DE19961973A1 - Agent for surface modification of fillers for polyamide composition comprises selected functionalized silane compounds - Google Patents

Abstract

An agent for the surface modification of fillers for polyamide compositions comprises: (A) an amino-functional silane, a bis-aminosilane a tertiary aminosilane or an oligomer of these; (B) a mixture of an amino-functional silane, bis-aminosilane and/or tertiary aminosilane and an alkyl-, alkenyl- or polyether-functional silane and optionally an oligomer of these; or (C) a mixture of an alkyl-functional silane and an alkenyl-functional silane and optionally an oligomer of these. An agent for the surface modification of fillers for polyamide compositions comprises either: (A) an agent comprising: (i) an amino-functional silane of formula (Ia); (ii) a bis-aminosilane (Ib); (iii) a tertiary aminosilane (Ic); or an oligomer of (Ia)-(Ic) with a degree of oligomerization (DO) of 2-20; (B) a mixture of: (i) a component comprising (a) an amino-functional silane of formula (IIa), (b) a secondary aminosilane (IIb) and/or (c) a tertiary aminosilane (IIc); and (ii) a component comprising either (a) an alkyl-functional silane of formula (III), (b) an alkenyl-functional silane of formula (IV), (c) a polyether-functional silane of formula (V); and optionally (iii) an oligomer of (IIa)-(IIc) and (III)-(V) with a DO of 2-20; or (C) a mixture of: (i) an alkyl-functional silane of formula (IIIa); and (ii) an alkyl-functional silane of formula (IV); and optionally (iii) an oligomer of (IIIa) and (IV) with a DO of 2-20. RNH-(CH2)3-Si(Me)x(Z)3-x (Ia) Z = 1-3C alkoxy, OH or Cl; x = 0 or 1; and R = 1-20C alkyl, 5-12C cycloalkyl or 6-12C aryl. R-Si(Me)x(Z)3-x (IIa) Z = 1-3C alkoxy, OH or Cl; x = 0 or 1; R = H2N((CH2)2NH)y(CH2)3; and y = 0-2. R'-Si(Me)x(Z)3-x (IIIa) Z = 1-3C alkoxy, OH or Cl; x = 0-1; and R' = optionally fluorinated 1-16C alkyl or cycloalkyl. CH2=CH(CH2)n-Si(Me)x(Z)3-x (IV) Z = 1-3C alkoxy, OH or Cl; x = 0 or 1; and n = 0-20. R(OCH2CHR')nO(CH2)mSi (Me)x(Z)3-x (V) z = 1-3C alkoxy, OH or Cl; x = 0 or ; R = 1-4C alkyl; R' = H or Me; n = 5-20; and m = 2 or 3. Independent claims are also included for the following: (1) a filler surface-modified with the above agent; (2) an article comprising the surface-modified filler; (3) a filled polyamide composition produced using the surface-modified filler; and (4) an article based on the filled polyamide composition.

Description

The invention relates to a process for the production of poly urethanes (PUR) with improved curing using special isocyanates or isocyanate mixtures.

The production of PUR using NCO-containing Connections has been known for a long time and has been used in many different ways wrote. A summary overview of the manufacturing of PUR z. B. in the plastics manual, volume VII, polyurethanes, Carl-Hanser-Verlag, Munich, 1st edition 1966, published by Dr, R. Vieweg and Dr. A. Höchtlen, as well as 2nd edition 1983 and 3rd edition 1993, published by Dr. G. Oertel.

As the isocyanate component are aliphatic, cycloaliphatic, araliphatic, heterocyclic and particularly aromatic di- and / or polyisocyanates, such as z. B. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pp. 75-136, for example those of the formula Q (NCO) _n , in which n = 2 to 4, preferably 2, and Q is an aliphatic hydrocarbon radical with 2 to 18, preferably 6 to 12 carbon atoms, a cyclo aliphatic hydrocarbon radical with 4 to 20, preferably 5 to 11 carbon atoms, an aromatic hydrocarbon radical with 6 to 20, preferably 6 to 13 carbon atoms, or one araliphatic hydrocarbon radical with 8 to 15, preferably 8 to 13 carbon atoms, mean, for. B. such polyisocyanates, as described in DE-A-28 32 253, pp. 10-11, are used.

The technically easily accessible are particularly preferred Polyisocyanates, e.g. B. the 2,4- and / or 2,6-tolylene diisocyanate as well as any mixtures of these isomers (TDI), diphenylmethane diisocyanates (4,4'- and / or 2,4'- and / or 2,2'-isomers), poly phenyl-polymethylene-polyisocyanates, such as those obtained from aniline form aldehyde condensation and subsequent phosgenation are (raw MDI), and "modified polyisocyanates" which, for. B. Carbodiimide groups, urethane groups, allophanate groups, iso cyanurate groups, urea groups and / or biuret groups point; especially those modified polyisocyanates that from 2,4- and or 2,6-tolylene diisocyanate and preferably from Derive 4,4'- and / or 2,4'-diphenylmethane diisocyanate. Become only bifunctional higher molecular compounds and given if only two-functional, further low molecular chain ver elongation means used, it is preferred to use modified  Polyisocyanates with a functionality of more than 2.0 or uses tri- and / or higher functional polyisocyanates.

For the reaction with the isocyanates, polyol components are used at least two isocyanate-reactive water Substance atoms with a molecular weight usually from 200 to 8000 used.

This means in particular 2 to 8 hydroxyl groups containing polyester and / or polyether, as for the Production of homogeneous and cellular polyurethanes known are and how they z. B. in DE-A-28 32 253, pp. 11-18 be.

The highest possible degree of crosslinking is required when producing the PUR in the matrix and thus a better hardening a constant Objective, so far in particular on the polyol component is controlled.

For the production of PUR, especially PUR foams for Isolation purposes, u. a. Aromatic polyols Amines used. The use of alkylene oxide adducts of Toluene diamines (TDA), especially 2,4- and 2,6-TDA and Mixtures of these have long been known (GB 972 772). In the last Work in the field has intensified since ten years since it has been found (US-A-4 209 609 = EP-A-0 001 800) that Rigid PUR foams based on TDA polyethers compared to conventional rigid PUR foams have some serious advantages sen if they are in the OH number range 400 to 630 mg KOH / g and be prepared in such a way that TDA initially with about 4 mol Ethylene oxide and then reacted with propylene oxide, d. H. in addition to a high OH number and a minimum proportion Ethylene oxide, all end groups must be secondary. As advantages are in particular an extremely low coefficient of thermal conductivity, a to name favorable flame retardancy and good toughness.

Pure propylene oxide polyether, by conventional methods are extremely highly viscous in the OH number range mentioned (<50,000 mPa.s / 25 ° C) and only supply rigid foams with the usual property level. The latter also applies to relative low-viscosity pure propylene oxide polyethers, as described in U.S. 4,391,728 in the presence of at least 0.8% alkali metal hydroxide can be produced at high temperatures. Pure Ethylene oxide polyethers, in turn, are primary OH groups too active for most rigid foam applications.  

In addition to TDA, diphenylmethane and / or polyamines are used as Starter used for the production of polyetherols.

These polyols are made directly or through the prepolymer stage production implemented with the isocyanates.

For special applications such as in paints and coatings sector or for the construction of isocyanurate structures Trimerized isocyanates and thereby converted into isocyanurates. EP-A-0 789 299 describes the manufacture and use thereof described in combination with other isocyanate derivatives.

All of these derivatizations via the polyol insert or via the use of isocyanate should be the properties in PUR foams, such as higher crosslinking, higher hardness and / or higher heat form consistency, improve, but also the basic product properties, such as viscosity, do not deteriorate. Bring like this also allophanates based on higher quality alcohol mixtures none Viscosity advantages over biuret or isocyanurate polyiso cyanates (DE-A-27 29 990). But they lead to a functional lowering of the crime and thus a slump in the actually desired o. g. Property improvements.

The invention was therefore based on the object of a method for the production of PUR, in particular PUR rigid foams, with improved curing, higher crosslinking, higher hardness and higher heat resistance through the use of special To develop isocyanates or isocyanate mixtures.

This object was achieved in that min at least a special isocyanate or isocyanate mixture for Use, which is caused by phosgenation of condensation products from aniline and toluenediamine and / or other amines with formaldehyde or by phosgenation of mixtures of these Condensation products obtained with amines from the diphenylmethane series becomes.

The invention thus relates to a method for the production of PUR by implementing organic and / or modified organic polyisocyanates (a) with at least one compound with at least two reactive hydrogen atoms (b) in the presence of catalysts (c), optionally blowing agents (d) and optionally other auxiliaries and additives (e) that there characterized in that component (a) has at least one contains special isocyanate or isocyanate mixture, which by Phosgenation of condensation products from aniline and toluene diamine and / or other amines with formaldehyde or through  Phosgenation of mixtures of these condensation products with Amines of the diphenylmethane series is obtained.

The invention furthermore relates to the special isocyanate, which by phosgenation of condensation products from aniline and toluenediamine and / or further amines with formaldehyde or by phosgenation of mixtures of these condensation products is available with amines of the diphenylmethane series, the use these isocyanates for the production of PUR as well as those based on them Way to produce PUR itself.

Used for the production of the PUR according to the invention special isocyanates or mixtures of isocyanates can be used as further Amines the usual amines known in PUR chemistry, ins special other aromatic mono- or polyamines used become. Phenylenediamines or toluidines are preferred used.

The molar ratio of the amines used to the formaldehyde is preferably 1.5 to 1 to 10 to 1, in particular 2 to 1 to 6 to 1. The molar ratio of aniline to toluenediamine and / or others Amines is preferably 2 to 1 to 15 to 1, in particular 3 to 1 to 10 to 1. The condensation reaction takes place with the addition of acidic catalysts. The molar ratio of catalyst to amines is preferably 0.01 to 1, in particular 0.1 to 0.5. As Acidic catalysts can be used generally for this implementation known catalysts are used, for example mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid are preferred hydrochloric acid is used.

The reaction of the amines with formaldehyde is more advantageous wise semi-continuous, d. H. Aniline, the acid catalyst, Toluene diamine and / or other amines are presented and form added aldehyde. The condensation reaction is common at temperatures of 20 to 100 ° C, preferably 20 to 50 ° C leads. In a preferred variant, aniline and the acidic Catalyst submitted and formaldehyde added. After finished Formaldehyde is added to a temperature of 60 to 90 ° C before pulls 65 to 75 ° C, heated and toluenediamine and optionally further amines added. Then there is one in both variants Tempering to <95 ° C, preferably 110 to 130 ° C, for a period of at least one hour, preferably 2 to 6 hours. The acidic amine Mixing can be done by conventional methods such as neutralization, phases separation and distillation are worked up.  

According to the invention, the special condens obtained in this way tion products with amines of the diphenylmethane series, in particular with methylene dianiline and higher oligomers that are based on the usual Kind of like B. in DD-A-238 042 or in DD-A-295 628, by acidic condensation of aniline with formaldehyde are to be mixed, the mixtures at least 20 wt .-%, preferably 40 to 60 wt .-%, of the Invention according to special condensation products.

The used for the production of the PUR according to the invention Isocyanates are by phosgenation of the condens described tion products or mixtures of these condensation products Diphenylmethane series amines available.

The phosgenation can be carried out in customary inert solvents, such as e.g. B. toluene, mono- or dichlorobenzene, in conventional reactors, for example stirred kettles or columns, with known tempera tures from 50 to 150 ° C, preferably 70 to 100 ° C, and a pressure from 0.5 to 10 bar, preferably 0.8 to 5 bar. The crude isocyanate produced by the phosgenation can by usual processes, for example distillation, can be cleaned. Falling film or thin film evaporators can be used as apparatus for this or packed columns can be used. This cleaning can done in two procedural steps. At a temperature of 50 to 150 ° C are first phosgene, HCl and solvent Stripping, if necessary under vacuum or by feeding in Inert gas, separated from the crude isocyanate. Then be at a temperature of 150 to 190 ° C, again by stripping or vacuum, the remaining solvent and any chlorine containing connections removed.

The polyurethanes according to the invention are produced by reacting the special isocyanates described above and optionally further organic and / or modified organic polyisocyanates (a) with at least one compound with at least two reactive hydrogen atoms (b) in the presence of catalysts (c), optionally blowing agents (d) and optionally other auxiliary substances and additives (e).

The special isocyanates or isocyanate mixtures (a) and compounds with at least two reactive hydrogen atoms (b) implemented in amounts such that the equivalence ratio of NCO groups of the isocyanates (a) to the sum of the reak tive hydrogen atoms of component (b) 1: 0.3 to 1: 2, before preferably 1: 0.4 to 1: 1.7 and in particular 10.9 to 1: 1.1 is.  

The following is to be explained in detail regarding the starting components to lead:

As organic and / or modified organic polyisocyanates (a) is at least one special isocyanate or isocyanate mixture used as described above. In addition, other organic and / or modified organic polyisocyanates with be used. For this come the well-known aliphati rule, cycloaliphatic, araliphatic and preferably aromatic polyvalent isocyanates in question.

The following may be mentioned as examples: alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpenta methylene diisocyanate 1,5, tetramethylene diisocyanate 1,4 and before preferably 1,6-hexamethylene diisocyanate, cycloaliphatic diiso cyanates, such as cyclohexane-1,3- and -1,4-diisocyanate and any Mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-iso cyanatomethylcyclohexane (IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the ent speaking isomer mixtures, and preferably aromatic di- and polyisocyanates, such as. B. 2,4- and 2,6-tolylene diisocyanate and the corresponding mixtures of isomers, 4,4'-, 2,4'- and 2,2'-di phenylmethane diisocyanate and the corresponding mixtures of isomers, Mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates, poly phenylpolymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenylpolymethylene poly isocyanates (raw MDI) and mixtures of raw MDI and toluene di isocyanates. The organic di- and polyisocyanates can individually or in the form of their mixtures. Especially mixtures of polyphenylpolymethylene polyisocyanate are preferred with MDI, preferably the proportion of 2,4'-MDI <30% by weight is.

So-called modified polyvalent iso are also common cyanate, d. H. Products made by chemical conversion of organic Di- and / or polyisocyanates are obtained used. Example ester, urea, biuret, allophanate, Carbodiimide, isocyanurate, uretdione and / or urethane groups containing di- and / or polyisocyanates. In detail come with Examples include: modified 4,4'-diphenylmethane diiso cyanate, modified 4,4'- and 2,4'-diphenylmethane diisocyanate mixtures, modified raw MDI or 2,4- or 2,6-tolylene diisocyanate, urethane-containing organic, preferably aromatic polyisocyanates with NCO contents of 43 to 15% by weight, preferably from 31 to 21% by weight, based on the total weight,  for example reaction products with low molecular weight diols, Triplets, dialkylene glycols, trialkylene glycols or polyoxy alkylene glycols with molecular weights up to 6000, especially with Molecular weights up to 1500, these as di- or polyoxy alkylene glycols can be used individually or as mixtures can. Examples include: diethylene and dipropylene glycol, polyoxyethylene, polyoxypropylene and polyoxypropylene polyoxyethylene glycols, triols and / or tetrols. Are suitable also prepolymers containing NCO groups with NCO contents of 25 up to 3.5% by weight, preferably from 21 to 14% by weight, based on the total weight made from those described below Polyester and / or preferably polyether polyols and 4,4'-di phenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenyl methane diisocyanate, 2,4- and / or 2,6-tolylene diisocyanates or Raw MDI. Liquid carbodiimide groups have also proven successful and / or polyisocyanates containing isocyanurate rings with NCO Contained from 43 to 15, preferably 31 to 21 wt .-%, be moved to the total weight, e.g. B. based on 4,4'-, 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4- and / or 2,6-tolylene diisocyanate.

The modified polyisocyanates can be used together or with unmodified organic polyisocyanates, such as. B. 2,4'-, 4,4'-diphenylmethane diisocyanate, crude MDI, 2,4- and / or 2,6-tolylene diisocyanate can be mixed.

Organic polyisocyanates and are therefore preferably used: mixtures of toluene diisocyanates and raw MDI or mixtures of modified Organic polyisocyanates containing urethane groups with a NCO content of 33.6 to 15 wt .-%, especially those based of tolylene diisocyanates, 4,4'-diphenylmethane diisocyanate, Di phenylmethane diisocyanate isomer mixtures or crude MDI and ins special raw MDI with a diphenylmethane diisocyanate isomer content of 30 to 80 wt .-%.

As compounds with at least two reactive hydrogen atoms (b) expediently those with functionality from 2 to 8, preferably 2 to 3, and a molecular weight from 300 to 8000, preferably from 300 to 5000.

For example, polyols selected from the group of polyether polyols, polyester polyols, polythioethers polyols, polyester amides, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates, or Mixtures of at least two of the polyols mentioned are used. The hydroxyl number of the polyhydroxyl compounds is in  generally 20 to 80 and preferably 28 to 56. In addition, can for example, polyether polyamines can also be used.

The polyether polyols used are for example by anionic polymerization with alkali hydroxides, such as. As sodium or potassium hydroxide, or alkali alcoholates such as B. sodium methylate, sodium or potassium ethylate or potassium isopropylate as catalysts and with addition at least one starter molecule containing 2 to 8, preferably 2 to 3, contains reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids such as antimony penta chloride, boron fluoride etherate u. a., or bleaching earth, as Kataly catalysts from one or more alkylene oxides with 2 to 4 carbons Substance atoms produced in the alkylene radical. For special use Monofunctional starters can also be used in the polyether construction.

Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately one after the other or as mixtures be used.

Examples of suitable starter molecules are: water, organic dicarboxylic acids, such as succinic acid, adipic acid, Phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl substituted Diamines with 1 to 4 carbon atoms in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, Diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexa methylenediamine, phenylenediamine, 2,3-, 2,4- and 2,6-tolylene diamine and 4,4 ', 2,4'- and 2,2'-diaminodiphenylmethane. As Starter molecules also come into consideration: alkanolamines, such as. B. Ethanolamine, N-methyl- and N-ethylethanolamine, dialkanolamines, such as B. diethanolamine, N-methyl and N-ethyldiethanolamine, and Trialkanolamines, such as. B. triethanolamine, and ammonia. Preferential wise are used, especially two and / or trihydric alcohols, such as ethanediol, 1,2-propanediol and 2,3, Diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, Glycerin, trimethylolpropane, pentaerythritol.

Polymer-modified poly are also suitable as polyether polyols ether polyols, preferably graft polyether polyols, in particular those based on styrene and / or acrylonitrile, which in In situ polymerization of acrylonitrile, styrene or preferably Mixtures of styrene and acrylonitrile, e.g. B. in weight ratio  90: 10 to 10: 90, preferably 70: 30 to 30: 70, expediently in the aforementioned polyether polyols analogous to the details of German patents 11 11 394, 12 22 669 (US 3 304 273, 3 383 351, 3 523 093), 11 52 536 (GB 1 040 452) and 11 52 537 (GB 987 618) are made, as well as polyether poly dispersions, which as disperse phase, usually in an amount of 1 to 50% by weight, preferably 2 to 25 wt .-%, contain: z. B. polyureas, Polyhydrazide, poly containing tert-amino groups urethanes and / or melamine and the z. B. are described in EP-B-011 752 (US 4 304 708), US-A-4 374 209 and DE-A-32 31 497.

The polyether polyols can be used individually or in the form of mixtures be used.

Suitable polyester polyols can, for example, from organic Dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms, polyhydric alcohols, preferably diols, with 2 to 12 carbons atoms, preferably 2 to 6 carbon atoms usual procedures are produced. Usually the organic polycarboxylic acids and / or derivatives and polyvalent Alcohols, advantageously in a molar ratio of 1: 1 to 1.8, preferably from 1: 1.05 to 1.2, catalyst-free or preferred wise in the presence of esterification catalysts, more appropriate as in an atmosphere of inert gas, such as. B. nitrogen, Carbon monoxide, helium, argon and the like. a., in the melt at Temperatures of 150 to 250 ° C, preferably 180 to 220 ° C, optionally under reduced pressure to the desired Acid number, which is advantageously less than 10, preferably is less than 2, polycondensed.

The PUR can be used with or without the use of chains extenders and / or crosslinking agents are produced. Used as a chain extender and / or crosslinking agent diols and / or triols with molecular weights smaller than 400, preferably 60 to 300. For example aliphatic, cycloaliphatic and / or araliphatic diols with 2 to 14, preferably 4 to 10 carbon atoms, such as. B. Ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, p-di hydroxycyclohexane, diethylene glycol, dipropylene glycol and preferred 1,4-butanediol, 1,6-hexanediol and bis- (2-hydroxyethyl) - hydroquinone, triols, such as 1,2,4- and 1,3,5-trihydroxycyclohexane, Triethanolamine, diethanolamine, glycerin and trimethylolpropane and low molecular weight hydroxyl-containing polyalkylene oxides Based on ethylene and / or 1,2-propylene oxide and the aforementioned Diols and / or triols as starter molecules.  

If for the manufacture of PUR chain extenders, Ver wetting agents or mixtures thereof are used expediently in an amount of up to 20% by weight, preferably from 2 to 8% by weight, in each case based on the weight of the polyol compounds.

As catalysts (c) for the production of the PUR according to the invention In particular, compounds are used to control the reaction the reactive hydrogen atoms, especially hydroxyl groups containing compounds of components (b) and (c), with the organic, optionally modified polyisocyanates (a) speed up hard. The isocyanate groups can by suitable Catalysts are also reacted with one another, preferably isocyanurate structures are formed. As a kata lysators are used in particular such substances accelerate the reactions of the isocyanates, especially the Urethane, urea and isocyanurate formation.

For example, organic metal compounds are suitable, preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, e.g. B. tin (II) acetate, tin (II) octoate, Tin (II) ethylhexoate and tin (II) laurate, and the Dialkyltin (IV) salts of organic carboxylic acids, e.g. B. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and Dioctyltin diacetate. The organic metal compounds are alone or preferably in combination with strongly basic Amines used. Examples include amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as Triethylamine, tributylamine, dimethylbenzylamine, N-methyl, N-ethyl, N-cyclohexylmorpholine, N, N, N ', N'-tetra-methylethylene diamine, N, N, N ', N'-tetramethylbutane diamine, N, N, N', N'-tetramethyl hexanediamine-1,6, pentamethyldiethylenetriamine, tetramethyldiamino ethyl ether, bis (dimethylaminopropyl) urea, dimethyl piperazine, 1,2-dimethylimidazole, 1-azabicyclo (3,3,0) octane and preferably 1,4-diazabicyclo- (2,2,2) octane, and amino alkanol compounds, such as triethanolamine, triisopropanolamine, N-methyl and N-ethyldiethanolamine and dimethylethanolamine. As Catalysts are also suitable: tris (dialkylamino alkyl) -s-hexahydrotriazines, especially tris- (N, N-dimethylamino propyl) -s-hexahydrotriazine, tetraalkylammonium hydroxides, such as Tetramethylammonium hydroxide, alkali hydroxide such as sodium hydroxide, and alkali alcoholates, such as sodium methylate and potassium isopropylate, and alkali salts of long-chain fatty acids with 10 to 20 carbon atoms and possibly pendant OH groups.

Tertiary amines, tin and bismuth compounds are preferred,  Alkali and alkaline earth carboxylates, quaternary ammonium salts, s-hexahydrotriazines and tris (dialkylaminomethyl) phenols.

The catalysts are preferably used in an amount of 0.001 to 5 wt .-%, in particular 0.05 to 2 wt .-% catalyst or catalyst combination, based on the weight of the compo nenten (b) to (e) used.

To produce the PUR according to the invention, in particular from Her position of PUR foams, is the use of blowing agents (d) sensible. Water is usually used as the blowing agent set which by the reaction with the isocyanate groups Cleaves carbon dioxide. The water content is preferably 0.1 up to 4% by weight, in particular 0.3 to 3% by weight, based on the Component (b) weight. The water additive can be combined with the use of physical blowing agents (d).

As a physically active blowing agent (d) from the Polyurethane chemistry generally known chlorofluorocarbons substances (CFCs) as well as highly and / or perfluorinated hydrocarbons fabrics are used. However, the use of these substances will severely restricted or entirely due to ecological reasons posed. In addition to HCFCs and HFCs, there are particularly: aliphatic and / or cycloaliphatic hydrocarbons as Alternative blowing agent. In particular, low boiling Hydrocarbons, lower monofunctional alcohols, acetals, such as B. methylal used. Low-boiling are preferred cyclic and acyclic saturated hydrocarbons with up to 12 carbon atoms, individually or in any mixture can be used together. In particular, pentanes used, both mixtures of the pentane isomers and pure isomers can be used. Due to the be Cyclopentane has particularly low thermal conductivity values used particularly preferably. These physical blowing agents are usually added to the polyol component of the system. However, you can also in the isocyanate component or as a combination nation of both the polyol component and the isocyanate component be added. The amount of physical used Blowing agent or the blowing agent mixture is 1 to 30 wt .-%, based on the weight of component (b).

The reaction mixture for producing the PUR according to the invention may be additional aids and / or additives (e) incorporated. Examples include surface-active ones Substances, foam stabilizers, cell regulators, fillers, colors  substances, pigments, flame retardants, hydrolysis protection agents, fungistatic and bacteriostatic substances.

Flame retardants can all be found in polyurethane chemistry usual materials are used for this purpose. Mainly halogen and phosphorus compounds are used, for example tricresyl phosphate, tris (2-chloroethyl) phosphate, Tris (2-chloropropyl) phosphate, tetrakis (2-chloroethyl) ethylenedi phosphate, dimethylmethanephosphonate, diethanolaminomethylphosphon acid diethyl ester and commercially available halogen-containing flame protective polyols. Because in the future the foams only come with halogen-free additives must also be manufactured the flame retardants should be halogen-free. Here come for example wise derivatives of phosphoric acid reactive towards isocyanate, phosphorous acid or phosphonic acid in question, optionally in combination with non-reactive liquid and / or solid halogen-free flame retardants, e.g. B. from organic derivatives of phosphoric acid, phosphorous acid or the phosphonic acid or salts of phosphoric acid and others substances that support flame protection, such as starch, cellulose, Aluminum hydrate u. a. In general, it has proven to be useful proven 5 to 40 parts by weight, preferably 5 to 25 parts by weight, of the flame retardants mentioned for 100 parts by weight of each Component (b) to use.

As surface-active substances such. B. Connections in Consider which to support the homogenization of the Aus serve and are also suitable, if necessary, the Regulate cell structure of plastics. May be mentioned at for example emulsifiers, such as the sodium salts of castor oil sulfates or fatty acids and salts of fatty acids with amines, e.g. B. oleic acid diethylamine, stearic acid diethanolamine, ricinol acidic diethanolamine, salts of sulfonic acids, e.g. B. alkali or Ammonium salts of dodecylbenzene or dinaphthylmethane disulfone acid and ricinoleic acid; Foam stabilizers, such as siloxane oxalkylene copolymers and other organopolylsiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and earth nut oil, and cell regulators such as paraffins, fatty alcohols and dimethyl polysiloxanes. The surface-active substances are becoming more common wise in amounts of 0.01 to 5 parts by weight, based on 100 parts by weight component (b) applied.

As fillers, especially reinforcing fillers substances are the usual organic and known per se inorganic fillers, reinforcing agents, weighting agents, Agents for improving the abrasion behavior in paints,  Understand coating agents, etc. In particular, be with Playfully called: inorganic fillers, such as silicate Minerals, for example layered silicates, such as antigorite, Serpentine, hornblende, ampibole, chrisotile and talc, metal oxides, such as kaolin, aluminum oxides, titanium oxides and iron oxides, Metal salts such as chalk, heavy spar and inorganic pigments, such as cadmium sulfide and zinc sulfide, and glass and. a. Preferably Kaolin (China Clay), aluminum silicate and Coprecipitates from barium sulfate and aluminum silicate as well as natural liche and synthetic fibrous minerals, such as wollastonite, Metal and in particular glass fibers of different lengths, the ge can be arbitrated if necessary. As organic fillers come into consideration for example: coal, rosin, cyclo pentadienyl resins and graft polymers and cellulose fibers, Polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarbon acid esters and especially carbon fibers. The inorganic and organic fillers can be used individually or as mixtures are used and the reaction mixture become more advantageous in amounts of 0.5 to 50 wt .-%, preferably 1 to 40% by weight, based on the weight of components (a) and (b), incorporated.

Details of the above and other starting substances are in the specialist literature, for example the monograph of J.H. Saunders and K.C. Frisch "High Polymers" Volume XVI, Poly urethanes, part 1 and 2, publisher Interscience Publishers 1962 and 1964, or the plastic handbook cited above, polyurethanes, Volume VII, Hanser-Verlag Munich, Vienna, 1st to 3rd edition, zu remove.

To produce the PUR according to the invention, the organic and / or modified organic polyisocyanates (a) and the Compounds with at least two reactive hydrogen atoms (b) implemented in such quantities that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of reactive hydrogen atoms of component (b) 0.80 to 1.25: 1, preferably 0.90 to 1.15: 1.

The PUR, especially PUR rigid foams, are becoming more advantageous with the one-shot process or prepolymer process Help of high pressure or low pressure technology in open or closed molds, for example metallic mold tools, or freely foamed. As special before it has proven to be partial, using the two-component process to work and the structural components (b), (c) and possibly (d) and (e) to combine in component (A) and as component (B)  the isocyanates or mixtures of the isocyanates mentioned (a) and optionally use blowing agent (d).

The starting components are at a temperature of 15 to 90 ° C, preferably from 20 to 60 ° C and in particular from 20 to 35 ° C, mixed and in the case of the production of molded foams placed in the open or in the closed mold. The mold temperature is advantageously 20 to 110 ° C, preferably 30 to 60 ° C and in particular 45 to 50 ° C.

In the case of free foaming, blocks become retroactive mechanical processing, for example by sawing, e.g. B. too Plates. It is also possible to use the inventive Adjust PU systems with regard to their reactivity so that them according to the known method of foam spraying (spray foam process) can be processed, the coating vertical, horizontal and hanging surfaces (above Head) is possible.

The PUR produced by the process according to the invention have improved curing, a higher degree of crosslinking and a higher hardness. This makes demolding faster possible, which is a reduction in batch production the cycle times or in the case of continuous production Increased belt speed allowed. The polymers have advantageously an increased network density. Thereby the mechanical strength (pressure, shear and bending strength) improved, the heat resistance increases and improved fire protection achieved.

The PURs according to the invention are common to all PURs Suitable applications. Rigid PUR foams are preferred manufactured, which are used in particular as thermal insulation panels, preferably in civil engineering, thermal insulation in piping systems and for thermal insulation of construction groups, parts and elements in apparatus and mechanical engineering.

The rigid foams produced by the process according to the invention have a density of 0.02 to 0.75 g / cm ³ , preferably 0.025 to 0.24 g / cm ³ and in particular 0.03 to 0.1 g / cm ³ , on.

The invention is illustrated in the following exemplary embodiments explained in more detail without this a corresponding one limit is made.

example 1 (Comparative example)

The A component, consisting of a mixture of
41.5 parts by weight of Lupranol® 3322, a polyetherol from BASF with an OH number of 400 mg KOH / g;
15.0 parts by weight of Lupranol® 3423, a polyetherol from BASF with an OH number of 490 mg KOH / g;
22.0 parts by weight of tris (2-chloroisopropyl) phosphate (TCPP);
10.0 parts by weight of a flame retardant mixture consisting of 50% TCPP and 50% tribromoneopentyl glycol;
10.0 parts by weight of Ixol® B 251, a flame retardant from Solvay;
0.5 part by weight of B 8466, a stabilizer from Goldschmidt;
0.5 part by weight of AC 3408, a stabilizer from Bayer;
0.5 part by weight of water;
2.4 parts by weight of a catalyst mixture consisting of Lupranol® 1200 (BASF), glycerin, 1,3,5-tris (3-dimethylamino propyl) hexahydro-s-triazine and triethanolamine (KX 315) and
3.2 parts by weight of ZM 99, a mixture of water, dipropylene glycol and glycerol,
was reacted with 133 parts by weight of the B component (diphenylmethane diisocyanate / polyisocyanate, NCO content: 31.0, viscosity: 620 mPa.s at 25 ° C.). A core hardening of 811.9 N / mm ^{2 was} determined.

Determination of the hardening inside the foam (core hardening):
Test pieces 100 mm × 100 mm × 150 mm are cut from an open-topped wood mold 150 mm × 150 mm × 150 mm with vertical guide slots 3 minutes after the beginning of the mixing, ie after the setting time, and left in the mold. 6 minutes after the start of mixing, these bodies are tested in a pressure test at 80 mm / min. The compressive force at the first maximum is a measure of the post-hardening in the core. The higher the pressure force in N, the better the post-curing.

Example 2 (Production of an isocyanate according to the invention from special condensation products)

In a reactor equipped with a mechanical stirrer, thermometer and a feed line for the formaldehyde solution, 651 g of aniline (7.0 mol) and 136.7 g of 32% hydrochloric acid (1.2 mol) are mixed together and cooled to 40.degree. Then 142.8 g of a 42% formaldehyde solution (2.0 mol) were added dropwise to the reaction mixture by means of a metering pump over the course of 60 min with stirring. After the addition of formaldehyde had ended, the reaction mixture was heated to 70 ° C., 85.4 g of toluenediamine (0.7 mol) were added, then heated to 100 ° C., held at this temperature for 3 hours, cooled to 70 ° C., neutralized with excess sodium hydroxide solution, the organic phase is separated off, washed with water virtually free of chloride and then the excess aniline and dissolved water are removed by gentle distillation. The condensation product thus obtained had a viscosity of 140 mPa.s at 100 ° C. This product was completely dissolved in monochlorobenzene and reacted in a two-stage process with phosgene at a temperature of 80 ° C and a pressure of 1 bar. After working up by distillation, the following characteristic values were obtained in the analytical characterization:
500 mPa.s viscosity at 25 ° C
35.0% NCO content.

Example 3 (Production of an isocyanate according to the invention from Mixtures of special condensation products with amines the diphenylmethane series)

In the same apparatus as in Example 2, 930 g of aniline (10.0 mol) mixed with 170.8 g of 32% hydrochloric acid (1.5 mol). Then 195.2 g of toluenediamine (1.6 mol) were added, the mixture cooled to 40 ° C and 142.8 g of a 42% form aldehyde solution (2.0 mol) metered in over 60 min. That on falling product was treated analogously to Example 2 and one received a condensation product with a viscosity of 800 mPa.s at 100 ° C.

In the same apparatus as in Example 2, 446.4 g of aniline (4.8 mol) mixed with 79.7 g of 32% hydrochloric acid (0.7 mol) Cooled 35 ° C and 142.8 g of a 42% formaldehyde solution inside metered in half 60 min. The resulting reaction product was treated analogously to Example 2 and had a viscosity of 35 mPa.s at 100 ° C.

The two reaction products were mixed together in a weight ratio of 1: 1 and phosgenated. After working up, the following analytical values were obtained for the isocyanate:
490 mPa.s at 25 ° C
34.6% NCO content.

Example 4

The A component, consisting of a mixture according to Example 1, was reacted with 133 parts by weight of the special isocyanate prepared according to Example 2. A value of 1082.0 N / mm ^{2 was} determined for the core hardening.

Example 5

The A component, consisting of a mixture according to Example 1, was reacted with 133 parts by weight of the special isocyanate mixture prepared according to Example 3. The core hardening was 1010.7 N / mm ² .

Claims (9)

1. A process for the preparation of polyurethanes by reacting organic and / or modified organic polyisocyanates (a) with at least one compound having at least two reactive hydrogen atoms (b) in the presence of catalysts (c), optionally blowing agents (d) and, if appropriate further auxiliaries and additives (e), characterized in that component (a) contains at least one special isocyanate or isocyanate mixture which is obtained by phosgenation of condensation products from aniline and toluenediamine and / or further amines with formaldehyde or by phosgenation of mixtures of these condensation reactions products with amines from the diphenylmethane series. 2. The method according to claim 1, characterized in that as further amines phenylenediamines and / or toluidines used become. 3. The method according to claim 1 or 2, characterized in that the molar ratio of amines to formaldehyde 1.5: 1 to Is 10: 1. 4. The method according to any one of claims 1 to 3, characterized records that the molar ratio of aniline to toluenediamine and / or further amines is 2: 1 to 15: 1. 5. The method according to any one of claims 1 to 4, characterized records that the condensation with the addition of acid Catalysts at a molar ratio of catalyst to Amine from 0.01 to 1 takes place. 6. The method according to any one of claims 1 to 5, characterized characterized in that the mixtures of these condensation products and the amines of the diphenylmethane series at least Contain 20% by weight of condensation products. 7. Isocyanate, obtainable by phosgenation of condensation products from aniline and toluenediamine and / or others Amines with formaldehyde or by phosgenation of Mixtures of these condensation products with amines Diphenylmethane series.   8. Use of the isocyanates according to claim 7, for the preparation of polyurethanes. 9. Polyurethanes, obtainable by the conversion of organic and / or modified organic polyisocyanates (a) with at least one compound with at least two reactive Hydrogen atoms (b) in the presence of catalysts (c), optionally blowing agents (d) and optionally further Auxiliaries and additives (e), where as component (a) min least a special isocyanate or isocyanate mixture which is set by phosgenation of condensation products from aniline and toluenediamine and optionally further amines with formaldehyde or by phosgenation of mixtures of these condensation products with amines the diphenylmethane series is obtained.