DE1945476A1 - Polyisocyanurate polyureas - Google Patents

Description

FARBENFABRIKEN BAYER AG LiVERKU S EN-Bcywwwk

T SEP. 1969

Polyisocyanurate-polyurea offe

The present invention relates to urea groups comprising polymeric isocyanates and a process for their preparation.

The polymerization of polyisocyanates to polyisocyanurates is generally known, and according to more recent processes a reproducible polymerization to be started at room temperature is also possible the polyisocyanates has become possible. (German patents 954 376, 1 112 285, British patent 1 104 394, Belgian patent documents 680 380, 697 411, 723 152, 723 153.)

According to this process, with the use of blowing agents, polymeric isocyanates are obtained in which the isocyanate content of the isocyanate groups originally present in isocyanurate " as well as in carbodiimide functions and their derivatives was convicted. Draw the foams obtained in this way by a high temperature resistance as well as by good anti-flan behavior. A manufacture of compact test bodies through a polymerization of polyisocyanates however, was previously not possible in a defined and reproducible manner, since the polymers already in one low degree of polymerization go into the insoluble state and as a result of those occurring in the formation of garbodiimS

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Carbon dioxide elimination tiat blistering occurs.

The present invention now describes a way of manufacturing of solid plastics based on isocyanates polymerize through, a process that is a further condensable Served intermediate stage. By polymerizing polyisocyanates, i.e. compounds or 'mixtures of compounds, which contain more than one NCO group in one molecule, if appropriate with the addition of blowing agents, he keep polymers that still contain free isocyanate. This isocyanate is then treated with ammonia, prim, or sec. Amines converted into urea groups, - which in the usual way according to the Methods of urea resin chemistry with, for example, oxo compounds or compounds that react in this sense can be converted into plastics.

The present invention relates to polymers of monomeric organic polyisocyanates with at least 2 NGO groups in the molecule, which are essentially isocyanurate and / or carbodiimide groups, which are formed by reacting 60-99 ^ of the isocyanate groups in the monomeric isocyanates with themselves have arisen, and in addition urea groupings of the general formula

-nh-oo-nC

in which R and R 'are identical or different and _{denote hydrogen or C 1} -C. ^ - hydrocarbon radicals, the urea groups having been obtained by converting 1-40,96 of the isocyanate groups originally contained in the monomeric isocyanates into urea groups .

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The present invention also provides a process for the preparation of Harnst off groups having Isocyanatpolymerisaten of compounds with more than one isocyanate group in the molecule, characterized in that compounds having more than one isocyanate group in the molecule, optionally in the presence of a blowing agent under the action of a trimerization the isocyanate groups and / or catalysts causing garbodiimide formation are converted into isocyanurate and / or carbodiimide groups and the remaining free isocyanate groups are converted into urea groups in a manner known per se.

The polyisocyanate polymers according to the invention correspond in their composition of the general formula

) XY vg, 'D cd

in which R and 'R' have the meaning already mentioned and

R "represents an n-valent radical, η corresponds to the sum a + b + c + d and a whole or

Fractional number from 2 to 4 means X =

1/3

Ik

Y =

a a value from 0 to (n - 1.5), b a value from 0.1 to (n - 1.2), c corresponds to one from 0.5 to (n - 0.1), d corresponds to one from 0 to (n - 1.7) and the sum of c + d> 1.2.

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As polyisocyanates for the preparation of the compounds according to the invention aliphatic and preferably aromatic polyvalent isocyanates are imprinted, e.g. alkylene diisocyanates such as Tetra- and hexamethylene diisocyanate, arylene diisocyanates and their alkylation products such as the phenylene diisocyanates and naphthylene diisocyanate e, diphenylmethane diisocyanate, tolylene diisocyanate, Di- and triisopropylbenzene diisοcyanates and triphenylmethane triisocyanates, Tri-Cp-isocyanatophenylJ-thiophosphate, Tri- (p-isocyanato-phenyl) -phosphate, aralkyldiisοcyanate such as ! - (Isocyanatophenyl) ethyl isocyanate or the Zylylene diisocyanate as well as the polyisocyanates substituted by a wide variety of substituents such as alkoxy, metal, chlorine or bromine, also with insufficient amounts of polyhydroxy compounds modified such as irimethylolpropane, hexanetriol, glycerine, butanediol Polyisocyanates.

The polyisocyanates which can be prepared according to Belgian patent 7H 850 are also suitable as polyisocyanates. As a preferred polyisocyanate, this is through Aniline-formaldehyde condensation and subsequent phosgenation Polyphenylene-polymethylene-polyisocyanate mixture that can be produced called. Mention may also be made, for example, of polyisocyanates capped with phenols, oximes or bisulfite, and acetal-modified isocyanates and partially polymerized isocyanates with isocyanurate rings, as well as higher molecular weight polyisocyanates, the duroh implementation can be prepared from monomeric polyisocyanates with low and / or higher molecular weight polyhydroxyl compounds. It can Mixtures of different isocyanates can of course also be used, monoisocyanates such as phenyl isocyanate also being used in this case or naphthyl isocyanate can also be used.

The polyisocyanates listed above are converted into polymeric isocyanates using the customary catalysts.

- 4th

Catalysts for the production of polymerized ^: Isocyanates are known in large numbers. For example, the salts of alcohols, phenols or carboxylic acids on the one hand and alkali and EriäUeliinetalltn on the other hand come into question, tert. Amines, optionally in combination with cocatalysts such as epoxides or hydroxymethylphenols, etc., as described in large numbers, for example in "Polyurethanes, Chemistry and Technology", Vol. I and II, Saunders-Frisch, Interscience Publishers 1962, p. 94, among others . In order to achieve a defined polymerization, it is advisable to use catalysts which effect polymerization of the isocyanate groups in the most uniform possible manner and without an incubation time. For example, solutions of the alkali alcoholates and phenates in polar solvents with dimethylformamide or N-methylpyrrolidone, combinations of Ν, ϊΙ ', Ν "-Tris-4i-dimethylamino-propy3) -hexahydro-triazine and epoxides or the in Belgian Patent 723 152 and 723 listed Mannich bases. These catalysts, which are generally used in amounts between 0.1 and 10, are preferably used 1 to 5 wt .- ^, initiate polymerization Ln defined '' / else and lead to a more or less brittle, easily crushable polymer, depending on the DAFL wndetoi comparable amount of catalyst, more or less high proportions of free isocyanate groups, preferably between 5 and 40 #, contains the originally present isocyanate groups.

To simplify the processing and the polymerization reaction, the polymerization can also or preferably take place in the presence of blowing agents, which lead to a slightly puffed and easily quantifiable material . As a blowing agent in this case the cleaved at a carbodiimide carbon dioxide and also additional blowing agents can be used from the class of halogenated hydrocarbons.

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1 0 9 8 1 1/2 0 1 8 BAD ORKälNAU-V - C

In addition to a trimerization reaction, the catalysts listed above lead to the formation of more or less high proportions of carbodiimide structures, which, as already stated, is associated with a certain propellant effect; this effect . can be promoted by the use of compounds that specifically catalyze the formation of carbodiimide groups such as phosphorus compounds (phosphines, phospholines, phospholine oxides, / cyclic / esters, amides, ester amides of phosphorous and phosphoric acid).

The production of the polymers can be carried out batchwise in small batches must, however, generally be carried out in a continuous manner due to the heat of reaction to be removed be carried out by using isocyanates and catalysts by machine, as was already the case with polyurethane foam production knownj be mixed and the mixture in appropriate generally open vessels are introduced.

In addition to the components mentioned, compounds with one or more hydrogen atoms reactive toward isocyanate groups, for example mono- or polyalcohols, mono- or polyamines or mono, can be added to a lesser extent, ie up to about 25 molar, based on the isocyanate groups present - or polycarboxylic acids, as they are known from polyurethane chemistry. Furthermore, the polymerization can be carried out in the presence of inactive fillers, pigments, flame retardants (antimony, phosphorus or halogen compounds), etc. and these can be incorporated or included in the polymer. With regard to the H-acidic compounds to be used, reference is made to "Polyurethanes, Chemistry and Technology", Vol. I and II; Saunda s- FriBch , Interscience Publishers, 1962, and Kunststoffhandbuch, Vol. VII, Vioweg-Höchtlen, Hanser-Verlag, 1966 .

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The isocyanate polymers obtained in this way essentially have Isocyanurate and garbodiimide structures, besides, can however, there are still secondary carbodiimide structures which can be attributed to a polymerization or a partial reaction of the carbodiimide groups formed with isocyanate groups. Alone For steric reasons, complete polymerization of the NCO groups is not achieved, so that the products still have different proportions of isocyanate groups, depending on the type and amount of catalyst.

To convert the polyisocyanate containing NCO groups into urine of groups containing polymer isocyanates are then, generally after comminution, with ammonia, a primary or secondary. Amine treated. This treatment can take place either via the gas phase or in inert solvents or in the presence of excess amine components.

The preferred amines are ammonia, primary and secondary amines of the R ₁ —NH ^ and S — HH-Hg type, where R ₁ and R _{2 are} an alkyl, cycloalkyl, aryl or aralkyl radical which may be interrupted by heteroatoms mean warning The preferred radicals are methyl, n-, iso-, tert-butyl, octyl, dodecyl, stearyl, cyclohexyl and also benzyl or phenyl groups.

In principle, this amine treatment can also be carried out with polyamines be carried out, depending on. Type and amount of used Polyamines an additional crosslinking reaction occurs or polymers are obtained that are additionally

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BATHROOM ORIGINAL

primary amino groups or their secondary products with the already treated isocyanurate-carbodiimide structures.

Such polyamines are preferably diamines of the general formula HJJ-E-KHp, where Eest R is a straight-chain or branched aliphatic hydrocarbon radical with a preferred number of hydrocarbon atoms up to 18, or an aromatic or cycloaliphatic hydrocarbon off rest represents. Preferred arylene or cycloalkylene diamines are ρ- and m-phenylenediamine, 2,4-tolylenediamine, 4,4 '-Diarnino-diphenylmethane, 4,4'-diamino-diphenyl ether and the corresponding hydrogenation products.

Another variant for producing the urea groups polymeric isocyanate consists of a water or. Steam treatment of the isocyanate groups containing poly, meren isocyanates, with the one with an enlargement of the molecule linked urea formation parallel formation of free amino groups goes.

The amount of urea groups to be introduced can be varied by only partially reacting the NCO groups with the amines or water listed above.

The process leads to generally solid, easily pulverizable, Polyisocyanates containing urea groups, the are stable in the resulting form and together with a wide variety of components that condense with a urea group can be processed into high molecular weight condensates.

In addition to formaldehyde and its polymeric forms, such compounds are preferably used as active components in question, the easily further condensable methylol forms

MJLJiLSSl - 8 -

hold, for example phenol containing methylol groups, Melamine or conventional urea resins.

Another variant of the process consists in using hexamethylenetetramine instead of formaldehyde. Since this splitting off ammonia in the condensation reaction can be obtained in this Pail directly from the polymeric isocyanates containing NCO groups can be assumed and the formation of the ureas are combined with the subsequent condensation reaction.

The advantages of the polymers used are their high thermal stability and their flame retardant properties. It can be assumed that from the isocyanate polymers ultimately largely aromatic when exposed to temperature with CQg splitting and bloating Polycarbodiimide structures are formed, which open the lower layers from further attack by heat and Protect flame.

Further details of the invention emerge from the following examples.

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Examples; '

example 1

In 10 kg of polyphenylene-polymethylene-polyisocyanate mixture, prepared by phosgenation of aniline-iormaldehyde condensation product, 600 g of catalyst A ^; stirred in. The polymerization starts immediately with development of heat. After cooling, the brittle mass is ground to a fine powder.

IR spectrum;

Isocyanurate band: 1410 cm "

Isocyanurate carbonyl band: 1710 cm "

Isocyanate band: 2260 cm "

This polymeric isocyanurate is six hours with gaseous Treated with ammonia. Approx. 6 to 8 wt .- ^ ammonia are absorbed with slight warming.

The catalyst A used in Example 1 is that in the Belgian Patent specifications 723 152 and 723 153 listed Mannich base, which was produced as follows:

To a mixture of 376 parts by weight of phenol and 1440 parts by weight of dimethylamine solution (25%) are added dropwise at 30 ° over one hour 850 parts by weight of malaldehyde solution (25%). Then hour at 30 ° and a further 2 hours at 80 ° is kept, after the addition of sodium chloride the organic phase separated and this at 90 ⁰ 0/12 Hg at eingtdampf t.
CP ₂₅ o: 25,000; Amine equivalent ι 105.

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Example 2

60 parts by weight of catalyst A are quickly stirred into 1000 parts by weight of 4.4 ^{l -diisocyanatodiphenylmethane at room temperature.} The mixture heats up immediately and solidifies after a few minutes with slight expansion to a brittle mass. The residual isocyanate content corresponds to 34 % of the isocyanate groups originally contained in 4,4'-diisocyanatodiphenylmethane.

IR spectrum;

Isocyanurate bands: 1410 cm

Isoeyanurate-carbonyl band: 1710 cm

Isocyanate band: 2260 cm ~

Example 3

60 parts by weight of catalyst A are quickly stirred into 1000 parts by weight of 2,4-diisocyanatotoluene at room temperature. The reaction proceeds as described in Example 8. The residual isocyanate content corresponds to 35 $> of the NCO groups originally contained in 2,4-diisocyanatotoluene.

IR spectrum;

_ · Ι Isocyanurate band: 1410 cm

_-] Isocyanurate-carbonyl band: 1710 cm

Isocyanate band: 2260 cm

Example 4

100 parts by weight of the polymeric isocyanate shown in Example 1 are suspended in 300 parts by weight of aqueous ammonia solution and stirred for 6 hours. Weight gain after suction and drying: $ 10.

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example 5

100 parts by weight of the polymeric isocyanate shown in Example 1 are suspended in 150 parts by weight of chloroform, treated with 30 parts by weight of n-butylamine and stirred for 6 hours. Ge. Weight gain after vacuuming and drying: 7 #.

Example 6

100 parts by weight of the polymeric Iso ~ shown in Example 1 cyanate are suspended in 150 parts by weight of ether, with 30 Parts by weight of n-dodecylamine are added and the mixture is stirred for 6 hours. Weight gain after vacuuming and drying: 25 #.

Example 7

100 parts by weight of the polymeric isocyanate shown in Example 1 are suspended in 150 parts by weight of chloroform, 20 parts by weight of hexamethylenediamine are added and the mixture is stirred for 6 hours. Weight gain after vacuuming and drying: $ 20,

Example 8

100 parts by weight of the polymeric isocyanate shown in Example 1 are suspended in 150 parts by weight of ether, treated with 20 parts by weight of aniline and stirred for 6 hours. Weight gain after vacuuming and drying: 5 / ».

Example 9

100 parts by weight of the polymeric isocyanate shown in Example 1 are suspended in 150 parts by weight of water, mixed with 50 parts by weight of methylamine solution (40 parts in water) and

Stirred for 4 hours. Weight gain after vacuuming and drying:

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Claims (5)

Claims; Polymers of monomeric organic polyisocyanates with at least 2 NCO groups in the molecule, which essentially Isocyanurate and / or carbodiimide groups, the by converting 60 - 99 ^ in the monomeric isocyanates containing isocyanate groups are formed with themselves, and in addition urea groups the general formula -nh-co-n in the R and R * are identical or different and are hydrogen or Cj-CjQ hydrocarbon radicals, whereby the urea groups by conversion of 1 - 40% the isocyanate groups originally contained in the monomeric isocyanates have been obtained in urea groups, exhibit. 2. Polyisocyanate polymers of the general formula / ^Rl
R «(NCO) _a (NHCON ( _R ) _b X _c Y _d in which Lt A 12 091 R and R * are identical or different and are hydrogen or Cj-G ^ hydrocarbon radicals, R ^w «represents an n-valent radical, where η corresponds to the sum a + b + c + d and a whole or fractional number from 2 to 4 means X = 1/3 - 13 - 109811/2018 = ^ -N = C = N- J a a value from 0 to (η - 1.3), b a value from 0.1 to (n - 1.2), c corresponds to a range from 0.5 to (n - 0.1), d corresponds to a range from 0 to (n - 1.7) and the sum of c + d> 1.2. 3. Organic isocyanate polymers according to claim 1 and 2, which urea groupings of the formula -NH-CO-NH ₂ exhibit. 4. Process for the production of urea groups Isocyanate polymers made from compounds with more than one isocyanate group in the molecule, characterized in that one Compounds with more than one isocyanate group in the molecule, possibly in the presence of a propellant under the action of a trimerization of the isocyanate groups and / or a carbodilmide formation causing catalysts in isocyanate and / or isocyanate polymers containing carbodiimide groups and the remaining free isocyanate groups converts to urea groups in a manner known per se, 5. The method according to claim 4, characterized in that the isocyanate groups are converted into urea groups by the action of ammonia _t G ^ - to C * g-alkylamines or C ^ - to C ^ Q-dialkylamine. Le A 12 091 -H- 109811/2018