DE1022789B - Process for the production of foams from polyoxy and / or polycarboxyl compounds and polyisocyanates - Google Patents

Description

GERMAN

kl. 39 b 22/04

INTERNAT. KL. C 08 g

PATENT OFFICE

F 21339 IVb / 39 b REGISTRATION DATE: SEPTEMBER 29, 1956

NOTICE
THE REGISTRATION
AND ISSUE OF THE
DEPLOYMENT: 16 JANUARY 1 9 5 8

Foams with a wide variety of physical properties are made using the isocyanate polyaddition process from compounds with several active hydrogen atoms, especially hydroxyl and / or compounds containing carboxyl groups and polyisocyanates, optionally with concomitant use of water, activators, emulsifiers and other additives have long been produced on an industrial scale (Angewandte Chemie, A 59, p. 257 [1948], pocket book? Bayer-Kunststoffe ", 1955). It is after this procedure is possible with a suitable choice of components, both elastic and rigid foams or to produce all variants lying between these groups.

It has also been proposed to use higher molecular weight foams by polymerization to prepare polyisocyanates accessible from isocyanates by means of tertiary amines. This way of working has a serious disadvantage which is to be found in the difficulty of mixing the components. the Higher molecular weight polyisocyanates are usually solid, high-melting substances or tough, high viscosity oils.

It has now been found that there are significant advantages in making the polyisocyanate-based foams achieved and the properties of the same are improved in numerous points when connections with several active hydrogen atoms, in particular compounds containing hydroxyl and / or carboxyl groups, with mixtures of higher molecular weight isocyanates with more than one isocyanate group and at least one isocyanuric acid ring in the molecule, which is obtained by polymerizing monomeric organic di- or Polyisocyanates, optionally with the concomitant use of monoisocyanates, are obtained with monomeric liquids Polyisocyanates are used.

The advantages of using higher molecular weight polyisocyanates mixed with monomers liquid polyisocyanates are achieved are manifold. The mixing of the foam-forming components with the sole use of monomeric liquid polyisocyanates, primarily diisocyanates, with the in any case of higher viscosity hydroxyl and / or carboxyl group carriers is often difficult, and often will be longer periods of time are required for the necessary homogeneous distribution of the components. But this is there is the possibility of premature undesirable reactions that have an unfavorable effect on the end product.

In contrast, the higher molecular weight polyisocyanates mixed with monomeric liquid polyisocyanates are liquids at room temperature whose viscosity is in any case higher than that of the monomeric polyisocyanate and can be set as required on a case-by-case basis

Method of manufacture

of foams made of polyoxy

and / or polycarboxyl compounds

and polyisocyanates

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Erwin Windemuth and Dr. Günther Braun,

Leverkusen have been named as the inventor

can. These higher viscosity polyisocyanate combinations can be easily and quickly with the Hydroxyl and / or carboxyl group carriers wear out the most types of construction and the other foam components mix. Undesired preliminary reactions of the non-homogenized mixtures are thereby reduced Minimum pushed back.

The rapid and intensive mixing of the components has other advantages. So become essential obtain more stable foams that show no tendency to collapse when they are formed, not even if larger batches are processed. The good mixing behavior of the polyisocyanate combinations It also makes it understandable that the foams produced with it are finer and more regular have formed pore structure, resulting in a generally improved property profile of the physical Data is expressed. The special structure of the trimerization reactions obtained polyisocyanates means that foams with increased compressive and tensile strengths, increased resistance to dynamic loads and significantly increased heat resistance can be obtained. It should be noted that all of the advantages mentioned are achieved in comparison to Foaming of the same density from the same starting materials, but using monomeric diisocyanates.

Polyisocyanate-based foams are preferably made by mixing liquid components Room temperature produced. This is an important advantage over other methods, but also a certain one Limitation as a number of accessible and also

709 849/428

3 4

suitable diisocyanates solid at room temperature are diisocyanate, 4,6-dimethyl-1,3-xylylene diisocyanate, cyclo- and therefore cannot be used without further ado. hexyl 1,4 - diisocyanate, dicyclohexyl methane - 4,4 '- diiso-diam the present process it is now possible cyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, have become, these solid diisocyanates after poly-l-alkylbenzene-2,4-diisocyanate, l-alkylbenzene-2,6-diisomerization (Trimerization) and mixing of the cyanate, 2,6-diethylbenzene-1,4-diisocyanate and diphenyl compounds higher molecular weight polyisocyanates with liquid methane-4,4'-diisocyanate, diphenyl-dimethylmethane monomers Polyisocyanates for the production of 4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-di-foams also to be used, whereby further valuable isocyanate, naphthalene-1.S-diisocyanate, 1-methylbenzene full Variations in the property profile of the end products 2,4,6-triisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate. be achieved. io The polymerization of the monomeric isocyanates that

The higher - at least one isocyanate group in aromatic bin molecular groups used for foam production Polyisocyanate combinations contain preparation, can also contain according to the process of weighed or in the desired metered amount tri- and German patent 951 168 take place. It is too higher functional isocyanates. This circumstance brings possible the isocyanates at elevated temperatures Advantages in particular in the production of rigid 15 by the action of oxygen and / or in organic Foam. The hydroxyl-solvent-soluble metal compounds suitable for this sector, such as and / or carboxyl group carriers must namely by, for example, tin tetrachloride, iron chloride, copper or a relatively high degree of branching distinguished zinc complexes of the Schiff base of stearylamine and be. The higher this degree of branching, the higher the salicylaldehyde to polymerize, is reactive even if the number is unchanged. 20 As a rule, the polymerized isocyanates are in Hydroxyl or carboxyl groups the viscosity of room temperature solids or viscous oils. For Links. Too high viscosities of the starting material, the production of the polyisocyanate components according to the invention However, if combinations are equally undesirable, they will be in liquid monomers like too low. Dissolved when using the present polyisocyanates. Suitable polyisocyanates for this Polyisocyanate combinations for the production of rigid 25 are z. B. l-methylbenzene-2,4-diisocyanate, 1-methyl foams you are now able to use less strong benzene-2,6-diisocyanate, l-methylbenzene-3,5-diisocyanate, branched, i.e. less viscous and thus more easily tetramethylene, hexamethylene, decamethylene diisocyanate processables Hydroxyl and / or carboxyl groups, m- or p-xylylene diisocyanate, 2,4,4'-diphenyl carriers to use, since part of the necessary ether triisocyanate (liquid crude product). Branches already in the higher molecular weight polyisocyanates. These polyisocyanates come in different cyanate combination is preformed. Amounts to apply depending on whether rigid or

The higher molecular weight polyisocyanates can be z. B. elastic foams are to be produced. as According to the general rule in patent application F 19371 IVb / 39c, it can be said that the proportion win the procedure described. According to this, the monomeric liquid polyisocyanates are kept small monomeric organic polyisocyanates, if necessary, should be added if highly crosslinked rigid foams together with organic monoisocyanates ^ are desirable in the presence, and that on the other hand much monomeric Small amounts of tertiary amines and polyisocyanate on nitrogen is used as a solvent when monosubstituted carbamic acid ester heated. Suitable more elastic types are to be made. In each tertiary amines for carrying out this process are in case it is expedient to use the polyisocyanate combinations z. B. aliphatic tertiary amines, while set as carbamide 40 so that liquid solutions at room temperature Acid ester carbamide monosubstituted on nitrogen can be obtained. Generally the amounts are acid methyl ester can be used. The poly-used polymeric isocyanates ί up to 80 merizing by weight The effect of the tertiary amines can be a percentage, based on the total weight of isocyanates, the polymerization by adding acidic reactants in the preparation of the polyisocyanate combinations

Connections are weakened or canceled. 45 auxiliaries, such as. B. fire retardants and / or Of course, only such products are suitable as plasticizers, provided that they are not which are still soluble and entim more than one NCO group with isocyanates reactive hydrogen atoms Molecule included. Hold monoisocyanates of the phenyl type. Trichloroalkylphosocyanate may be mentioned as examples are therefore unsuitable phate, highly chlorinated paraffins, esters based on ali starting components, provided they are used alone. 50 more phatic, hydroaromatic or aromatic morein Mixture with monomeric di- or triisocyanates of basic carboxylic acids.

on the other hand, they can be used as modifying components as hydroxyl and / or carboxyl group carriers

can also be used, whereby the quantities are chosen so that numerous types are suitable for foam production, that the above requirement - more than one NCO group may be named from mono- or polyfunctional alcopro End molecule - is met. 55 catch up and catch up with carboxylic acids or oxycarboxylic acid

Most meaningfully produced linear or branched for the described known process are those made from monomeric diisocyanates and polyesters, which also contain heteroatoms, double or triple isocyanates obtained higher molecular weight polymer bonds as well as saturated or unsaturated fatty acids station products. The di- or polyisocyanates or fatty alcohols can contain as modifying components the production of which can be used on its own or can hold 60, linear or branched polyester amides, also in a mixture with one another, which gives the possibility of linear or branched polyalkylene ethers or thio is, numerous types of ether, solid at room temperature, accessible from di- or polyols and styrene oxide to be used for foam production. As ethers with terminal hydroxyl groups, epoxy resins, Examples of the production of the higher molecular weight polyhydrogenation products of ethylene-olefin-carbon oxide isocyanates suitable isocyanates may be mentioned: phenyl copolymers, reacted with alkylene oxides isocyanate, the tolyl isocyanate, p-nitrophenyl isocyanate, phenol-formaldehyde resins.

p-chlorophenyl isocyanate, a-naphthyl isocyanate, benzyl- The foam itself is produced according to known

isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate process at room temperature or elevated temperature isocyanate, Decamethylene diisocyanate, m-xylylene diisocyanate by simply mixing the polyisocyanate cyanate, p-xylylene diisocyanate, 1-tert. Butyl-3,5-xylylene 70 combinations with the hydroxyl and / or carboxyl

group carriers, where appropriate Wassei, accelerator, Emulsifiers and other auxiliaries can also be used. (The addition of water can in cases become superfluous, in which as compounds with several reactive hydrogen atoms polyester or other high molecular weight compounds containing free carboxyl groups are used.) Here one uses advantageously machine facilities, such as z. B. in the French patent 1074713 are described.

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

example 1

Polyesters produced with a hydroxyl group content of 13.2% are treated with the same activator mixture Thoroughly mixed as described in Example 1 and with the addition of 139 parts of a 40% Solution of a polymer obtained from 2,4-tolylene diisocyanate with 25.3% NCO in monomeric tolylene diisocyanate foams after vigorous stirring. A foam is obtained which, like the following table shows, is characterized by an improved compressive strength, thermal stability and water storage. aside from that the foam does not show any shrinkage, in contrast to the comparison foam using of monomeric tolylene diisocyanate.

80 parts of one made from 5.1 moles of adipic acid, 1 mole of phthalic anhydride and 8.4 moles of hexanetriol recovered polyester containing 8.5% hydroxyl groups are with 20 parts of 1.43 moles of adipic acid,

1 mole of hexanetriol and 1 mole of 1,3-butylene glycol were obtained Polyester mixed with a content of 6.5% hydroxyl groups and made with an activator mixture

2 parts of an ester obtained from 2 moles of diethylethanolamine and 1 mole of adipic acid and 5 parts of one 54% aqueous solution of the sodium salt of castor oil sulphate was intensively stirred together. This mixture 92 parts of a 30% solution of one of toluene-2,4-diisocyanate are added with thorough stirring obtained polymer with 24.7% N C O in monomeric tolylene diisocyanate. Under heavy foaming it will receive a foam that is characterized by the following values:

35

40

45

The polymeric isocyanate was obtained by adding 100 parts of tolylene-2,4-diisocyanate in the presence of 6 parts of the Reaction product of 2 moles of phenyl isocyanate and 1 mole of methyl diethanolamine and 4 parts of methanol were heated to 160 ° C. until the NCO content reached the value of 24.7%.

The polyisocyanate combination described above can be incorporated very easily into the polyester mixture. A Comparison of the physical values of the foam obtained shows versus the use of pure Toluylene diisocyanate improves compressive strength and heat resistance. Come in addition, that the foam shows no signs of shrinkage after foaming. Even with one no shrinkage occurs after quarter-hour storage in boiling water. Using a foam made of monomeric toluene diisocyanate, however, shows very strong shrinkage both shortly after after foaming as well as after a quarter of an hour 6g cooking test.

Example 2

100 parts of one made from 1 mole of adipic acid, 2 moles of phthalic anhydride, 1 mole of oleic acid and 5 moles of glycerol

foam Comparison according to
example foam. Physical data with
monomeric
Toluene 35 diisocyanate Volume weight, kg / m ³ .... 1.39 32 Compressive strength, kg / cm ² .. 0.07 1.18 Impact strength, kg / cm ... 194 0.07 Heat resistance, ⁰ C 164 Water absorption, 0.5 Volume percentage 1.8

foam Comparison according to
example foam Physical data with
monomeric
Toluene 34 diisocyanate Volume weight, kg / m ³ .... 1.76 32 Compressive strength, kg / cm ² .. 0.15 1.29 Impact strength, kg / cm ... 0.12 Water absorption, 1 Volume percentage 140 1 Heat resistance, ° C 124

Example 3

80 parts of one from 2 moles of adipic acid, 0.4 moles of phthalic anhydride, 2.4 mol of trimethylolpropane and 0.8 mol of 1,3-butylene glycol produced polyester with a Hydroxyl group content of 10% in a mixture with 20 parts of 1.43 moles of adipic acid and 1 mole of hexanetriol and 1 mole of 1,3-butylene glycol obtained polyester with a hydroxyl content of 6.5% are with the in Example 1 described activator mixture and with the addition of 102 parts of a 46.5% solution of one of Toluylene-2,4-diisocyanate obtained polymer with 25.1% NCO in monomeric toluene diisocyanate intensive stirring. A rigid foam is obtained, compared to a foam that is used on its own produced by monomeric toluene diisocyanate shows no signs of shrinkage and is also distinguished by an increased resistance to pressure and heat.

foam Comparative according to
example foam Physical data with
monomeric
Toluene 40 diisocyanate Volume weight, kg / m ³ .... 2.12 32 Compressive strength, kg / cm ² .. 0.09 1.52 Impact strength, kg / cm ... 133 0.09 Heat resistance, ^C C 115 Water absorption, 2.9 Volume percentage 2.3

Example 4

A mixture of 50 parts of one of 2.5 moles of adipic acid, 0.5 moles of phthalic anhydride and 4 moles of glycerin obtained polyester with a hydroxyl content of 14% and 50 parts of one from 2 moles of adipic acid, 0.4 moles Phthalic anhydride, 2.4 mol of trimethylolpropane and 0.8 mol of 1,3-butylene glycol produced polyester with a hydroxyl group content of 10% is with a

Activator mixture mixed as in Example 1 and then mixed with 98 parts of a 20% solution of one Toluylene-2,4-diisocyanate obtained polymer with 25.1% NCO in monomeric toluene diisocyanate intensive stirred. Immediately pour into molds, in which the mixture foams strongly, and into a rigid foam reacted out. The foam is characterized by the following values:

a polymer obtained from toluene-2,4-diisocyanate containing 24.7% N CO, stirred vigorously. the The mixture soon begins to foam and solidifies to form an elastic foam, which after a period of storage of 24 hours is characterized by the following values:

foam Comparison according to foam
with Physical data example monomeric Toluene 34 diisocyanate Volume weight, kg / m ³ .... 2.98 32 Compressive strength, kg / cm ² .. 0.12 0.95 Impact strength, kg / cm ... 0.19 Water absorption, 0.5 Volume percentage 156 6.9 Heat resistance, ⁰ C 123

lo physical data foam
according to
example Comparison
foam
with
monomeric
Toluene
diisocyanate Volume weight, kg / m ³ ....
¹⁵ elasticity,%
Notch strength, kg / cm ...
Tensile strength, kg / cm ²
Strain, % 44
24
0.60
1.66
224 51
24
0.40
0.78
125

As can be seen, the foam produced using the toluene-2,4 polymer gives a strong one Improvement of the physical values compared to the comparison foam. Furthermore, the foam shows neither at room temperature still shrinkage when boiling in water, while the comparison foam shows these.

Example 5

100 parts of one prepared from 15.6 moles of adipic acid, 16.3 moles of diethylene glycol and 1 mole of trimethylolpropane Polyesters with a hydroxyl group content of 1.8% are mixed with 3 parts of one made from 2 moles of diethylaminoethanol and 1 mole of adipic acid-recovered ester, 1.5 parts of diethylammonium oleate, 1.5 parts of a 54% aqueous solution of the sodium salt of castor oil sulfate and 1.5 parts of water are thoroughly mixed and then with 37 parts of tolylene diisocyanate, which is 2%. As can be seen, the foam described a significant increase in tensile strength and elongation compared to the comparison foam.

Claims (2)

Patent claims: 1. Process for the production of foams from polyoxy and / or polycarboxyl compounds and Polyisocyanates, characterized in that the polyisocyanates are solutions of more than one NCO group and at least one isocyanuric acid ring-containing polyisocyanates composed of monomeric Di- or polyisocyanates, optionally with the addition of monoisocyanates ^ are obtained in liquid monomeric polyisocyanates are used. 2. Embodiment of the method according to claim 1, characterized in that the production the foams are made in the presence of liquid plasticizers and / or flame retardants, these are preferably added to the polyisocyanate solution. © 709 849/428 1.58