CA1227203A - Liquid isocyanurate group-containing polyisocyanate mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanate, method for their preparation and their use in polyurethane or polyisocyanurate plastics - Google Patents

Liquid isocyanurate group-containing polyisocyanate mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanate, method for their preparation and their use in polyurethane or polyisocyanurate plastics

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CA1227203A
CA1227203A CA000447165A CA447165A CA1227203A CA 1227203 A CA1227203 A CA 1227203A CA 000447165 A CA000447165 A CA 000447165A CA 447165 A CA447165 A CA 447165A CA 1227203 A CA1227203 A CA 1227203A
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mixture
weight percent
weight
mixtures
polyisocyanate
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Gisbert Schleier
Matthias Marx
Dietmar Nissen
Wolfram Frank
Robert Gehm
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BASF SE
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BASF SE
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78Nitrogen
    • C08G18/79Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/794Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

LIQUID ISOCYANURATE GROUP-CONTAINING
POLYISOCYANATE MIXTURES OF 4,4'- AND
2,4'-DIPHENYLMETHANE DIISOCYANATE, METHOD
FOR THEIR PREPARATION AND THEIR USE IN
POLYURETHANE OR POLYISOCYANURATE PLASTICS
Abstract of the Disclosure Isocyanurate group-containing polyisocyanate mixtures which are liquid at room temperature and which have an isocyanate group content of from 23 to 31 weight percent are obtained through the partial trimerization of a mixture comprised of from about 80 to about 30 percent by weight 4,4'-diphenylmethane diisocyanate and from about 20 to about 70 percent by weight 2,4'-diphenylmethane diisocyanate in the presence of a trimerization catalyst, preferably an adduct of tri(dimethylaminopropyl)-s-hexahydrotriazine, 1,2-propylene oxide, and 2-ethylhexanoic acid, and, in some cases, after chemical deactivation of the catalyst.

Description

` Case 1416 LIQUID ISOCYANURATE GROUP-CONTAINING
POLYISOCYANATE MIXTURES OF 4,4'- AND
2,4'-DIPHENYLMETHANE DIISOCYANAT~, METHOD
FOR THEIR PREPARATION AND THEIR USE IN
POLYURETHANE OR POLYISOCYANURATE PLASTICS
I
1. Field of the Invention This invention pertains to the field of modified isocyanates. More specifically, it relates to isocyanurate-containing diphenylmethane diisocyanates 2. Description of the Prior Art It is known that organic isocyanates can be trimerized into isocyanurates with the aid of catalysts.
In existing literature, for example in High Polymers, Vol. XVI, "Polyurethane, Chemistry and Technology," Pt. I, by J. H. Saunders and K. C. Fresh (Verlag Intrusions Publishers: New York, London 1962), p. 94 if., numerous catalysts are described for cyclization and polymerization. Typical examples are: strong bases like qua ternary ammonium hydroxides, for example, benzyltri-methyl ammonium hydroxide, alkali metal hydroxides, for example sodium or potassium hydroxide, alkali metal alkox-ides, for example sodium methyl ate and potassium is-propylate, trialkylphosphines, for example triethylphos-pine, alkylaminoalkylphanols, for example trussed-methylaminomethyl)phenol, 3- and/or 4-substituted pardons, for example 3- or 4-methylpyridine, metal-organic salts, for Lo example tetrakis(hydroxyethyl)-sodium borate, Friedel-Crafts catalysts, for example aluminum chloride, iron (III3 chloride, boron fluoride, and zinc chloride, and alkali metal salts of weak organic acids and nitrophenolates, for example, potassium octet, potassium 2-ethyl hexoate, potassium bonniest, sodium pirate, and potassium phthali-mode.
Of particular commercial interest in this regard is the polymerization of organic polyisocyanates to form polymerization products having an isocyanurate structure and free isocyanate groups. To do this, it is necessary to stop the formation of the isocyanurates after the desired degree of in- or polymerization is achieved. One way to accom-polish this it by decomposing or neutralizing the gala-lystq. Thus, basic catalysts can be neutralized, for example, by acids such as hydrochloric acid.
According to U. S. Patent 2,993,870, various treason derivatives have proven to be very good catalysts for the polymerization of aromatic polyisocyanates. The disadvantage with these catalysts is, on the one hand, thaw they are already so extremely effective at room temperature that special measure must be taken involving cleavable, capped groups if one wishes to obtain polymerization products with an isocyanura~e structure and free isocyanate groups. On the other hand, these same treason compounds ~227~3 are nearly ineffective in the polymerization of aliphatic polyisocyanates.
In order to overcome this disadvantage in DE-A-26 16 415 co-catalyst systems comprising 1,3,5-~ris(dimethyl-aminopropyl)-s-hexahydrotriazine and an organic moo- and/or dicarboxylic acid are used.
The trimerization of aliphatic, cycloaliphatic, and aromatic polyisocyanates in the presence of complexes of basic alkali metal compounds and cyclic organic compounds as catalysts is described in DE-A-31 00 263 REP 56 159). In this process, the diisocyanates are partially trimerized and then the excess monomeric diisocyanate it separated off by means of distillation. The resulting products are print supply used as paint binders.
In DE-A-25 51 634 (U. S. 4,115,373) Mannish bases are used as catalysts, and the trimerization is performed in the presence of inert solvents at temperatures less than 60C. In this method, the solvent must also be separated from the reaction mixture after completion of trimerization.
The complicated preparation of isocyanurate group-containing polyisocyanates in the above processes was done in the desire to obtain relatively high molecular weight polyisocyanates with a low vapor pressure from extremely toxic aliphatic or low-boiling point aromatic dozes-notes. This trimerization unavoidably led to pulses-7~g~3 notes with r01atively high functionalities, for example, functionalities of three or more.
However, polyaddition reactions of polyfunctional compounds with reactive hydrogen atoms and in- and/or higher functionality polyisocyanates are very difficult to control and they frequently lead to brittle polyurethane or pullers which also have low abrasion strength.
Summary of the Invention The objective of the invention at hand way to develop polyisocyanates with low vapor pressure which are liquid at room temperature, storage stable, and easily processed, and which can be processed into cellular or noncellular polyurethane, polyisocyanurate, and/or puller group-containing plastics which exhibit high wear strength, low flammability, and, in particular, low shrinkage.
Such properties are present in the liquid pulse-sonority group-containing polyisocyanate mixtures of this invention. Said mixtures have an isocyanate group content of from 23 to 31 weight percent and are obtained through the partial trimerization of a mixture of from about 80 to about 30 weight percent 4,4'-diphenylmethane diisocyanate, based on the total weight, and from about 20 to about 70 weight percent 2,4'-diphenylmethane diisocyanate, based on the total weight, in the presence of a trimerization catalyst with the subsequent deactivation of the trimerization catalyst.

~L227Z~33 The polyi~ocyanate mixture of the invention are not only highly storage stable but they are easy to process in the preferred range of isocyanate content due to their viscosity. Cellular and noncellular polyurethane or polyp urethane group-containing polyisocyanurate plastics prepared from the polyisocyanates are surprisingly colorless and exhibit almost no shrinkage. In this way nearly white rigid foams with good mechanical and flame retardant properties as well a a low smoke density can be obtained based on diphenylmethane diisocyanates. Light colored rigid foams are particularly desired for refrigerator insulation and in sporting goods applications, for example, in surfboards.
Noncellular polyurethane prepared from the polyisocyanates of the invention exhibit a significantly lower reduction in impact strength after conditioning at high temperatures, for example, at 200C, as is common in the oven baked painting of thermobreak window moldings with powder paints. In particular, such plastics exhibit high dimensional stability at elevated temperatures.
Another advantage of the present invention is that it is easier to control the reaction used to prepare isocyanurate group-containing polyurethane foams. Unlike isocyanurate group-containing polyurethane foams from mixtures of diphenylmethane diisocyanates and polyphenyl-polyethylene polyisocyanates, subsequently referred to as ~27~ I

crude MID, the polyi~ocyanates of the invention harden all the way through in comparable tire period.
The functionality of the polyisocyanate mixture can be adjusted across a wide range by altering the degree of trimerization and the isocyanurate group content. This leads to a wider range of possibilities for adjusting the foams to meet desired mechanical properties such as abrasion resistance, shrinkage, dimensional stability at elevated temperatures, flammability, etc., in the vinyl product.
Description of the Preferred Embodiments The following is noted relative to the initial components and auxiliaries used for the polyisocyanate mixtures of the invention:
The diphenylmethane diisocyanate mixtures which are partially trimerized contain from about 80 to about 30 weight percent, preferably from 60 to 40 weight percent, and more preferably from 55 to 45 weight percent, 4,4'-diphenyl-methane diisocyanate and from about 20 to about 70 weight percent, preferably from 40 to 60 weight percent, and more preferably from 45 to 55 weight percent, 2,4'-diphenyl-methane diisocyanate, whereby the weight percents are based on the total weight of 4,4'- and 2,4'-diphenylmethane diisocyanate.
However, mixtures which also contain Dow-phenylmethane diisocyanate in amounts of maximum 5 weight Lyle percent, preferably less than 2 weight percent, based on the weight of 4,4'- and 2,4'-diphenylmethane disunites are also suitable. Such diphenylmethane diisocyanate mixtures can be prepared through the phosgenation of diphenylmethane dominoes or through complete or partial distillation ox the diphenylmethane diisocyanate fraction off the crude MID.
The following typically may be used as trimmers-lion catalysts: alkali or alkaline earth hydroxides, strong organic bases such as, for example, Mannish bases and 1,3,5-tris(N,N-dialkylaminoalkyl)-s-hexahydrotriazines, tertiary amine, for example, triethylamine, basic salts of organic carboxylic acids, for example, potassium acetate, Friedel Craft catalysts, alkali metal oxides, alkali metal alcohol-ales, fanlights, and carbonates, opium compounds of nitrogen, phosphorus, and sulfur, and mono-substituted monocarbamates. The following are preferably used: 1,3,5-tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine,, co-catalyst systems of 1,3,5-tris(N,N-dimethylaminopropyl)-s-hexahydrotriazines, and organic moo- and/or dicarboxylic acids, 2,4,6-tris(dimethylaminomethyl)phenols, ortho- Andre para-dimethylaminomethylphenol, and adduces of one mole 1,3,5-tris(dialkylaminoalkyl)-s-hexahydrotriazine,, one mole alkaline oxide, preferably ethylene or l,2-propylene oxide, and one mole of an aliphatic or aromatic carboxylic acid.
An adduce of 1,3,5-tris(dimethylaminopropyl)-s-hexahydrotri-~Z~7~2~3 amine, 1,2-propylene oxide and 2-ethylhexanoic acid ha proven to be an especially good trimerization catalyst and it, therefore, preferably used for this purpose. One advantage in using this adduce it that the catalyst does not need to be deactivated after trimerization is completed, provided that the conversion takes place at temperature between 25 and Luke. Here the required amount of catalyst depends on the desired isocyanate content in the pulse-Nate mixture and on the content of easily hydrolyzable chlorine in the diphenylmethane diisocyanate mixture. The trimerization catalysts are best used in amounts from 0.005 to 1.0 parts by weight, preferably from 0.01 to 0.1 parts by weight, per 100 parts by weight of the mixture of 4,4'- and 2,4'-diphenylmethane-diisocyanate.
After the desired isocyanate content ha been attained, the trimerization it stopped. If the trimmers-lion catalyst doe not slowly decompose under the applied reaction condition so that its final concentration is - nearly zero, or if it does not lose it activity at room temperature, it must be deactivated by the addition of a suitable additive. Strong acids or carboxylic halogenide~
are among the suitable deactivation agents. Typical deactivators are acids, for example, phosphoric acid, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid and 2~3 toluenesulfonic acid, and acid halogenide~ such as acutely chloride, bouncily chloride, and toluenesulfonyl chloride.
In general, the trimerization reaction is effectively ended by the addition of approximately 1 to 20, preferably 1 to 3, equivalents of strong acid, carboxylic acid halogen ides and/or toluenesulfonyl chloride per equivalent catalyst and/or by cooling or quenching the reaction mixture.
The polyisocyanate mixtures of the invention can be directly processed into nearly colorless polyurethane or polyurethane group-containing polyisocyanurate plastics.
However, when the inherent color in the final product is less important and other properties needed for the applique-lion must be modified effectively, it is desirable to mix the polyisocyanurate group-containing polyisocyanate mixtures with other aliphatic, cycloaliphatic, or aromatic polyisocyanates. Polyisocyanate mixtures of the type cited are comprised of approximately 100 to 60 weight percent, preferably about 95 to about 60 weight percent, of the polyisocyanate mixture of the invention containing issues-curate groups and approximately 0 to 40 weight percent, preferably 5 to 40 weight percent, of an aliphatic, cycle-aliphatic, and preferably aromatic polyisocyanate.
Typical isocyanates which may be used in admixture with the modified isocyanates of this invention are:
aliphatic diisocyanates such as 1,4-butane-, try-~22~

methyl-1,6-hexane- and, preferably, 1,6-hexane-diisocyanate, cycloaliphatic polyi~ocyanate~ such a 3-isocyanatomethyl-
3,5,5-trimethylcyclohexyl isocyanate, 1-methyl-2,4- and/or 2,6-cyclohexane diisocyanate, 4,4'-, 2,4'-, duskily-hexylmethane diisocyanate, mixtures of 4,4'- and 2,4'-dicyclohexylmethane diisocyanate, or mixtures of 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate, and polycyclohexyl polyethylene polyisocyanates, and preferably aromatic, in some cases carbodiimide and/or preferably urethane group-containing polyisocyanates such as 2,4-and/or Tulane diisocyanate, crude MID, naphthylene disunites, urethane modified 4,4'-diphenylmethane diisocyanates, urethane modified mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanaes, and urethane modified mixtures of crude MID. The polyisocyanates can be singly or in the form of mixtures.
To prepare the isocyanurate group-containing polyisocyanates, the mixtures of 4,4'- and 2,4'-diphenyl-methane diisocyanates, which can be utilized in accordance with the invention, are mixed at temperatures from 0C to 160C, preferably from 0C Jo 30C, with the trimerization catalyst, whereby the quality of the final product is improved by adding the trimerization catalyst at the lowest possible temperatures up to room temperature. Finally, the reaction is allowed to take place at these temperatures, ~22~7~3 however, preferably at from 25C to 100C and more prefer-ably at from 30C to 80C, whereby mixing it desirable, until an isocyanate content of from 23 to 31 weight percent, preferably from 25 to 28 weight percent, based on the weight of the polyisocyanate mixture is attained. To do this, generally reaction times of from 0.3 hour to 60 hour, preferably from 0.75 hour to 4 hours, are required. After the desired isocyanate content has been attained, the reaction mixture is allowed to cool and the trimerization catalyst is deactivated to the extent necessary. The deactivating agent can be incorporated in the reaction mixture but can also be incorporated at the trimerization temperature.
When using diphenylmethane diisocyanate mixtures with high 4,4'-diphenylmethane diisocyanate contents, the resulting polyisocyanate mixtures can exhibit a slight turbidity which may be filtered off if needed.
The isocyanurate group-containing polyisocyanate mixtures of the invention possess, as already stated, an isocyanate content of from 23 to 31 weight percent, prefer-ably from 25 to 28 weight percent, an isocyanurate group content of from 10.0 to 2.6 weight percent, preferably from 8.6 to 5.6 weight percent, and a viscosity of from 20 to 200,000 ma preferably from 300 to 12,000 maps, at 25C.

7;2~

The compounds are valuable raw materials for the preparation of cellular or dense polyurethane or polyp urethane group-containing pQlyisocyanurate plucks, in particular for the preparation of essentially colorless rigid foams.
The polyi~ocyanate mixtures of the invention can also be trimerized in the presence of organic solvent.
Solvents which do no react with isocyanates can be utilized, for example, ethylene chloride, chloroform, chlorobenzene, acetone, methylethylketone, ethyl acetate, bottle acetate, tetrahydrofuran, Dixon, dimethylformamide, Tulane, and zillion.
After completion of trimerization, the non-converted 4,4'- and 2,4'-diphenylmethane diisocyanates and, if desired, the solvent, can be separated off under non-destructive conditions. This can be achieved by high vacuum distillation in suitable evaporators or through extraction with solvents in which only the diphenylmethane diisocyanate but not the isocyanurate group-containing polyisocyanates are soluble, for example, in aliphatic or cycloaliphatic hydrocarbons.
The solvent-containing polyisocyanate mixtures of the invention are typically used for polyurethane paints or adhesives.

Z7;2~3 The preparation of the polyurethane or polyp urethane grsup-containing polyisocyanurate plastics is achieved by reacting the iqocyanurate group-containing polyisocyanates of the invention with polyols and, in some caves, chain extenders in the presence of catalyst and, in some cases, blowing agents, auxiliaries, and additives.
Typical pOlyOlA utilized for this purpose are:
polyester polyols bayed on organic dicarboxylic acid, preferably aliphatic dicarboxylic acids having from 2 to 12, preferably 4 to 8, carbon atoms in the alkyd residue, and polyfunctional alcohols, preferably dills, having function-amities from 2 to 6, preferably 2 to 4, and hydroxyl numbers from 20 to 700, whereby preferably polyester polyols hazing hydroxyl numbers from 20 to 85 are used for the preparation of flexible plastics, preferably polyester polyol~ having hydroxyl numbers from 85 to lS0 are used for the preparation of semi-rigid plastics, and preferably polyester polyols having hydroxyl numbers from 200 to 490 are used for the preparation of rigid cellular plastics. Typical examples are aliphatic dicarboxylic acids such as succinic acid, glutaric acid, pimelic acid, undecanedioic acid, dodecane-Dick acid, and, preferably, adipic acid and aromatic dicarboxylic acids such a phthalic acid and terephthalic acid. Examples of dip and polyfunctional alcohols, in particular difunctional alcohols, are: 1,2~ or 1,3-propane-~27;~3 dill, dipropylene glycol, 1,5-pentamethylene glycol, 1,8-octamethylene glycol, l,lO-decamethylene glycol, glycerine, trimethylolpropane, pentaerythritol as well a sugar alcohols, for example, sorbitol and, preferably, ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexa-ethylene glycol. In addition, alkanolamine~, dialkanol-amine, and trialkanolamines, for example, ethanol amine, diethanolamine, triethanolamine, and triisopropanolamine can be used as polyfunctional alcohols. The cited dicarboxylic lo acids and polyfunctional alcohols can be utilized in the form of mixtures. Especially successful, and thus prefer-ably used, are: polyester polyols of adipic acid or mixtures of succinic, glutaric, and adipic acid and dip ethylene glycol, and alcohol mixtures of ethylene glycol/1,4-butanediol, ethylene glycol/diethylene glycol, ethylene glycol/trimethylolpropane, diethylene glycol/tri-methylolpropane, ethylene glycol/pentaerythritol, ethylene glycol/triisopropanolamine, and diethylene glycol/triiqo-propanolamine.
In place of the cited polyester polyols, which can be utilized either individually or as mixtures, homogenou~
mixtures of polyester polyol~ and soluble organic combo-newts, which are liquid at temperatures from lo to 30~C, can be utilized, for example, hydroxyl group-containing polyp esters of aromatic dicarboxylic acids and, preferably, unsubstituted, linear Doyle.

2~3 However, polyether polyols having functionalitie~
from 2 to 8, preferably 2 to 4, and hydroxyl numbers from 25 to 800, preferably from 25 to 85, are preferably used for flexible, dense or cellular plastic while such polyols having hydroxyl number from 85 to 180 are utilized for semi-rigid plastics and those having hydroxyl numbers from 200 to 600 are utilized for rigid, dense or cellular plastic, are prepared according to known procedures, for example, through anionic polymerization with alkali hydroxides such as sodium or potassium hydroxide, or alkali alcoholates such a sodium or potassium methyl ate, ethyl ate, or potassium isopropyl ate as catalysts, or through cat ionic polymerization with Lewis acids such as antimony pent-chloride, boron fluoride ether ate, etc., as catalysts from one or more cyclic ethers having from 2 to 4 carbon atoms in the alkaline residue and an initiator molecule having from 2 to 8 active hydrogen atoms, preferably from 2 to 4.
Suitable cyclic ethers are, for example: twitter-hydrofuran, 1,3-propylene oxide, 1,2- or battalion oxide, styrenes oxide, epichlorohydrin, and, preferably, ethylene oxide and l/2-propylene oxide. The alkaline oxides can be utilized individually, alternating one after another, or as mixtures. Typical initiator molecules are: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid, and terephthalic acid, aliphatic and art-%7~3 matte, in some kiwi, N-mono-, NUN-, and N,N'-dialkyl-substituted Damon having from 1 to 4 carbon atom in the alkyd residue such as, in some case, moo- and dialkyl-substituted ethylenediamine, diethylenetriamine, in-ethylenetetramine, l,3-propanediamine, 1,3- or 1,4-butane-Damon, 1,2-, 1,3-, 1,4-, 1,5-, or 1,6-hexanediamine, phenylenediamines, 2,4- or 2,6-toluenediamine, and 4,4'-, 2,4'-, or 2,2'-diaminodiphenylmethane. Particularly interesting polyether polyols prepared from the compounds of the group cited are: N,N,N',N'-tetrakis(2-hydroxyethyl)-e~hylenediamine, N,N,N',N'-tetra~iq(2-hydroxypropyl)-ethylenediamine, N, N, N ', N", N 1 -pentakis~2-hydroxypropyl)-diethylenetriamine, phenyldiisopropanolamine, and higher molecular weight alkaline oxide adduces of aniline.
Further starter molecule are alkanolamines such as ethanol amine, diethanolamine, N-methyl- and N-ethyl-ethanol amine, N-methyl- and N-ethyldiethanolamine, and in-ethanol amine, ammonia, hydrazine, and hydrazides. Prefer-ably used are polyfunctional, in particular dip and/or in-functional, alcohols such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, glycerine, in-methylolpropane, pentaerythritol, sorbitol, and sucrose.
The polyether polyols can be utilized individually or in the form of mixtures just as the polyester polyols.

I

Crystallite suspensions, as described in German Patent Application P 30 01 462.1, can Allah be utilized as polyols. They can either be utilized individually or in the form of mixtures.
Among the blowing agents which can be used to prepare cellular plastic is water, which react with isocyanate groups to form carbon dioxide. The amounts of water which can be used to advantage are from 0.1 to 3 weight percent based on the weight of polyisocyanate, respectively from 0.1 to 2 weight percent based on the total weight of the polyisocyanate and polyol. In some cases, larger amounts of water can also be used.
Other blowing agents which can be used are low-boiling-point liquids which evaporate due to the exothermic polyaddition reaction. Here liquids which are inert with respect to the organic polyisocyanate and have boiling points of less than 50C are suitable. Examples of such preferably utilized liquids are halogenated hydrocarbon such as ethylene chloride, trichlorofluoromethane, dip chlorodifluoromethane, dichloromonofluoromethane, dichloro-tetrafluoroethane, and l,1,2-trichloro-1,2,2-trifluoro-ethanes Mixtures of these low-boiling-point liquid together and/or with other substituted or unsubstituted hydrocarbons can also be used.

~t72~3 The most suitable amount of low-boiling-point liquid used for the preparation of the cellular plastics depend on the desired foam density and, in some caves, on the additional utilization of water. In general, amounts ranting from 5 to 40 weight percent based on 100 parts by weight organic polyisocyanate, respectively from 2 to 30 percent based on the total weight of the polyisocyanate and polyol offer satisfactory results.
Suitable kettle is to function between the polyols, in Rome cases water, and the polyisocyanates are, for example, tertiary amine such as dimethylbenzylamine, 2-(dimethylaminoethoxy)ethanol, NUN ,N'-tetramethyldiamino-ethyl ether, bis(dimethylaminopropyl)urea, N-methyl-respectively N-ethylmorpholine, dimethylpiperazine, 1,2-dimethylimidazole, l-aza-bicyclo(3,3,0)octane, and, prefer-ably, triethylenediamine, metal salts such as tin dictate, lead octet, tin diethylhexoate, and, preferably, tin (II) salts and dibutyltin dilaurate as well as, in particular, mixtures of tertiary amine and organic tin salts, from 0.1 to 5.0 weight percent catalyst bayed on the tertiary amine and/or from 0.1 to 1.0 weight percent metal salts based on the weight of the polyols are preferably used.
The standard cyclization and polymerization catalysts for polyisocyanates have proved successful in preparing polyurethane group containing polyisocyanate plastic. Typical examples are: strong bases such a qua ternary ammonium hydroxides, for example, benzyltrimsthyl ammonium hydroxide, alkali metal hydroxides, for example, sodium or potassium hydroxide alkali metal alkoxides, for example, sodium methyl ate and potassium isopropyl ate;
trialkylphosphenes, for example, triethylphosphene, alkyd-aminoalkylphenol~, for example, 2,4,6-tris(dimethylamino-methyl phenol 3- and/or substituted pardons, for example, 3- or 4-methylpyridine, metal organic salts, for example, tetrakis(hydroxyethyl) sodium borate, Friedel-Crafts catalyst, for example, aluminum chloride, iron (III) chloride, boron fluoride, and zinc chloride, and alkali metal salts of weakly organic acids and nitrophenolates, for example, potassium octet, potassium 2-ethyl hexoate, potassium bonniest, sodium pirate, and potassium phthal-imide. Preferably, the strongly basic N,N'N"-tris(dialkyl-aminoalkyl)-s-hexahydrotriazines are utilized, for example, theN,N'N"-tris(dimethylaminopropyl)-s-hexahydrotriaziire, in some cases in combination with aliphatic low molecular weight moo- and/or dicarboxylic acids, for example acidic acid and/or adipic acid, or aromatic carboxylic acids such as benzoic acid.
The desired amount of isocyanurate group-forming catalyst depends on the effectiveness of the catalyst being used. In general, it has been found to be desirable to 7Z~3 utilize from 1 to 15 parts by weight, preferably from 3.5 to 10 parts by weight catalyst, per 100 parts by weight organic polyisocyanate.
In order to prepare urethane and polyisocyanurate group-containing plastics, the catalysts assisting the formation of urethane and isocyanurate groups can also be mixed together.
The rigid foams are preferably prepared in the presence of chain extenders or cross-linking agents. On the other hand, it has been found to be advantageous to prepare flexible cellular or dense polyurethane or polyurethane group-containing polyisocyanurates with additional chain extenders or cross-linking agents. Suitable chain extenders or cross-linking agents possess molecular weights from 30 to 600, preferably from 60 to 300, and they preferably have two active hydrogen atoms. Typical substances are: aliphatic and/or aromatic dills having from 2 to 14 carbon atoms, preferably from 2 to 6, such as propanediol, pentanediol, 1,6-hexanediol, and, preferably, ethanediol, 1,4-butanediol, and bis(2-hydroxyethyl)hydroquinone, dominoes such as ethylenediamine and, in some cases, 3,3'- respectively Dow- respectively tetraalkyl-substituted 4,4'-diaminodiphenylmethanes, ethanolamines such as triethanol-amine, and polyhydroxyl compound such as glycerine, trimethylolpropane, and low molecular weight hydroxyl group-3~%~27;2~3 containing polyalkylene oxide from the previously mentioned starting ~ub~tances.
Auxiliaries and additives can also be incorporated in the reaction mixture. Typical are stabilizers, hydrolysis inhibitors, pore regulator, fungi static and bacteriostatic agents, colorant, pigments, fillers, surfactants, and plasticizers.
Typical organic fillers are: rigid resins such as those known a binders for the printing industry, for example, those based on phenol, pine resin, or mailmen and formaldehyde, polyester with melting points greater than 190C, preferably cross-linked polyesters based on dip functional or higher functional carboxylic acids with divers or with monomers, for example, (meth)acrylic acid derive-lives, home- and copolymers of cyclopentadiene, kitten resins, for example, those bayed on cyclohexanone, and rigid polyurethane materials with melting points greater than 190C, for example, cross-linked polyurethane and issues-curate group-containing polyurethane, polyvinyl chloride, polyamide-6, and 6,6-acrylate graft rubbers, butadiene graft rubbers, as well as polyvinyl acetate.
Inorganic fillers have proven to be particularly suitable and are thus preferred: the conventional fillers, reinforcing materials, weight increasing materials, agents to improve the wear characteristics of paints, coatings, etc. However, inorganic pigment can also be used. Typical example are: silicate minerals, for example, lamellar, silicates such as antigorite, serpentine, horn blends, amphiboles, crystal, talcum, metal oxides such as kaolin, aluminimum oxide hydrate, titanium oxides, iron oxides, metal salts such as chalk, heavy spar, barium sulfate, inorganic pigments such a cadmium sulfide, zinc sulfide, and glass.
Typical auxiliaries are, for example, surfactant~
used to support the homogenization of the initial substances and, in some cases, are also suitable for regulating the cell structure. Typical examples are siloxane-oxyalkylene heteropolymers and other organic polysiloxanes, oxyethylated alkyd phenol, oxyethylated fatty alcohol, paraffin oils, castor oil or acid esters of castor oil, and Turkish Red Oil used in amount ranging from 0.1 part to 5 parts by weight per loo parts by weight of the mixture of the polyisocyanate and polyols.
Further information on the other additives cited above can be found in the technical literature on the subject, for example, in the monograph by J. H. Saunders and K. F. Fresh, High Pollers Vol. XVI, Polyurethane Puts. 1 and 2, Verlag Intrusions Publishers, 1962 and 1964.
In order to prepare the flexible semi-rigid or rigid cellular or dense polyurethane, the organic pulse 272~3 sonnets are reacted with the polyols, preferably polyester and/or polyether polyols, and, in some kiwi, with chain extenders or cross-linking agents in such amounts that the ratio of reactive hydrogen atoms to isocyanate groups is from 1:0.8 to 1:2.5, preferably from 1:0.9 to 1:1.2, and more preferably approximately 1:1.
For polyisocyanates containing dense polyurethane groups, the initial components are reacted in reactive hydrogen atom-to-isocyanate group ratios of from 1:40 to 1:5, preferably from 1:30 to 1:15, and for corresponding cellular polyisocyanurates from 1:40 to 1:2, preferably from 1:10 to 1:2.
The polyurethane or polyurethane group-containing polyi~ocyanurate plastics are preferably prepared in a one-; shot process. were the polyisocyanates are mixed with the polyols, catalysts, and, in some cases, chain extenders or cross-linking agents, blowing agents, auxiliaries, and additives in a vigorous manner with the cited quantitative ratios at temperatures from 0 to 50C, preferably from 15 to 40C, and then the reaction mixture is allowed to cure or expand in open or closed molds.
The rigid foams produced from the polyisocyanate mixtures of the invention are essentially white, exhibit good flame inhibiting properties, produce a low smoke gas density, and have good mechanical properties, in particular compressive load strength.

~L22~ 3 The example which follow are designed to enable those skilled in the art to practice the invention. The parts referred to in the examples are by weight and the temperature are in degrees centigrade unless otherwise stated.

eye Preparation of isocyanurate group-containing polyisocyanate mixtures of 4,4'- and 2,4'-diphenylmethane disunites.
Example 1 0.6 part try dimethylaminopropyl)-~-hexa-hydrotriazine was dissolved in 5 parts dim ethyl phthalate and were added to 3000 parts of a mixture comprising 47 weight percent 4,4'-diphenylmethane diisocyanate and 53 weight percent 2,4'-diphenylmethane diisocyanate in a 4-liter glass flask. The resulting reaction mixture was trimerized at this temperature for two hours while being stirred, and then the formation of isocyanurate was teem-inated by the addition of 1.5 parts bouncily chloride.
The resulting polyisocyanate mixture had an isocyanate content of 26.9 weight percent and a vacuity of 1060 maps at 25C.
Example 2 0.72 part 1,3,5-tris(3-dimethylaminopropyl)-s-hexahydrotriazine dissolved in 5 parts dimethylphthalate was added to 3000 parts of the above-cited 4,4'- and 2,4'-diphenylmethane diisocyanate mixture in a 4-liter glass flask while mixing at 40C. The reaction mixture was then trimerized for approximately 90 minutes at 80C. After an isocyanate content of 25.7 weight percent was reached, the 72~

mixture was Wylie cooled to 23C, mixed at this temperature for 18 hours, and the reaction was terminated by the addition of 1.5 parts bouncily chloride. The resulting polyi~ocyanate mixture had an isocyanate content of 24.1 weight percent and a viscosity of 10,700 mPaq at 25C.
Example 3 A series of three equal portions of 0.9 part of an adduce prepared from one mole 1,3,5-tris(3-dimethylamino-propyl)-s-hexahydrotriazine, one mole l,2-propylene oxide, and one mole 2-ethyl hexanoic acid in the form of a 15 weight percent solution in dimethylphthalate was added to 3000 parts of a mixture of 4,4'- and 2,4'-diphenylmethane diisocyanate in a weight ratio of 47:53 with an easily hydrolyzable chlorine content of I ppm in a 4-liter glass flask while mixing at 40C. After a reaction time of two hours, the trimerization was stopped by adding 1 part bouncily chloride.
The resulting polyisocyanate mixture had an isocyanate content of 25.8 weight percent and a viscosity of 4500 maps measured at 25~C.
Example 4 14 parts of the above-cited trimerization catalyst dissolved in 200 part dimethylphthalate was added in two equal portions to 40,000 parts of a mixture comprising 4,4'-and 2,4'-diphenylmethane in a weight ratio of 47:53 with an ~27~3 cagily hydrolyzable chlorine content of 70 ppm while stirring at 40C. After a second addition of catalyst, the temperature briefly rose to from 77 to 80C and then returned to 40C. After an isocyanate content of 24.8 weight percent was reached, the reaction was terminated by the addition of 13.5 parts bouncily chloride.
The resulting polyisocyanate mixture had a viscosity of 9700 maps at 25C.
Examples 5-15 Here the same procedure was used as in Example 3, except the 4,4'-/2,4'-diphenylmethane diisocyanate mixture composition was varied, the amount of catalyst, and the temperature of the added catalyst was also varied, so that the isocyanurate group-containing polyisocyanate mixture given in Table I were obtained.

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z 0 a o, Example 16 Eighty parts by weight of the isocyanurate group-containing polyi~ocyanate mixture prepared in accordance with Example 6 were mixed at room temperature with 20 parts by weight of a mixture of 2,4- and Tulane doesn't in a weight ratio of 80:20.
The resulting polyisocyanate mixture had an isocyanate content of 29.5 weight percent and a viscosity at 25C of 550 ma Example 17 The same procedure was followed as in Example 12, however, the isocyanurate group-containing polyisocyanate mixture and the Tulane diisocyanate mixture were combined in a 90:10 weight ratio.
The no ulting polyisocyanate mixture had an isn't content of 27.1 weight percent and a viscosity at 25C of 2100 ma Preparation of rigid polyurethane group-containing pulse-sonority foam.

General specifications for preparation:

A-Com~onent: Mixture of polyol, catalyst, foam stabilizer, blowing agent, and, in some caves, flame retardant.

~L~2~3 B-Componen~: Mixture of diphenylme~hane diisocyanates and polyphenyl-polymethylene polyisocyanate~ having an issues-Nate content of 31 weight percent (crude MID).

Components A and B were vigorously mixed together at 23C and allowed to expand freely in a box (dimensions 20x22x22 cm).
The type and quantity of initial components used, the characteristic values and mechanical properties are summarized in Table IT
The following abbreviations were used for the initial components in Table II:

Crystallite Suspension: Crystallite suspension having a hydroxyl number of 265, comprised of 48 parts by weight sucrose polyol, 28 parts by weight diethylene glycol adipate, and 24 part by weight neopentyl glycol isophthalate.
Swoop: Polyether polyol having a hydroxyl number of 400, prepared from a mixture of sucrose, triethanolamine, and water as initiator molecules, and 1,2-propylene oxide.

I

Pi: Polypropylene glycol having a hydroxyl number of 240.
Ethanol: Thinly R 350 X, Jefferson polyether polyol.
TCEP: Trichloroethyl phosphate.
DC 193: Foam stabilizer bayed on silicone, Dow Corning product.
B 1903: Foam stabilizer based on silicone, Gold Schmidt, En en product.
PI: Desmorapid~ PI polyurethane catalyst from Bayer AGO
Cat. 1: Catalyst adduce based on pentamethyl-diethylenetriamine, 1,2-propylene oxide and 2-ethylhexanoic acid.
Cat 2: Potassium format, 35 weight percent solution in ethylene glycol.

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Preparation of Rudy Polyurethane Foam example 21 A-Com~nent: Mixture comprising 19.6 parts by weight of a polyether polyol having a hydroxyl number of 400 prepared from a mixture of sucrose, glycerine, and water as starter molecules and 1,2-propylene oxide, 9.0 part by weight N,N,N',N'-tetraki~(2-hydroxypropyl)ethylenediaminee, 25 parts by weight phosphorus-containing flame retardant polyol Idol B 251, Sylvia), 3 parts by weight glycerine, 16 parts by weight tris(chloroethyl)phosphate, 1 part by weight silicone stabilizer (Bayer A stabilizer OX 710), 0.7 part by weight dimethylcyclohexylamine, 0.7 part by weight water, and 32.5 parts by weight trichlorofluoromethane.

B-Component: 121.6 parts by weight of a partially issues-unrated mixture of 2,4'- and 4,4'-diphenylmethane dozes-notes in a 53:47 weight ratio with an isocyanate content of 25.6 weight percent prepared in accordance with Example 15.
The A and B components were vigorously mixed together at 23C and were allowed to expand freely in a carton having dimensions 20x22x22 cm.
The characteristic data measured for the resulting polyurethane rigid foam and the mechanical characteristics of same are summarized in Table III.

Z72~3 I

Example 22 A-Component: As in Example 21, but instead of 32~5 parts by weight, only 30~8 parts by weight trichlorofluoromethane.

115.2 parts by weight of a partially issues-unrated mixture of 2,4'- and 4,4'-diphenylmethanediisocya-notes having an isocyanate content of 27.0 percent by weight prepared in accordance with Example 14.
The A and B components were mixed together and allowed to expand as in Example 21.
The characteristics and mechanical properties of the resulting rigid polyurethane foam are summarized in Table III.

A-Component: As in Example 21, but instead of 32.5 parts by weight, 33.4 parts by weight trichlorofluoromethane were used.
B-Component: 125 parts by weight of a partially issues-unrated mixture of 2,4'- and 4,4'-diphenylmethane dozes-notes hazing an isocyanate content of 24.9 weight percent were prepared in accordance with Example 13.
The A and B components were mixed together and allowed to expand as in Example 21.
The resulting rigid polyurethane foam coworkers-tics and mechanical properties are summarized in Table III.

7~3 TABLE III
Examples 21 22 23 Characteristics:
Mixing time, sec. 20 15 20 Cream time, eke. 32 25 35 Gel time, eke. 96 80 95 Rise time, sec. - 135 Mechanical Properties:
Density, g/l 24.4 25.8 26.7 Compression Strength per DIN 53 421, N/mm2 0.226 0.249 0.26 Compression at Failure per DIN 53 421, 7.4 7.8 7.0 Flexural Strength per DIN 53 423, (N/mm2) 0.243 0.282 0.30 Deflection at Break per DIN 53 423, mm 13.1 11.5 11.5 Dimensional Stability at Elevated Temperatures per DIN 53 424, C 175 170 187 Preparation of Dense Polyurethane Group-Containin~ Polxiao-senoritas Examples aye and 24b A-Component: Mixture comprising 98.2 parts by weight of a graft polyether polyol dispersion having a hydroxyl number of 29 and a copolymer content of 20 wright percent based on the total weight prepared by in situ polymerization of a mixture of styrenes and acrylonitrile at a 3:2 weight ratio in the presence of a polyether polyol based on trimethylol-propane, propylene oxide, and ethylene oxide, 0.5 part by weight ortho-tetraethyl silicate, 1.20 parts by weight 40 percent solution of potassium acetate in ethylene glycol, and 0.15 part by weight of an amidine tin Walt complex.
B-Component: Isocyanurate group containing polyisocyanate mixture of 4,4'- and 2,4'-diphenylmethane diisocyanate in a 47:53 weight ratio having an isocyanate content of 26.2 lo weight percent prepared in accordance with Example 3.
One hundred parts by weight of the A component and 140 parts by weight (Example aye) or 160 parts by weight (Example 24b) of the B component were processed with the aid of a high pressure model Permute 30 Elastogran Maschinenbau metering machine (Strasslach near Munich) and was processed into molded boards in a closed metal mold having interior dimensions of 4x400x400 mm using reaction injection molding technique. The boards were able to be remolded after 20 seconds. The temperature of the A and B components in the metal mold was 50C.
The mechanical properties of the molded board are summarized in Table IV.

~L22~7Z~3 Comparison Example IV
_ opponent: As in Example aye.
B-Component: Mixture of 4,4'- and 2,4'-diphenylmethane diisocyanate in a 47:53 weight ratio with an isocyanate content of 33.6 weight percent.
With an OH:NCO group ratio corresponding to that in Examples aye and 24b, in other words, a mixture ratio of 100 parts by weight A component to 110 parts by weight, respectively 125 parts by weight of the B component, the formulation could no longer be processed since the reaction mixture golfed within from 1.5 to 3 seconds due to the higher rate of isocyanuratization, 90 that the mold gore could no longer be filled.
Comparison Examples Via and Vb A-Component: Mixture comprising 98.67 parts by weight of a graft polyether polyol dispersion as in Examples aye and 24b, 0.50 parts by weight ortho-tetraethyl silicate, 0.75 parts by weight 40 percent solution of potassium acetate in ethylene glycol, and 0.08 parts by weight of an amidine zinc salt complex.
B-Component: Mixture of 4,4'- and 2,4'- diphenylmethane diisocyanate in a 47:53 weight ratio with an isocyanate content of 33.6 weight percent.
One hundred parts by weight of the A component and 110 parts by weight (Comparison Example Vat respectively 125 122~72~

parts by weight (Comparison Example Vb) of the B component were processed as in Examples aye and 24b into molded boards. Because of the greatly reduced catalyst content, remolding time was 60 second.
The mechanical properties measured on the molded boards are summarized in Table IV.

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~2~%~3 Example aye and 24b show that the use of the isocyanurate group-containing polyi~ocyanate mixture of the invention produce molded board with a high impact strength, which only are reduced by approximately 40 percent at elevated temperatures (up to 120 minutes at 200C), whereby this reduction does not increase progressively with time. Particularly worth noting is the high dimensional stability of the molded boards at elevated temperatures, in particular the higher index.
In Comparison Examples Via and Vb, on the other hand, a board was obtained whose impact strength reduced sharply and progressively at elevated temperatures until the material became unusable. A further disadvantage was the low dimensional stability at elevated temperatures, making the material unsuitable for thermal breaks in aluminum window moldings which are subsequently powder coated.

Claims (9)

The embodiments of the invention in which an exclusive privilege or property is claimed are defined as follows:
1. Liquid, isocyanurate-containing polyisocyanate mixtures having an isocyanate group content of 23 to 31 weight percent which are obtained by partial trimerization of a mixture consisting of about 80 to about 30 weight percent of 4,4'-diphenylmethane diisocyanate and about 20 to about 70 weight percent of 2,4'-diphenylmethane diisocyanate based on total weight of diisocyanate in the presence of a trimerizing catalyst and subsequent deactivation of the tri-merizing catalyst.
2. The polyisocyanate mixtures of claim 1 containing an amount of isocyanurate groups of about 10 to about 2.6 weight percent.
3. The polyisocyanate mixtures of claim 1 having a viscosity of 20 to 200,000 mPas at 25°C.
4. Polyisocyanate mixtures comprising about 100 to about 60 weight percent of an isocyanurate group-containing polyisocyanate mixture of claim 1 and about 0 to about 40 weight percent of another aliphatic, cycloaliphatic or aromatic polyisocyanate with the weight percentages being based upon the total weight of the polyisocyanate mixture.
5. Polyisocyanate mixtures comprising about 95 to about 60 weight percent of an isocyanurate group-containing polyisocyanate mixture of claim 1 and about 5 to about 40 weight percent of an aromatic polyisocyanate selected from the group consisting of (1) the 2,4- and 2,6-toluene diisocyanates or mixtures thereof; (2) mixtures of 4,4'-, 2,4'-, 2,2'-diphenylmethane diisocyanates and polyphenyl-polymethylene polyisocyanates; (3) urethane-modified 4,4'-diphenylmethane diisocyanates, (4) urethane-modified mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates;
and (5) urethane-modified mixtures of 4,4'-, 2,4'-, 2,2'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates.
6. A process for the preparation of liquid, isocyanurate group-containing polyisocyanate mixtures comprising trimerizing a mixture of about 80 to about 30 weight percent of 4,4'-diphenylmethane diisocyanate and about 20 to about 70 weight percent of 2,4'-diphenylmethane diisocyanate based on the total weight of the mixture at temperatures of 0°C to 160°C in the presence of trimerizing catalysts until the polyisocyanate mixture has an isocyanate group content of 23 to 31 weight percent, and subsequently cooling the mixture and deactivating the trimerizing catalyst.
7. The process of claim 6 wherein the trimerizing catalyst is incorporated in the mixture of 4,4'- and 2,4'-diphenylmethane diisocyanate at temperatures of 0°C to 30°C, and wherein the mixture is subsequently trimerized at temperatures up to 100°C.
8. The process of claim 6 wherein an adduct of 1 mole of tris-(dimethylaminopropyl)-s-hexahydrotriazine, 1 mole of 1,2-propylene oxide and 1 mole of 2-ethylhexanoic acid is used as trimerizing catalyst, wherein the trimeri-zation is carried out at temperatures at 25°C to 100°C, and wherein the reaction mixture is subsequently allowed to cool without chemically deactivating the trimerizing catalyst.
9. Cellular or non-cellular polyurethane or polyurethane group-containing polyisocyanurate plastics prepared from the isocyanurate group-containing polyisocya-nate mixture of claim 1 as the isocyanate component.
CA000447165A 1983-02-12 1984-02-10 Liquid isocyanurate group-containing polyisocyanate mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanate, method for their preparation and their use in polyurethane or polyisocyanurate plastics Expired CA1227203A (en)

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DE19833304889 DE3304889A1 (en) 1983-02-12 1983-02-12 LIQUID POLYISOCYANATE MIXTURES CONTAINING ISOCYANURATE GROUPS OF 4,4'- AND 2,4'-DIPHENYLMETHANE DIISOCYANATES, METHODS FOR THE PRODUCTION THEREOF AND THE USE THEREOF FOR POLYURETHANE OR POLYISOCYANURATE ART

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US5250608A (en) * 1991-08-02 1993-10-05 Imperial Chemical Industries Plc Curable compositions
AU645290B2 (en) * 1990-03-07 1994-01-13 Huntsman Ici Chemicals Llc Polyisocyanate composition
US11560446B2 (en) * 2016-12-27 2023-01-24 Basf Se Polyurethane foam article and method of forming same

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DE4026474A1 (en) * 1990-08-22 1992-02-27 Bayer Ag Isocyanurate Gp.-contg. poly-isocyanate mixts. for PU foam prodn. - by partial trimerisation of mixt. of specified amts. of 4,4-, 2,4- and 2,2-MDI isomers contg. 0-20 wt. per cent higher poly-isocyanate(s)
DE502008000184D1 (en) * 2007-03-05 2009-12-31 Basf Se Compact polyisocyanurate with improved processing and product properties and process for its preparation
WO2017046274A1 (en) 2015-09-18 2017-03-23 Covestro Deutschland Ag Method for producing a rigid polyurethane-polyisocyanurate foam
EP3728384B1 (en) * 2017-12-21 2023-03-01 Covestro Deutschland AG Method for producing isocyanate mixtures containing isocyanurate groups

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US3960788A (en) * 1974-09-23 1976-06-01 Jefferson Chemical Company, Inc. Modified isocyanate foams
DE2525017C3 (en) * 1975-06-05 1981-11-26 Basf Ag, 6700 Ludwigshafen Process for the production of possibly flame-retardant polyisocyanurate foams containing urethane groups
DE2616416C2 (en) * 1976-04-14 1982-11-11 Basf Ag, 6700 Ludwigshafen 1,3,5-Tris- (N, N-dialkylaminoalkyl) -shexahydrotriazine addition compounds and their use as trimerization catalysts for polyisocyanates
DE2616415A1 (en) * 1976-04-14 1977-11-03 Basf Ag Isocyanurate-contg. polyisocyanates prepn. - by polymerising aliphatic diisocyanates and opt. aromatic diisocyanates using a catalyst-cocatalyst system
DE2722400C2 (en) * 1977-05-17 1985-05-30 Bayer Ag, 5090 Leverkusen Process for the production of heat-resistant, bubble-free plastics containing isocyanurate groups
DE3041732A1 (en) * 1980-11-05 1982-06-09 Bayer Ag, 5090 Leverkusen SOLUTIONS OF ISOCYANATO-ISOCYANURATE IN SOFTENERS FOR POLYVINYL CHLORIDE, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS ADDITIVE ADHESIVES IN COATING AGENTS BASED ON SOFT-MADE POLISHED POLYMER
DE3100263A1 (en) * 1981-01-08 1982-08-12 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING POLYISOCYANATES CONTAINING ISOCYANURATE GROUPS AND THE USE THEREOF IN THE PRODUCTION OF POLYURETHANES
US4382125A (en) * 1981-11-30 1983-05-03 Basf Wyandotte Corporation Isocyanurate-modified polymethylene polyphenylene polyisocyanate compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU645290B2 (en) * 1990-03-07 1994-01-13 Huntsman Ici Chemicals Llc Polyisocyanate composition
US5250608A (en) * 1991-08-02 1993-10-05 Imperial Chemical Industries Plc Curable compositions
US11560446B2 (en) * 2016-12-27 2023-01-24 Basf Se Polyurethane foam article and method of forming same

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