DE1495369A1 - Process for the production of polyether melamines - Google Patents

Description

CHEMISCHE WERKE HÜLS AG. Mar}, July 21, 1964

- Patent Department - 1408 / Br

U95369

TJhser sign: O. Z. 1869

Process for the production of polyether melamines

It is well known that melamine-formaldehyde resins are obtained in the production of melamine-formaldehyde resins Depending on the melamine-formaldehyde ratio used, initially via mono-, bis- and tris-methylol compounds Hexa-r methylol compounds of melamine

NH-CH ₀ OH

CH ₀ -HN- C C-NH-CH ₀ -OH or ·

CH- 1 \ N CH ₀ OH
CH ₂ OH OH M.
C. ^f N HO / I CH ₀ ^CH 2 _C _ _N / 2 OH '\ HO ^CH 2

which then lead to higher molecular weight condensates during the hardening under water penetration, mainly with the formation of methylene bridges:

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, HN-CH ₀ -HN- C

-NH-

NH-CH - NH ...,

N N

-NH-CH- -NH-C. * / *%

■ N N

.... HN-CH ₂ -NH-

NH

NH

To a lesser extent, methylene ether bridges can arise if the concentration of formaldehyde is chosen to be higher than the ratio Formaldehyde: Melamine equivalent to 3: 1.

. It is also known to use precondensates of melamine and formaldehyde

a p “value between 5 and 6 with alcohols at the boiling point of ti

to etherify applied alcohol while continuously removing the released water. The ether groups are formed on the N-methyiol groups of the melamine that did not take part in the condensation. These ether groupings take therefore only in very subordinate Degree of hardening under the influence of heat and acid, part, so that an essential content of N- methylol groups for further condensation must be maintained in order to cure to reach.

One uses the fact that etherified N-methylol groups practically not participate in the further curing, for example to obtain water-soluble polyethers of melamine by one alkaline condensed melamine-formaldehyde resins with a larger excess of glycols, z. B. diethylene glycol, etherified (U.S. Patent 2,358,276). The second hydroxyl group is glycol Obviously does not react with another N-methylol group

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ORIGINAL INSPECTED

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of another melamine molecule, as there are no cross-linked products can be obtained. A significant disadvantage of all of these divestments is the constant elimination of significant amounts of formaldehyde.

It has now been found that polyether melamines can be obtained in a very simple manner Way can be obtained by adding one or more mono- and / or polyhydric half-formals of polyhydric alcohols, if desired Mixture with half-formals of monohydric alcohols *, reacted with melamine in the presence of acidic or basic catalysts.

Suitable monohydric or polyhydric half-formals of polyhydric alcohols which can be obtained from a polyhydric alcohol and formaldehyde by an advantageous process which does not belong to the prior art and which is not the subject of this application have, for. B. the constitution HO-CH ₂ -ORO-CH ₂ -OH, where R is the residue of a dihydric alcohol. or HO-CH ₂ -OR-, where R. is the residue of a monohydric alcohol.

Possible dihydric alcohols are, for example: Glycol, propylene glycol-1,2, propylene glycol-1,3, butanediol-1,3, butanediol-1,4, pentanediol-1,5, 2,2-dimethylpropanediol-1,3, butanediol- (1,4), . 2,2, -Dimethylpropanediol- (1,3), hexanediol- (1,6), decanediol- (1,10), diethylene glycol, triethylene glycol, thiodiglycol, diethanolamine, thiodiglycol sulfoxide, 3-amino-2,5-dimethylhexanediol- ( 2.5), 3.5-bis (oxv- -isopropyD-pyridine, hexadiene (2,4) diol (l, 6), butenediol (1,4) and other diols in which there is a double bond in the carbon chain or there is a triple bond.

Cyclohexanediol- (1,4), 2,5- or 2,6-norbornenediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol _> cis, trans and 1: 1 cis / trans are also suitable - Mixture of 2,2,4,4-tetramethyl-1,3-cyclohexanedimethane ₁ ol-1,4, furthermore diols of the structure

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HO-CH ₂ -Ch ₂ -OC ₆ H ₄ -CC ₆ H ₄ -O-CH ₂ -CH ₂ -OH

or

CH,

HO-CH ₂ -CH ₂ -OC ₆ H ₁₀ -CC ₆ H ₁₀ -O-CH ₂ -CH ₂ -Oh.

CH _A

. Dihydric phenols are also suitable, ζ. B. catechol, Resorcinol, hydroquinone and ρ, ρ '-dioxydiphenyl-dimethylmethane.

High-quality polyols can also be used, e.g. glycerine, hexanetriol, dioxyacetone, pentaerythritol and polyvinyl alcohol, triethanolamine, Pyrogallol, oxyhydroquinone.

The new polyether melamines can easily be obtained by that together melamine and the multi-valued semi-formal. heated with the addition of some acid, the melamine in solution goes before polycondensation starts. At a temperature below 90 ° C, precondensates are usually formed, which at temperatures cure above 100 * C.

Suitable temperatures for the precondensation are generally between 30 and 95 ° C; a range of 60 to 90 ^° C is preferred, but also below 60 ^° C, for example at 40 ° C,

one can achieve an implementation, albeit a slow one.

ι ·

Possible catalysts are, for example:

Concentrated sulfuric acid, perchloric acid, hydrochloric acid, hydrogen bromide acid, p-toluenesulfonic acid; also Lewis acids, such as. B. boron fluoride, Boron fluoride etherate, tin tetrachloride, iron-HI chloride and

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Oxonium fluoborates are suitable; also acidic salts of polybasic Acids; such as B. KaUumhydrogensulfat, sodium dihydrogen phosphate, Potassium hydrogen sulfate. .

Substances which only occur at a higher temperature are particularly suitable release protons through thermal decomposition if hardening is only desired at higher temperatures, Such substances are: acidic salts of ammonia, such as. B. ammonium chloride, ammonium hydrogen sulfate and diazonium. · fluoborate, such as e.g. B. Benzoldiazoniumfluoborate, p-Nitrophenyldiazöniuxnfluoborate and butadiene sulfone.

The acidic catalysts are used in amounts of 0.0001-5%, preferably 0.01 - 3%, based on melamine used. The choice of acid catalyst depends on whether you have a fast or a slow condensation preferred. This is how the condensation works with concentrated sulfuric acid, perchloric acid or boron trifluoride etherate extremely quickly, while with p-toluenesulfonic acid is much more moderate. ,

But you can also use alkaline condensation before curing and then acidic curing. The alkaline catalysts used are alkali hydroxides such as lithium, sodium or potassium hydroxide, finely divided in solid form or in aqueous or alcoholic solution, also calcium oxide, barium oxide, sodium carbonate, potassium carbonate, magnesium carbonate and the like. Since most of the condensation takes place in the absence of water, metal alcoholates, such as. B. Natriuramethylat, potassium ethylate or aluminum isopropylate, particularly suitable.

The basic catalysts are used in amounts of 0.001 to § % based on melamine. '

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The use of basic catalysts has the advantage that you converts the semi-formal in a stage in which they are largely still in free form, in a medium in which they are from

By nature are more stable.

In principle, it is also possible. Prepare precondensates without a catalyst. This is needed but much higher Kbndensationstemperaturen between 110 and 13O ⁰ C and longer condensation times than with catalysts.

The reaction is expediently carried out in such a way that the two components and the catalyst are brought together and then heated until a uniform precondensate has formed, which can be seen from the fact that the mixture is completely homogeneous; Of course, you can also harden it by adding more heat. In order to achieve a uniform pre-condensate, it is beneficial to ensure that the reaction mixture moves well. In general, the condensation is carried out in the presence of air, uncolored substances being obtained throughout. However, if the semi-formal component contains a constituent which is autoxidizable particularly at a higher temperature, such as e.g. B. a nitrogen group, it is expedient to work in an inert gas atmosphere such as nitrogen.

But it is also possible to work in solvents.

Condensation in solvents is particularly advantageous if you want to use spreadable pastes, such as those that can be used for paper coating or textile impregnation, or if you are interested in precondensates that are viscous at room temperature to achieve thin layers for paint purposes. As the solvent are suitable any substance which is at least "the planned for the condensation components ine good and the

solve others to a limited extent. We can use water, alcohols, alcohol

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■ '·· ■■■■.'. ·· ' Mixtures of water, dimethylformamide, dimethyl sulfoxide, benzene. and cyclic formals such as 1,3-dioxolane, 1,3-dioxepan or diethylene glycol formal. The use of water is limited to the extent that as contents of more than 35%, based on the mass of the components to be reacted, cause a partial dissociation of the semi-formals into alcohol components and formaldehyde hydrate, in which case Formaldehyde-melamine resins can be obtained in the conventional sense with only a partial polyether structure. ·

The new process allows the properties to be changed to a very large extent of polyether melamines to vary, depending on which diol or Polyol component is used and what proportion of semi-formal: melamine is chosen. If you choose z. B. Semi-formal with. only a relatively small proportion of paraffin hydrocarbons, like glycol, very hard, relatively brittle materials are obtained; the same applies to an aromatic or bulky cycloaliphatic

Formally. Semi-formals with a relatively large proportion of paraffin hydrocarbons, such as hexylene glycol (l, 6) -bish-half-formal or polyethylene oxide (or, CO) to-semi-formal, on the other hand, result in soft, elastic materials, so that you can adjust hardness and elasticity simply by choosing the semi-formal component for a given molar ratio of 3: 2. In the case of more highly functional half-formals, in order to achieve equimolarity between poly-half-formal and melamine, 'of course, different ones have to be used Choose ratios, · «, B. Glycerin trisemi-formal to melamine such as 1: 1 etc. ·

But it is also possible with a given semi-formal by variation the molar ratio of e.g. B. Semi-formal to melamine from 0.5: 8 and 8.0: 0.5 to vary hardness and elasticity. So react z. B. at a molar ratio of half-formal to melamine 6: 2 no longer all semi-formal groups with melamine. The "excess"! Semi-formal groups cross-link to form full acetal bridges, partly with water leakage.

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whereby clear, soft and at the same time elastic materials are obtained will.

Another way to vary the properties of the products, consists in the simultaneous condensation of two or more bis- or poly-half-formals with melamine, the proportions largely are variable and depend only on the desired property. If you combine a "hardening" semi-formal with a "plasticizing" Semi-formal, the condensation process gives melamine a hard and at the same time elastic material.

Tris and higher functional ones are used instead of the semi-formal ones For formals, their ratio to melamine should be selected according to the 3: 2 ratio when using half-formals with melamine. They are usually opaque pastes if they have been obtained by briefly heating the components (10 to 30 minutes) to between 70 and 95 ° C are. They are all miscible in all proportions with polar solvents such as water, alcohols, dimethylformamide, etc.

But heating the components a long time in the presence of alkaline catalysts at these or higher temperatures, then the precondensates are increasingly waxy to solid, wherein in contrast to the Cond ensation using urea with melamine at temperatures of 120 to 160 ⁰ C completely cured Products can be obtained which are in the common organic solvents, such as. B. benzene, acetone, alcohols, chlorinated hydrocarbons are insoluble. .

The waxy to solid precondensation stages can also be used either on its own or in a mixture with fillers, such as cellulose, wood or rock flour, filled in molds and with acidic catalysts are cured with the application of heat to form solid moldings.

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You can increase the polyether content considerably by Bis- or poly-half formals mixed with mono-half formals with Melamine condenses. Suitable mono-semi-formals are derived, for example, from methanol, ethanol, n-propanol, iso-propanol, n-butanol, isobutyl alcohol, η-amyl alcohol, iso-amyl alcohol, n-hexyl alcohol, n-heptanol, n-octanol, n-decyl alcohol, l'auryl alcohol, Myristyl alcohol, benzyl alcohol, cyclohexanol, diethylene glycol monoethyl ether, Triethylene glycol monoethyl ether, triethylene glycol mono-butyl ether, Phenol, o-, m-, p-cresol, o-, m-, p-chlorophenol, p-bromophenol, o-, m-i p-nitrophenol, guaiacol, anol, Eugenol, saligenin, o-, m-, p-oxyacetophenone, salicylaldehyde and o-cyclohexalphenol. -

Mono-semi-formals suitable for modification are also the Mono-half-formal polyhydric alcohols, for example glycol-mono-half-formal, propanediol- (1,3) -mono-half-formal, butanediol- (1,3 ) -mono-semi-formal, glycerine-mono-semi-formal, cyclohexanedi-

m ethanol- (1,4) -mono-half-form al and res ore in mono-half-form al. These

Shape ; ^r

Substances are suitable both in pure and as a mixed product, such as it is obtained when a polyhydric alcohol is reacted with less formaldehyde than the functionality of the alcohol itself corresponds, for example, 1 mole of glycol with 1 mole of formaldehyde.

In each case, polyether ureas are produced, which have a higher value Show degree of etherification with lower precondensation and also contain free alcohol groups .. '.

The precondensates of these resins are particularly valuable because they are extremely soluble in chlorinated hydrocarbons and ethers and ketones and can be cured in solution to form paints, which are particularly adhesive due to the proportion of polar hydroxyl groups are. They are also extremely compatible with alkyd resins ».

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. It has also been found that it is possible to produce mixed polyether urea melamines by using a part of melamine replaced by urea or thiourea. You can use the properties of the polyether ureas in an advantageous manner with those of. Combine polyether melamines, especially when less cross-linked and consequently softer products are desired are. The proportion of urea can vary within wide limits, for example from 5 to 95 percent by weight, based on melamine. The way of working is the same as described above.

The new pure and modified polyether melamines are suitable in excellent for the production of casting resins, molding compounds, lacquers and adhesives. As a result of their excellent tolerance with known synthetic resins and Preßmas sen, for example with usual Melamine, urea and phenolic resins, they are also excellent to modify them. They can also be used with success. those for paper coating and textile impregnation.

example 1

In a beaker provided with a beaker, thermometer and external heating, 30.5 parts of glycol bis-half formal with 21.1 parts of melamine and 0.1 part of p-toluene-sulfonic acid are intimately mixed and heated slowly to 85 ° C. over the course of 30 minutes. If the temperature rises further, the. The mass is increasingly more viscous and solidifies at 12 ° C. After further heating to 140 ^° C. (15 minutes), a glassy, brittle block is obtained, which consists of polyether melamine. The substance is insoluble in water and in all organic solvents.

Example 2 .

A beaker provided with a stirrer, thermometer and external heater 30.5 parts of glycol bis-half-formal are intimately mixed with 21.1 parts

Melamine and 0.1 part of powdered solid caustic potash and heated slowly from 30 ⁰ C to 85 * C within 30 minutes, whereby a

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viscous mass forms, which solidifies ^{on further awakening to 90 ° C.} Hardening occurs when heated to 130 "C for 15 minutes. A block of white color is formed, consisting of polyether melamine. ■ ·

Example 3 .

In the experimental setup as described in Example 1, 21.1 parts of melamine are slowly heated with 51.1 parts of glycol bis-half formal and 0.01 parts of p-toluenesulfonic acid. At 75 ° C a clear solution, which is solid at passing through a temperature of 110 ⁰ C is formed. The curing takes place at 13G ° C in 10 minutes. A solid white body is obtained which, however, is softer than the substance obtained according to Example 1.

Example 4

In the experimental set-up as described in Example 1, 21.1 parts of melamine are triturated with 0.02 part of concentrated sulfuric acid in a mortar and the mixture is added to 35.04 parts of butanediol- {1,4> -bisformal. During heating, an exothermic condensation starts at a temperature of 40 ° C, which heats the mixture to 100 C ^e. After curing for 15 minutes at 140 ° C., an elastic, colorless, relatively soft substance is obtained, which is the polyether melamine of butanediol (1,4) bisformal.

Example 5

In the test arrangement as described in Example 1, 21.1 parts of melamine, 45.6 parts of thiodiglycol bis-half formal and 0.05 part of p-toluenesulfonic acid are intimately mixed and ^{heated to 90 °} C. over the course of 1.5 hours. The initial product is a viscous mass, which upon reaching of 9 O ⁰ C is determined. Curing is carried out within 1 hour by heating at 140 ⁰ C. The result ein'sehr hard substance block which has a pure white ITarbe and can not be scratched with a knife.

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Example 6

31.6 parts of melamine are mixed p-toluenesulfonic intimately together with 45.5 parts and 0.1 parts Glycerintrishalbformal and heated within 1 hour at ⁰ C 1QO arrangement in the manner described as in Example 1 trial. It forms a solid body which is cured at 140 ⁰ C. A white, relatively brittle solid is obtained, which is the polyether melamine.

" Example 7

In the experimental set-up as described in Example 1, 21.1 parts of melamine, 7.5 parts of urea and 30.5 parts of glycol bis-half formal together with 0.1 part of p-toluenesulfonic acid are initially heated to 50 ° C. for 80 minutes, the condensate being formed , which solidifies on further heating at 80 ⁰ C and is cured at 110 ° C ₍ . An opaque, white substance is obtained, which is the polyether melamine urea.

Example 8

In a vessel equipped with a stirrer, thermometer, nitrogen inlet and deflection 3-necked flask is charged 31.6 parts of melamine, together with 59.8 parts Triäthanolamintrishalbacetal and 0.2 parts of p-toluenesulfonic acid under a nitrogen stream over 60 minutes at 120 ⁰ C., whereby a solid block is formed which is cured at 14O ⁰ C within 10 minutes. The result is a glassy, very hard body that is not colored. If you work without an inert gas, you get a yellowish colored material.

Example 9 "

In the manner described as in Example 1 experimental arrangement 51 parts of cyclohexanedimethanol (l, 4) are -bishalbformal heated together with 21.1 parts of melamine and 0.05 parts of p-Toluolsulfos & ure: 25 minutes at 40 ⁰ C for 40 minutes at 80 ⁰ C. and 30 minutes at 120 ^° C.

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A white, tough, somewhat sticky substance is obtained.

Example 10

Ih the test arrangement as described in Example 1, 22.9 parts of glycol bis-half formal, 6.5 parts of butanol half-formal and 12.6 parts of melamine together with 0.1 part of p-toluenesulfonic acid are heated to 80 ° C. over the course of 1 hour, the precondensate being formed , which solidifies with further heating at 100 ⁰ C and is hardened within 6 minutes by heating to 14O ^{0 C.} A white solid block is created. · '

Example 11 '

Ih the arrangement are as described in Example 1 15.3 parts Glykolbishalbformal experiment, 20.8 parts Diglykolbishalbformal, 21.1 parts of melamine and 0.08 parts of p-toluenesulfonic acid are intimately mixed and then kept for 90 minutes at 5O ⁰ C, wherein the precondensate forms. Within a further half an hour, the ^{mixture is heated to 100 °} C., with crosslinking already occurring. Curing takes place within 10 minutes at 140 ^e C. It is a colorless Polyäthermelamin is obtained which has a high proportion of ether.

Example 12

Iq the experimental set-up as described in Example 1, 70.1 parts of butanediol (1.4) bis-half formal, 10.5 parts of melamine, 22.5 parts of urea and 0.05 part of 70 percent perchloric acid are intimately mixed and slowly heated. At 40 ^° C., a strongly exothermic reaction sets in, which causes the temperature of the mixture to rise to 90 ° C., with solidification occurring at the same time. 5 minutes of heating at 13O ⁰ C allowed to cure the substance. A clear, tough, soft mass is obtained. ''

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Example 13

Iq the test arrangement as described in Example 1, 115 parts of polyethylene glycol bis-half formal (MW 660), 21.1 parts of melamine and 0.1 part of concentrated sulfuric acid are intimately mixed and ^{heated to 95 °} C. over the course of 35 minutes. After a further 15 minutes at this temperature, a homogeneous, clear solution (precondensate) is formed, which hardens at 120 to 130 ° C within 20 minutes to form a solid, elastic, opaque, uncolored mass.

Example 14

Ih the test arrangement as described in Example 1 42.5 parts of resorcinol bis half formal, 21.1 parts of melamine and 0.01 part concentrated sulfuric acid thoroughly rubbed together and slowly heated. The strongly exothermic condensation reaction starts at 35 ° C a, which increases the temperature to 120 ° C within 5 minutes leaves, whereby a yellow, very hard, brittle resin, consisting of polyether melamine, arises. · ·

Examples - 17

Ih the test arrangement as described in Example 1, the from Table 1 visible bis- or polyhalbformal components together with melamine and the catalyst intimately mixed and with the temperatures and times given in the table condensed. ■ It hardenable precondensates arise.

Examples 18-20

The precondensates prepared according to Example 15-17 are stirred with concentrated sulfuric acid under the conditions shown in Table 2 and placed in a bore closed on one side. Then, by supplying heat from the outside, it is ensured that a temperature range of 50 to 130 ^° C. is continuously passed within 40 to 65 minutes. Hard, uncolored, solid bodies in the form of a round rod are created. They are insoluble in common solvents

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such as water, alcohols, ketones, gasoline, benzene and chlorinated, Hydrocarbons.

•>

Example 21-23

In the experimental set-up as described in Example 1 the bis-half formal components under the conditions shown in Table 3 together with melamine, solvent and the catalyst intimately mixed and condensed as usual.

Solid vitreous resins are formed after hardening. But you can also ^{apply the precondensates formed at 70 0} C to a metal sheet, where they pull up as a thin film and then harden. Very hard, solvent-resistant layers are obtained.

Example 24-27 '.

In the experimental set-up as described in Example 1, mono-semi-formals of polyhydric alcohols are used alone with melamine or condensed in a mixture with half-formals according to the information described in Table 4. It will be solid, partly opaque, partly transparent Resins obtained.

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Production of precondensates from bis- and tris-half-formals with melamine in Presence of basic catalysts

No. Bis- or poly-semi-formal components
Parts melamine
Parts catalyst
Parts Cond.
temp ..
^e C Cond.
Time
Min. Nature of the
Precondensate 15th 41.6 diglycol bis semi-formal 21.1 0.05 NaOH 75 '30 clear, viscous
liquid 16 45.6 thiodiglycol bis semi-formal
• ■ 21.1. 0.1 KOH 75 40 L clear, viscous
liquid 17th 56.3 trim ethylolpropane semi-
for times
« 31.6 0.0.8 NaOH 40-70 60 pasty

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Hardening of precondensates from bis- or tris-half-formals with melamine in the presence
acidic catalysts

No. • Precondensate consisting of Catalyst for that - Hardening temp. Hardening time Remarks Curing • c Min ... . 18th 41.6 TIe. Diglycolbish semi-formal. 0.1 part concentration H SO 70-120 40 solid at 80 ° C- I. 21.1 "melamine becoming
White 19th 45.6 TIe. Thiodiglycol bis 0.1 TIe. " 60-110 45 fixed at 7O ^{0 C} semi-formal + dend 21.1 "melamine White ·' · 20th 56.3 tIe. Trimethylol propane 0.05 TIe. " 50-130 65 firm at 85 ° C + ■ dend .. Sl, 6 "melamine White

OO O co

- 18-

Table preparation of polyether melamines in solution

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No. melamine
Tie, • 21.1 catalyst
conc. H ₀ SO- TIe, Condensate;
temp.
«C Remarks 40-120 100 at 70 ^° C. clear, viscous
Solution, after hardening
solid, glass-like Solvent content
TIe. 10 water 40-120 90 at 70 ⁰ C viscous solution,
• after hardening, solid,
white resin 20 n-butanol 21.1 ition
Time
Min. t
Bis-formal component: 30.6 parts of glycol bis-half formal 40-80 ■ 55 clear, highly viscous
resin • - 15 ethyl alcohol
8 water 21 0.05 Half-way components: Cyclohexanedimethanol- (1.4) - half-way 22nd 21.1 0.0 5 0.05 23
1*

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Polycondensation of mono-semi-formals of polyhydric alcohols alone with melamine or as a mixture
with half-marks ".

No. melamine
TIe. catalyst
TIe. Mono-semi-formal component
TIe. Bishalbf or m alkom ponent e
TIe. Condensation
temp. . Time
^e C min. 24 31.6 0.05 NaOH 23 Glycol monoform al 40-120 ° 120 25th 15.8 0.1 conc. H SO 11.5 glycol monoform al 22.8 glycerin up to half-r
formally 40-130 ° 130 26th 31.6 0.05 70% HClO ₄ i.
18.7 butanediol {1,4) mono-
half formal 22.8 thiodiglykoibis -
semi-acetal 50-130 ° 115 27 31.6 0.1 conc; H ₂ SO ₄ 43.3 Cyc lohexanedimethanol -
- (1.4) mono-half-form al * 50-135 ° 120

Claims (2)

" ²⁰ "" OZ 1869 •. July 21, 64 Claims •1. Process for the preparation of polyether melamines, thereby characterized in that one or more one and / or polyvalent half-formals of polyhydric alcohols, if desired in a mixture with half-formals of monohydric alcohols, with melamine in the presence of acidic or basic catalysts. 2. The method according to claim 1, characterized in that that the melamine is reacted in the presence of 5 to 95 percent by weight of urea, based on the melamine. / 7 / 809813/1254