DEF0015911MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: October 14, 1954. Advertised on November 8, 1956

GERMAN PATENT OFFICE

It is known to convert compounds with more than one reactive hydrogen atom with polyisocyanates to form high molecular weight plastics. From this polyaddition reaction is; made use of in manifold variations for the production of flat structures. So z. B. from a mixture of hydroxyl-containing polyesters and diisocyanates cast self-supporting films or glue objects together. According to other processes, polyesters dissolved in a suitable solvent, which may have already been modified with a deficit of a diisocyanate, can be used with a polyiso ¹ cyanate also in solution or a low molecular weight reaction product of a diisocyanate with free NCO groups for coating objects. Numerous processes for lamination of fabrics have also become known, in which, for example, reaction products of polyesters or polyethers with an excess of a polyisocyanate, which accordingly still contain free NCO groups, are applied to the substrate and post-crosslinking is carried out, for example by the air humidity or by the action of dissolved or vaporous diamines. The options mentioned are examples of a large number of procedures for manufacturing

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F 15911 IYbI 39b

development of fabrics that are based on the isocyanate polyaddition process. serve.

In the production of such flat structures ^; The main aim is to find suitable combinations which lead to end products which are as lightfast as possible and in which the isocyanate component shows the high reactivity of aromatically bound isocyanate groups with good storage stability and physiologically perfect behavior. The numerous combinations proposed so far have not been able to meet these requirements in all respects.

It has now been found that this goal is achieved by the use of diisocyanates from the achieve the following general formula: lets:

OCN

OCN-

(R 'or R ₁ = alkyl, isoalkyl, cycloalkyl radical, where R and R _{3 can be} identical or different; R + R ₁ = cycloalkyl _{radical; R 2} , R ₃ = hydrogen atom, alkyl radical, halogen atom).

Such diisocyanates are known in the art by phosgenation of the corresponding diamines.

accessible, such as B. from the diaminodiphenyldimethylmethane, the diamino-di-o-tolyl-dimethylmethane, the diaminodiphenylmethylethylmethane, the i, i'-diamino-diphenylcyclohexane (from cyclohexanone and aniline) and the 1, i'-diamino-diphenyl-3-methylclohexane (from 3 - methylcyclohexanone and aniline). The C-alkylation and halogenation products of the above diamines are used as starting materials for the preparation suitable diisocyanates can be used.

The diisocyanates mentioned can be used as such for the production of flat structures will. Since some of these monomeric diisocyanates, in particular the 4, /(.'-diaryl-dialkylmethane-diisocyanate. however, it has a relatively high melting point and a strong tendency to crystallize have, there are difficulties in this way of working because, for example these diisocyanates are present in the production of a film after the solvents have evaporated their final implementation precipitate again in crystalline form, unless at elevated temperature is being worked on. These difficulties, a use of the monomeric diisocyanates for the described Often make use at room temperature impossible, are avoided according to the invention, if low or high molecular weight isocyanate-containing reaction products of the diisocyanates with a deficit of connections ^ which are more than. a reactive hydrogen atom are used for the production of flat structures. Suitable for implementation Compounds are, for example, polyfunctional alcohols, amines or oxyamines, such as trimethylolpropane, Glycerine, triethanolamine; Diethylene glycol, diethanolamine, methyl diethanolamine, linear or branched polyesters, for example those made from adipic acid, diethylene glycol and / or trimethylene propane with preferably terminal hydroxyl groups, polyester amides, linear or branched ones Polyalkylene ethers, such as those used, for. B. by polyaddition of alkylene oxides to polyfunctional alcohols can be obtained .. Further technically valuable variants arise when the connections of the aforementioned classes of substances. still tert. Nitrogen atoms or polymerizable double bonds contained in the molecule at the same time.

When using compounds of the above general formula, in which RIR _{1 represents} a cycloalkyl radical, the detour via isocyanate-containing intermediates is not necessary in the production of flat structures, since these special compounds only have a very low tendency to crystallize and a very low vapor pressure, which leads to them become particularly valuable for the required area of application. ■,;

The compounds that are used as counter-components "to the diisocyanates mentioned or their isocyanate-containing Implementation products are used in the manufacture of fabrics, should contain more than one reactive hydrogen atom. Particularly suitable are di- and / or higher basic carboxylic acids and di- and / or higher alcohols linear or branched condensation products too of the alkyd resin type, which come under the trade name "Desmophene" have become known from the literature (cf. paints, varnishes, paints, 2, 123, 1948). But also modified alkyd resins, for example those with the use of saturated or unsaturated fatty acids are available, conversion products, especially the reduction products of copolymers of carbon monoxide and olefins or epoxy resins, can with the best Success can be used as counter components to the claimed diisocyanates. Further such classes of substance have proven useful, using the claimed Diisocyanates are produced, for example linear or branched condensation products with terminal hydroxyl groups, made from linear or branched polyesters and the above Diisocyanates. Of course, simple defined connections such as Water, bi- or polyfunctional alcohols, amines or carboxamides and the claimed Diisocyanates high-quality flat structures can be produced.

■ The advantages of using the claimed Diisocyanates are manifold. Due to their high molecular weight, they have one

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very low vapor pressure 'and are from this Reasons to be regarded as physiologically sound.

The diisocyanates are reactive products that allow it to work at room temperature in a technically appropriate time sheet with high-quality properties, which at other combinations, for example in the case of oil-modified alkyd resins in conjunction with urea or melamine-formaldehyde resins, only

ίο can be achieved through increased temperature.

Those obtained by the present process

Flat structures remain practical against sunlight or the light from carbon filament lamps unchanged. This fact is particularly astonishing and unforeseeable, especially also not because the flat structures from the corresponding, ■ not on the methane carbon atom substituted diisocyanates tend to yellow to a high degree in sunlight. So stand for example Flat structures made from 4,4'-diphenylmethane diisocyanate, from 3, 5, 3 ', 5'-tetramethyl-4, / i'-diphenylmethane diisocyanate and from 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate in terms of resistance to sunlight in stark contrast to those made from 4,4'-diphenyl-dimethylmethane-diisocyanate. -

And finally, further advantages of the claimed class of compounds are its excellent ones Compatibility with the many counter-components suggested, the good running of surface paints produced with their implementation products, which means the additional use makes special leveling agents superfluous, as well as the hydrophobic character of them manufactured substances, which lead to improved resistance to aging the fabric leads, called.

The measures known to accelerate the reaction in isocyanate reactions by activators or reaction inhibition by retarders can also be used in the same way during production of the process products. The same can be said for the use of additives such as fillers, organic or inorganic pigments, metal powders, dyes, Plasticizers take place in the usual way. Likewise, is the use of isocyanates Indifferent solvents in the production of the process products are very often an advantage.

Furthermore, such modification products of the diisocyanates mentioned can also be used, in which the isocyanate groups only become effective when elevated temperatures are used. Such compounds are z. B. by reacting the diisocyanates with phenols or compounds with active methylene groups, such as. B. diethyl malonate obtained.

In the following examples the parts given are parts by weight.

Example II

To ι moles of trimethylolpropane in 134 parts of ethyl acetate are 4.5 in a known manner at the boiling point of the solvent. Moles of 4,4'-diphenyldimethylmethane diisocyanate in. 1251 parts of ethyl acetate were added over the course of 1 hour. After heating to the boil for a further 2 hours, a 50 ° 70 solution in ethyl acetate of the condensation product containing isocyanate groups and containing iy, y ^o / o NCO has formed. After many days of storage with the exclusion of moisture, this solution shows no increase in viscosity and is. remained constant in their NC O content. Applied in a thin layer on a base, a hard, crystal-clear and brittle film is formed which does not show any tendency towards crystallization in contrast to the free 4,4'-diphenyl-dimethylmethane-diisocyanate.

Example 2

100 parts of a polyester made from adipic acid and diethylene glycol and having free hydroxyl groups and having an average molecular weight of 2350 are, after complete dehydration, after addition of 0.13 part of trimethylolpropane with 11.5 parts of 4,4'-diphenyi-dimethylmethah ^ diisocyanate at 13b ⁰ to implement . Obtained is a high molecular weight, organic solvent-soluble condensation product which .is characterized by a specific viscosity j / b / c, measured at o, i ° / o solution in m-cresol at 25 ^0, of 0.242. Its at 8o ° measured deformation value is 850 with an elastic component of 31.

Are in 100 parts of a 30% solution this condensation product in ethyl acetate with 7.5 parts of the isocyanate group-containing described in Example 1 Reaction product of 4,4'-diphenyl-diimethylmethane-diisocyanate and with 0.5 parts of one from 1 mole of N-methyldiethanolamine and 2 moles of phenyl isocyanate produced accelerator are added and this mixture is based on A thin layer of glass underlay is obtained after about 1 day of storage at Room temperature a transparent / highly elastic film. This shows after many hours Exposure in the light of a carbon filament lamp only a slight yellowing in contrast to one Film made under otherwise identical conditions, but using 4,4'-diphenylmethane diisocyanate was produced. , '

Example 3'-HS

66 parts of a 75% solution in ethyl acetate of one of 2.5 moles of adipic acid, 0.5 moles of phthalic anhydride and 4 moles of trimethylolpropane made polyester with a hydroxyl group content of 8.7% with 180 parts of a 5o% solution in ethyl acetate one of 500 parts 4,4'-Diphenyl-dimethylmethane-diisocyanate and 80 parts of trimethylolpropane produced condensation product with a content of "12.3 ° / o NCO, calculated on the solid matter." the

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with this mixture. Manufactured at room temperature .Surface protective coatings show a good flow and after 0.2 hours exposure in the light of a carbon filament lamp only a weak one Angil'bung. . .

B e i s ρ i e 1 4

To 100 parts of a 5o% solution in ethyl acetate of one of 2.5 mol of adipic acid, 0.5 mol Phthalic acid and 4 moles of trimethylolpropane produced polyester with a hydroxyl group of 8.5% are 40 parts of 1,1'-diphenylcyclohexane - (4, 4 ') - diisocyanate given the following formula:

OCN

OCN

Coatings produced with this combination bind in the course of 24 hours at room temperature to a hard, glossy film with practically no signs of yellowing indicates. This combination is in connection with pigments such. B. titanium dioxide, suitable for the Manufacture of 'refrigerator paints.

•. ■ example

A reaction product containing isocyanate groups which, for crosslinking, contains hydroxyl groups Polyester is suitable, is obtained in a manner known per se if 876 parts of 4,4'-diphenylmethylethylmethane diisocyanate the formula

CH,

OCN

OCN

with 134 parts of trimethylolpropane in 1010 parts Ethyl acetate, dissolved, by heating for 1 hour, for Boiling to be implemented. 100 parts of the 5o% solution described in Example 4 are mixed with 170 parts of the above combination mixed. Surface protection coatings produced with this mixture cure in 8 hours at room temperature and show practically no signs of yellowing. Reaction products containing isocyanate groups which instead of the abovementioned diisocyanate in equivalent amounts of 4,4 '- diphenyl - methyl - isopropyl methane diisocyanate

OCN

OCN

CH,

CH,

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or 4, 4'-diphenyl diethyl methane diisocyanate contain. . '

OCN

OCN

Example 6

Are 100 parts of a 50% solution of a condensation product obtained from 3 moles of adipic acid, 2 moles of trimethylolpropane and 2 moles of i, 3-butylene glycol with a content of 5> 8 ° / o Hydroxyl groups with 26 parts of 3,3'-dimethyl-4,4'-diphenyl-dimethyl-methane-diisocyanaf

CH

OCN

OCN- /

CH,

CH,

or with 30 parts of 3,3'-dichloro-4,4'-dipheny.1-dimethylmethane diisocyanate relocated and are

CH,

CH,

With these mixtures, lacquering, for example of wood, is carried out, firmly adhering, moderately hard films are obtained which have practically no yellowing phenomena.

Claims (2)

. PATENT CLAIMS: i. Process for the production of lightfast flat structures from polycondensation products of diisocyanates and compounds with more than one reactive hydrogen atom, characterized in that as a diiso- F 15911 IVb / 39b cyanate compounds of the following general formula can be used: OCN- ίο OCN (R or R ₁ = alkyl, isoalkyl, cycloalkyl radical, where R and R _{1 can be} identical or different; R + R ₁ = cycloalkyl _{radical, R 2} , R ₃ = hydrogen atom, alkyl radical, halogen atom). 2. Modification of the method according to claim i, characterized in that in place of the diisocyanates, the lower or higher molecular weight reaction products of these diisocyanates with a deficit of compounds that have more than one reactive hydrogen atom included. Considered publications: U.S. Patent No. 2284896;
German Patent Nos. 728981, 831604, 831772.,