum and at a bubble temperature of 35 ° C dried.

The product thus obtained was dissolved in 435 g of n-butanol and this solution was filtered and distilled. At a temperature of 94 to 100 ° C., a mixture of n-butanol and water passed over. Upon reaching 300 g of n-butanol were added to a distillation temperature of 100 ° C. The distillation continued until the distillation temperature rose to 120 ° C. The etherified one produced in this way Resin was made with such an amount of a 40% solution of that described in Example 1 Glycidpolyäthers in a mixture of equal parts of diacetone alcohol and xylene added that the The ratio of the polyether to the phenolic resin was 75:25. The resulting solution was IV2 hours heated for a long time to a temperature of 135 to 140 ° C, with at the beginning or 1 and IV2 hours after heating Samples were taken from the solution and treated further in the manner described in Example 1 became.

The cured films made from the first samples showed craters and pores, while the films from the sample taken one hour after the start of heating, this deficiency was only very limited showed a low degree. The last sample yielded films that were perfectly smooth and free from defects was.

The films also showed very good flexibility, hardness and impact resistance. Resilience to solvents was also excellent as it was treated for 30 minutes no softening occurred with acetone at room temperature.

It was also found that the water resistance (more than 6 hours of treatment with boiling distilled water) and the resistance to caustic alkalis was very good, for example, it was found after treatment with 20% caustic soda solution for 8 hours practically no damage.

No protection is claimed here for the production of the coatings.

Claims (1)

Claim: Process for the production of soluble reaction products which result in pore-free coatings on curing from glycidyl polyethers and phenol-aldehyde condensation products, thereby characterized in that a glycidyl polyether of a polyhydric phenol with a average molecular weight of 1200 to 4000 V2 to 4 hours at a temperature between 110 and 150 ° C with a resol, preferably in solution, to react, the resol an average number of more than two reactive groups in the form of phenolic per molecule and contains etherified or non-etherified alcoholic hydroxyl groups and the Glycidyl polyether and the resole are present in weight ratios between 70:30 and 80:20 are. Considered publications:
U.S. Patent No. 2521912.