DE2552340A1 - HIGH MOLECULAR, INSOLUBLE CARBODIIMIDIZATION CATALYSTS - Google Patents

Description

High molecular weight, insoluble carbodiimidization catalysts

The present invention relates to new carbodiimidization catalysts, those made of a high molecular weight, insoluble, swellable matrix and via covalent bonds on or in this matrix fixed low molecular weight carbodiimidization catalysts are constructed. The new high molecular weight catalysts are suitable for the production of catalyst-free and therefore storage-stable Polyisocyanates containing carbodiimide and / or uretonimine groups or storage-stable solutions of optionally Carbodiimides and / or uretonimines containing isocyanate groups in polyisocyanates free from carbodiimide groups. With help If appropriate, the catalysts of the invention can be individual isocyanates in a mixture of different isocyanates selectively carbodiimidize.

Carbodiimides can be prepared from isocyanates in a particularly simple manner in an elegant reaction even at room temperature after basic procedure of the German patent DBP 1 130 594 produced with phospholine oxides as catalysts will. The technically most important and most effective catalysts, the aromatic mono- and poly-

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Carbodiimidize isocyanates very quickly even at room temperature and less reactive aliphatic or cycloaliphatic mono- and polyisocyanates at temperatures above about 150 C in Convert carbodiimides are those of the general formulas

(Ib)

" ^RI and (Ic)

^{0 R} (Γ »

aromatic or aliphatic hydrocarbon radical with 1 to 14, preferably 1 to 4, carbon atoms. R ¹ can also represent a hydrogen atom. Such catalysts have already found industrial use for the production of polycarbodiimide foams. Regarding (Ic) see J. org. Chemistry £ 2, 4066 (1967).

As experience has shown, it is not possible to stop the carbodiimide formation which takes place in the homogeneous phase with the easily soluble catalysts mentioned. that high-quality storage-stable carbodiimides or polycarbodiimides containing isocyanate groups are obtained; Likewise, it is not possible to use stable solutions of diisocyanatocarbodiimides or ■ < , cJ -diisocyanato-bis-carbodiimides, ■ <' , <^ -> -diisocyanatotris-carbodiimides or the isocyanato-uretonimines resulting from the reaction between carbodiimide and isocyanate groups , for example

- CH,

NCO

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ii to produce excess monomeric mono- or polyisocyanates. The carbodimiidization under the influence of the catalytically highly effective soluble phospholine oxides can be carried out with Deactivating agents such as phosphorus oxychloride, zinc chloride, Dimethyl carbamic acid chloride, benzoyl chloride, hydrochloric acid, boron trifluoride, Practically do not stop alkylating agents, etc., so that high molecular weight, insoluble, inferior products are formed .

As a result of the progressive, albeit slowed, formation of carbodiimides A high excess carbon dioxide pressure soon arises in closed vessels, which can lead to dangerous accidents can.

Surprisingly, it has now been found that carbodiimidization catalysts are successful without significant impairment of their catalytic effect via covalent bonds to or in a high molecular weight, swellable one which is insoluble in polyisocyanates to bind organic matrix. In this way, high molecular weight swellable, insoluble catalysts that can be removed from the reaction table at any time can be, which makes it possible, mono- or preferred Polyisocyanates in storage-stable carbodiimides or polycarbodiimides or their uretonimines with functional NCO groups and / or in storage-stable mixtures of (poly) carbodiimides or their ^ to convert uretonimines with polyisocyanates.

The present invention thus relates to high molecular weight carbodiimidization catalysts which are insoluble in polyisocyanates, those of a high molecular weight matrix and one covalently bound in this matrix or one covalently bound to this matrix low molecular weight carbodiimidization catalyst, preferably a saturated or unsaturated five-membered or saturated one four-membered cyclic phosphine oxide.

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The molecular weight of the catalysts of the invention is generally> -2OOO. According to the invention, highly crosslinked Products used.

The present invention also provides a process for preparing the catalysts of the invention, which characterized in that one has a high molecular weight matrix containing functional groups or to build up a high molecular weight matrix Matrix suitable monomers with low molecular weight carbodiimidization catalysts or their precursors for Brings reaction which contain reactive groups with respect to the functional groups of the matrix or the monomers.

For the preparation of the high molecular weight carbodiimidization catalysts according to the invention are in principle any low molecular weight carbodiimidization catalysts known per se or their precursors are suitable, which are only converted into the catalytically active form when they are incorporated into the matrix will. The low molecular weight carbodiimidization catalysts known per se may need for the purpose of incorporation into the high molecular weight matrix by functional Groups modified with functional groups the matrix or with those used to build the matrix Monomers can react.

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The link between low molecular weight carbodiimidation catalyst and high-molecular matrix can be made via any covalent bonds, e.g. carbon-carbon bonds, Ether, ester, urethane, amide, sulfide groups etc. take place. Ester groups and in particular are preferred according to the invention aliphatic carbon-carbon bonds.

According to the invention, cyclic phosphine oxides are particularly preferred of the type described above (formula Ia), as well as cyclic phosphine oxides derived therefrom, which are additionally still on the ring Substituents with functional groups for the formation of covalent bonds can have, as low molecular weight carbodiimidization catalysts used to produce the high molecular weight carbodiimidization catalysts according to the invention.

Another preferred type of compound for making the compounds according to the invention high molecular weight carbodiimidization catalysts are cyclic phosphine oxides, which are of the general formula (Ib) are derived. However, they contain alkyl, aryl or aralkyl substituents with functional substituents on the ring or on the phosphorus atom Groups through which covalent bonds can be made to the polymer matrix.

Compounds of this type are, for example, those of the general formulas

(HIa)

O R

O R

O R

(HIb)

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(HIc)

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whereby
R ¹

- S-

for halogen, for an alkoxy group, aryloxy group with up to to 14 carbon atoms or for an amino group with alkyl, alkenyl, aryl or aralkyl radicals with up to 14 carbon atoms can be substituted, or for an alkyl, alkenyl, Aryl or aralkyl radical with up to 14, preferably 1 to

4 carbon atoms, stands, and

4 5
R; R is hydrogen, halogen, a carboxyl group, C ₁ to C 1 J, preferably C ₁ to C alkyl or alkoxycarbonyl radicals, phosphonic acid ester or C 1 to C alkoxy or alkyl mercapto radicals, which may also be contain functional groups such as olefinic CC double bonds, amino or hydroxyl groups.

Typical representatives of such compounds are, for example:

, 6

0 (CH ₀ -CH -O) H £ a a

R ⁶

0 (CH ₀ -CH -O) JH 2 b

-CH ₂ -CH = CH ₂

X = O; S.

(IV)

a, b = 1 to 30 R ⁶ = H; CH-

or

• AT ^H

.P.

OC ₂ H ₅

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'jfä.

Low molecular weight catalysts of this type can be prepared in the following way:

Compounds of type (IV) by reacting a compound of the formula.

X 0-H

(X = 0; S.)

with ethylene oxide or propylene oxide.

The reaction takes place at 0-180 ° C., preferably at 50-150 ° C., and can either be under normal pressure or under normal pressure at elevated pressure, if necessary also in an inert solvent, are executed.

Low molecular weight carbodiimidization catalysts alkyl-substituted on the phospholane ring of type (IV) are accessible in an analogous manner (see also DOS 2 504 400).

Compounds of the kind (V) can be obtained by reacting

7 H compounds of the general formula R ^ ι ^

whereby

R is an alkyl or an aryl radical with up to

14 carbon atoms means and

7 8 9
R, R, R independently of one another for a C ₁ - to C--

Alkyl radical or hydrogen,

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with a compound of the general formula

E ¹⁰ - O - H

whereby
R ¹⁰

denotes an alkyl, aryl or aralkyl radical with 1 to 14, preferably 1 to 4, carbon atoms, which optionally also have functional groups such as olefinic C-C double bonds contains,

Catalysts.

in the presence of alkaline

Compounds of type (VI) are created by converting the general link

Izvestiya Akademii NaukSSSR, Seriya Khimicheskaya, No. 8, pp. 1847-1848 (there further literature)

whereby
X

R ² , R ³ , R ⁴

for a halogen atom (e.g. chlorine, bromine or iodine) and

independently of one another represent a C ₁ to C alkyl radical or hydrogen.

with an organometallic compound such as Grignard compounds, the organic radical of which can contain the desired functional groups such as olefinic C-C double bonds. Hydrocarbons and ethers (THF) can be used as solvents for this reaction.

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Compounds of type (VII) are formed in the hydrolysis of 3,4-epoxyphospholane-1-oxides

A. Arbusov, A.P. Rakow, A.O. Vizel, Izv. Akad. Nauk SSSR, 1969, 2230-2234).

The phosphorus content is in high molecular weight catalysts according to the invention based on the compounds of the formulas (I) or (III) generally between 0.05 and 23% by weight, preferably between 0.3 and 8% by weight.

Under 'precursors ^{1 of} the low molecular weight carbodiimidization catalysts, for example, compounds of the type

R ³

HH ₂

^R (see U.S. Patent

_H '■ 3 723 52O)

(VIII)

^ P / χ ₁

X
to understand,

whereby

R ¹ , R ² and R ^{3 are} hydrogen or C ₁ "to C ₁₄ -, preferably

C ₁ - to C ₄ -alkyl radicals and χ denote halogen.

Such compounds can be incorporated into a high molecular weight matrix, for example, as shown in the following scheme with the formation of the catalytically active cyclic phosphine oxide grouping i

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OH

, Macromolecule

-HX

(IX)

Heat

(Alkyl iodide as a catalyst)

Another possibility is the Arbusov reaction:

RO-P

Arbusov reaction

¹ Γ

^CH 2- ^.

+ RX

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Further 'precursors' of carbodiimidization catalysts are, for example, compounds of the type R-PX ₂ (X = halogen), the radical -PX' being bonded to an alkyl, aryl or aralkyl radical which in turn can already be part of a high polymer . The conversion products of PX- are an example of this. with polystyrene.

By reaction with dienes and subsequent hydrolysis, compounds R ^- PX ₂ can easily be converted into cyclic phosphine oxides:

X X P

As a high molecular weight basic structure for the catalysts according to the invention Polymers are suitable which have functional groups for a covalent bond to the low molecular weight carbodiimidization catalyst included. On the other hand, you can of course in the preparation of the invention Catalysts also start from monomers that form a high molecular weight product in the course of the polymerization incorporate suitable functional groups-bearing low molecular weight carbodiimidization catalyst.

A preferred matrix for the catalysts of the invention are unsaturated polyester resins. In this variant of the process according to the invention, condensation is first carried out according to methods known per se dicarboxylic acids and diols, where-

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if at least one of the components is unsaturated, to an unsaturated polyester. About 10-70% by weight (based on polyester) of a phospholine oxide, which may contain a substituent with an additional olefinic double bond , is then added, and the mixture is heated together with reaction initiators.

Instead of the free dicarboxylic acids, it is also possible according to the invention to use the corresponding dicarboxylic acid anhydrides or corresponding carboxylic acid esters of lower alcohols or mixtures thereof for producing the polyesters. The carboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms. Examples include: malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride tetrahydrophthalic anhydride, hexa- hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, glycol ester of terephthalic acid, optionally in admixture with monomeric fatty acids, TerephthalsäurediitEthylester and also any mixtures thereof. Ethylene glycol, propylene glycol- (1,2) and - (1,3), butylene glycol- (1,4) and ■ * - (2, 3), hexanediol- (1,6), octanediol- (1 , 8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, the isomeric butenediols, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, and dibylene glycols.

Preferred acid components are malonic acid and its esters, maleic anhydride, maleic acid and its esters, fumaric acid and its esters, and also muconic acid and its esters.

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Preferred diols are ethanediol, propanediol and the polycondensates from these, preferably up to a molecular weight of 400, butenediols, butanediols and mixtures of these diols.

As reaction initiators for the implementation of polyesters with double bonds containing phospholine, phospholane or phosphetane oxides are active radical formers in the temperature range from about 50 to 300 ° C, especially organic ones Peroxides, aliphatic azo compounds and high-energy radiation in question, e.g. diacyl peroxides, such as di-tert.-butyl peroxide, Diacyl peroxides such as dibenzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, succinyl peroxide, Nonanoyl peroxide, lauroyl peroxide, peroxy esters such as tert-butyl peroctoate, tert-butyl perisobutyrate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perpivalate, and peroxyketals and percarbonates, azoisobutyric acid nitrxl, azo-bisisobutanol-di-acetate as well as UV radiation, X-rays or gamma radiation.

Polyester-based catalysts according to the invention can also be prepared by, in the known preparation of Polyesters part of the diol component by phospholine oxides or phospholane oxides substituted with dihydroxyalkyl groups of the type described above (formulas I, III, IV and VIl) replaced.

The low molecular weight carbodiimidization catalysts can be used in an analogous manner Via suitable functional groups (for example —OH, —NH “or —COOH), of course, into others as well Polycondensation or polyaddition resins are incorporated, e.g. in polyamides, polyurethanes or epoxy resins.

There are also a number of possibilities according to the invention high molecular weight catalysts by incorporating low molecular weight carbodiimidization catalysts into - preferably crosslinked - Manufacture of polystyrene. For example, one of the compounds of the formulas I, III or VIII can be mixed with styrene and, if necessary,

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copolymerize approx. 1-10% by weight divinylbenzene with the aid of the above-mentioned reaction initiators.

Another method is to use a halogenated polystyrene (see Houben-Weyl XIV /, 764 (1963)) to metalate (preferably with the help of tert-butyl lithium) and then with halogen-substituted ones To implement phospholine or phospholane oxides, preferably with 1-chloro-phospholine oxides.

Analogously to the method of preparation described above for compounds of the formula (v), it is also possible to attach to a matrix with anionic Groups (e.g. alcoholate groups on polyvinyl alcohol) phospholine oxides (preferably 1-methyl-1-phospha-2- or 3-cyclopentene -1-oxide).

Catalysts according to the invention can also be started with -PX_- Groups (X = Cl, Br) functionalized polymers, e.g. copolymers from styrene and divinylbenzene (see ζ B. Houben-Weyl , P. 821 (1961)).

With the addition of 1,3-dienes, e.g. 1,3-butadiene, isoprene or 2,3-Dimethy1-1,3-butadiene '(see formula scheme X) on Phosphorus atom forms the catalytically active phospholine ring.

In an analogous manner, compounds of the formulas I, III or VIII, which may also contain substituents with olefinic CC double bonds, or compounds of the type R-PX ₂ (X = Cl, Br) in which R represents an alkenyl radical, can of course be used. can also be copolymerized with other olefinically unsaturated monomers (for example ethylene, propylene, butene, butadiene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, etc.) and incorporated into a high-molecular matrix in this way.

Catalysts according to the invention are also obtained, for example, by adding a phospholine halide of formula (VIII), the can optionally also be saturated, with high molecular weight

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■ AV

Polyhydroxy compounds, e.g. polyvinyl alcohols, possibly in the presence of bases and with catalytic amounts of alkyl halides heated. According to formula scheme (IX) the catalytically active phospholine oxide is attached to the matrix with an additional carbon-phosphorus bond (US patent 3,723,520; Houben-Weyl, XII / 1, p. 150 (1963)).

With the aid of the catalysts according to the invention can in principle any aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates be carbodiimidized, as described e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, are described, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3, SiS-tri-methyl-S-isocyanatomethyl-cyclohexane (DAS 1 202 785, U.S. Patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate, as well as any Mixtures of these isomers, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers, diphenymethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, Triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in British Patents 874,430 and 848,671, m- and p-isocyanatophenylsulfonyl isocyanates according to the American patent 3 454 606, perchlorinated ary! polyisocyanate, as for example in the German Auslegeschrift 1 157 601 (American Patent 3 227 138) are described as containing carbodiimide groups. ■

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pointing polyisocyanates, as described in German Patent 1 092 007 (American Patent 3 152 162) are described, diisocyanates as described in US Pat. No. 3,492,330, aliphanate groups containing polyisocyanates, such as those in British Patent 99 4 890, Belgian Patent 761 626 and published Dutch patent application 7 102 524 are isocyanurate groups containing polyisocyanates, as for example in the American patent 3 001 973, in the German Patents 1 022 789, 1 222 067 and 1 027 394 as well as in the German Offenlegungsschriften 1 929 03 4 and 2 004 to be discribed. Polyisocyanates containing urethane groups, as described e.g. in Belgian patent specification 752 261 or in American patent specification 3 39 4 164 are polyisocyanates containing acylated urea groups according to German Patent 1 2 30 77 8, polyisocyanates containing biuret groups, such as those used, for example, in German Patent 1 101 394 (American patents 3,124 6O5) and 3,201,372) as well as in British patent specification 889 050, by telomerization reactions Polyisocyanates produced, as described, for example, in US Pat. No. 3,654,106, Polyisocyanates containing ester groups, such as those described, for example, in British patents 965 474 and 1 072 956, in the American patent 3,567,763 and in the German patent 1,231,688, reaction products of the abovementioned isocyanates with acetals according to of German Patent 1,072,385, polyisocyanates containing polymeric fatty acid residues according to the American U.S. Patent 3,455,883.

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It is also possible to use the isocyanate group-containing distillation residues obtained in the technical production of isocyanates, optionally dissolved in one or more of the the aforementioned polyisocyanates to be used. It is also possible to add any desired mixtures of the aforementioned polyisocyanates use.

Aromatic polyisocyanates preferred according to the invention are: 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and any Mixtures of these isomers, m-phenylene diisocyanate, p-phenylene diisocyanate and approx. 10-40% by weight solutions of biuretization, allophanation, urethanization, trimerization and dimerization products of these polyisocyanates in monomeric polyisocyanates, especially in monomeric tolylene diisocyanate.

Among the aliphatic, cycloaliphatic and araliphatic polyisocyanates are tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, Lysine ester diisocyanates, m- and p-xylylene diisocyanate and their mixtures are preferred, or solutions their biuretization and dimerization products in the corresponding monomeric polyisocyanates.

Of course, monoisocyanates can also be carbodiimidized. Suitable monoisocyanates are e.g. methyl isocyanate, Ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, Diisopropylphenyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, Cc? -Chlorhexyl isocyanate, phenyl isocyanate, tolyl isocyanate, p-chlorophenyl isocyanate, 2,4-dichlorophenyl isocyanate and Trifluoromethylphenyl isocyanate.

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The carbodiimidization of these mono- and polyisocyanates or their mixtures takes place in such a way that the isocyanates - optionally dissolved in inert solvents such as toluene, xylene, chlorobenzene, o-dichlorobenzene, decalin, dimethylformamide, dimethyl acetamide, butyl acetate, carbon tetrachloride, trichlorethylene, Tetramethylurea with preferably 0.2 to 10% by weight, particularly preferably 1 to 4% by weight, of the matrix loaded with catalyst molecules (based on isocyanate) at temperatures between about 50 and 200 ° C, preferably 80 to 185 ° C, and optionally brings into contact under pressure. The easiest way to do this is to add the catalyst to the liquid or dissolved isocyanates with stirring and, after reaching the desired degree of carbodiimidization, to remove it again by decanting or filtering. The degree of conversion can easily be followed by measuring the volume of the CO 2 formed during the carbodiimidization reaction. The catalysts of the invention can generally be reused more than 10 to 20 times without impairing their effectiveness. It is of course also possible to carry out the carbodiimidization. to run continuously in a column, provided that a suitable arrangement ensures _{unhindered escape of the CO 2 formed during the reaction.}

Of course, the (optionally only partially) carbodiimidized mono- and / or or polyisocyanates are subsequently mixed with other polyisocyanates. In this way, storage-stable Mixtures of high and / or low molecular weight polyisocyanates with, if appropriate, isocyanate groups containing high and / or or produce low molecular weight carbodiimides or uretonimines.

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* W.

Since the carbodiimidization catalysts according to the invention can be completely removed after the reaction, in contrast to the previously known catalysts, can basically produce mixtures with any carbodiimide group content. According to the invention, however, are preferred Mixtures containing about 3 to 70% by weight, particularly preferably up to 60% by weight, of carbodiimides or polycarbodiimides or uretonimines contain. Of particular technical importance are the following polyisocyanate / carbodiimide mixtures:

a) Mixture of 100 parts by weight of 4,4'-diisocyanatodiphenylmethane and / or 1,5-naphthylene diisocyanate and 5 to 3O Parts by weight of diisocyanatocarbodiimides of tolylene diisocyanate or the corresponding triisocyanatouretonimines.

b) Mixtures of 100 parts by weight of 4,4'-diisocyanatodiphenylmethane and / or 1,5-naphthylene diisocyanate and 10 to parts by weight of carbodiimides of phenyl isocyanate, hexamethylene diisocyanate, Tetramethylene diisocyanate, cyclohexyl isocyanate or tolyl isocyanate or their uretonimines.

c) Mixtures of 100 parts by weight of toluene diisocyanate and 5 to 30 parts by weight of carbodiimidized phenyl isocyanate or tolyl isocyanate or their uretonimines.

d) mixture of 100 parts by weight of modified toluene diisocyanate, which 10 to 40 wt .-% of biuret, AlIophanat-, urethane or isocyanurate polyisocyanates Basis contains toluene diisocyanate, and 10 to 20 parts by weight of toluene diisocyanatocarbodiimide or the corresponding Triisocyanatouretonimine.

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- Xl.

e) Mixture of 100 parts by weight of biuret polyisocyanates of hexamethylene diisocyanate (preferably reaction products from 1 mole of water and about 2 to 3 moles of hexamethylene diisocyanate) and 10 to 30 parts by weight of the carbodiimide of hexamethylene diisocyanate or the corresponding uretonimine polyisocyanates.

f) Mixtures of 100 parts by weight of vC , £ * ■> diisocyanato prepolymers from 1 mol <x>, c *> dihydroxy polyesters or polyethers of the type described below and 1.4 to 2.5, preferably 1, 6 to 2 moles of tolylene diisocyanate, diisocyanatodiphenylmethane or hexamethylene diisocyanate and 5 to 30 parts by weight of carbodiimides or carbodiimide diisocyanates or the corresponding uretonimine polyisocyanates of phenyl isocyanate, tolyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or tolylene diisocyanate.

Those prepared with the catalysts of the invention, if appropriate Carbodiimides containing isocyanate groups and Their solutions in polyisocyanates free from carbodiimide groups are valuable starting materials for the diisocyanate polyaddition process and can be used to produce a wide variety of hard to elastic, optionally cellular, plastics can be used for the production of paints, coatings, foils and moldings. Manufactured this way Polyurethanes contain solid in the polymer molecule built-in carbodiimide groups or uretonimine groups (= masked Carbodiimide groups), which at the same time represent anti-aging agents against the hydrolysis of ester bonds and also reduce the flammability of the plastics.

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Polyurethanes are produced in a manner known per se by reacting the polyisocyanate mixtures with them high and possibly also low molecular weight compounds which contain at least two isocyanate-reactive compounds Have hydrogen atoms.

The following examples serve to illustrate the present Invention.

Unless otherwise stated, figures are to be understood as parts by weight or percentages by weight.

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Example 1

a) 70 weight parts of a polyester with an acid number

of about 8, made from 4-6 parts by weight of maleic anhydride and 438 parts by weight of diethylene glycol, wprrlpp with 30 parts by weight of 1-methyl-i-phospha -2 and 3-cyclopentene-1-oxide (1-methyl-phospholine oxide) in the presence of 1.5 g Benzoyl peroxide slowly to 15ΟC gently while stirring at 110 ° C a solid, crumbly product is formed. After 4 days of extraction of residual monomers, first with toluene and then with chloroform, the polymer contains 1.25 weight percent phosphorus.

b) Example 1a is repeated, but with the addition of 3.5 parts by weight Styrene to the reaction mixture. A somewhat harder product is obtained with a phosphorus content of 0.5 percent by weight.

To 34.8 parts by weight of an isomer mixture of 2,4- and 2,6-tolylene diisocyanate (80:20), 25 parts by weight of Catalyst from Example 1a and 40 parts by weight of toluene and heated to 110.degree. After one hour it was 3.6 liters Carbon dioxide was formed and the NCO content of the solution of the isocyanate mixture fell to 8.6 percent by weight.

Example 2

a) 35 parts by weight of an unsaturated polyester composed of 1 mole of maleic anhydride and 1 mole of tetraethylene glycol (Acid number 9) with 15 parts by weight of 1-methyl-1-phospha -3-cyclopentene-i-oxide and 0.75 parts by weight of benzoyl peroxide mixed well and slowly heated to 150 ° C with stirring. The resulting crumbly product has after washing out with toluene and chloroform a phosphorus content of 0.75 percent by weight.

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b) Example 2a is repeated, but instead of 1-methyl-1-phospha-3-cyclopentene-1-oxide 1-methyl-1-phospha -2-cyclopentene-i-oxide used, then the phosphorus content of the reaction product is 0.2 percent by weight.

Example 3

14 parts by weight of the unsaturated polyester from Example 2 are with 6 parts by weight · 1-allyl-1-phospha -2 and 3-cyclopentene-1-oxide and 0.3 parts by weight of benzoyl peroxide and slowly heated to 150 ° C with stirring. It falls a crumbly Product which, after extraction with toluene and chloroform, has a phosphorus content of 2.7 percent by weight.

When heating 5 parts by weight of the catalyst with 150 parts by weight a mixture of 2,4- and 2,6-toluylene diisocyanate (80:20) at 90 C are formed with carbodiimide oxidation within one hour 3 liters of carbon dioxide.

Example 4

9.8 parts by weight maleic anhydride and 5.2 parts by weight Diethylene glycol with 25.6 parts by weight of a diester of an isomer mixture of 1-methyl-2 or. 3-phosphoric acid phospholane oxide and polypropylene glycol (molecular weight 511) below Heated nitrogen to 175 ° C and distilled off the water formed during the esterification reaction. The gel-like product is mixed with 0.6 parts by weight of benzoyl peroxide and heated to 150.degree. From the resulting crumbly product soluble components are extracted with toluene and chloroform.

If 1 part by weight of the catalyst is combined with 34.8 parts by weight of a mixture of 2,4- and 2,6-tolylene diisocyanate (80:20) heated to 110 ° C., 2 liters of carbon dioxide are evolved within 10 minutes.

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Example 5

9.8 parts by weight of maleic anhydride with 9 parts by weight of diethylene glycol and 3.7 parts by weight of a product-3-phosphonate is formed by heating 1 mole of 1-methyl-phospholane-2 and with 2 mol of diethanolamine, 3 hours at 175 ⁰ C under a nitrogen atmosphere condensed. The resulting water is continuously distilled off and then the condensate is treated with toluene and chloroform in order to extract residual soluble components. The product thus obtained has a phosphorus content of 0.6 percent by weight.

1 part by weight of this product is heated to 190 ° C. with 84 parts by weight of hexamethylene diisocyanate 5 hours 2 liters of carbon dioxide are produced.

Hexamethylene diisocyanate heated to 190 ° C, within

10 parts by weight of the product are 174 parts by weight a mixture of 2,4- and 2,6-tolylene diisocyanate to 70 ° C heated. As a result of the carbodiimidization of the isocyanate, 10 liters of carbon dioxide develop within 30 minutes.

Example 6

To 150 ml (0.22 mol) of a n-butyl lithium solution in toluene are added dropwise 7.1 parts by weight of a 2 -gewichtsprozentigen solution of PoIyp-iodostyrene in toluene at 0 ⁰ C. Then 35.5 parts by weight of 1-chloro-3-methyl-1-phospha-2 and 3-cyclopentene-i-oxide are quickly added at 20 ° C. After stirring for 1 hour, the reaction mixture is mixed with 5 ml of HO, concentrated, digested with a little water and then dried over phosphorus pentoxide in a desiccator.

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With the help of the resulting highly effective catalyst can Carbodiimidize tolylene diisocyanate at 60 ° C.

Example 7

15 parts by weight of poly-p-iodostyrene / crosslinked with 2% divinylbenzene , are swollen in 100 ml of toluene and 200 ml of a 1.5 normal solution of n-butyllithium in η-hexane are added dropwise. The metallized Solid product is suctioned off under nitrogen and 9.7 parts by weight of 3-chloro-1-methyl-1-phospha-2 are added at room temperature and 3-cyclopentene-i-oxide, made from chloroprene and dichloromethylphosphine, brought to reaction. The product is filtered off and treated with toluene and chloroform.

With the aid of the catalyst, toluylene diisocyanate can be removed at 100.degree carbodiimidize.

Example 8

50 parts by weight of polystyrene are mixed with 268 parts by weight of phosphorus trichloride and the mixture is reacted at 200 ° C. for 5 days (see also US Pat. No. 2,844,546). The excess Phosphorus trichloride is then distilled off, the residue is taken up 3 more times with perchlorethylene and the solvent each distilled off.

190 parts by weight of the solid product purified in this way are added under nitrogen Isoprene and 0.6 parts by weight of ionol were added and the mixture was allowed to stand at room temperature for 10 days. The solid product is washed with perchlorethylene, hydrolyzed / filtered off with suction in 1 l of ice water and dried over phosphorus pentoxide.

34.8 parts by weight of an isomer mixture of 2,4- and 2,6-tolylene diisocyanate (80:20) are "carbodiimidized" with the aid of 3 parts by weight of the catalyst at 140 ° C. Within 1 liter of carbon dioxide is produced every 1 hour.

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Example 9

- ZI-

A mixture of

3 parts by weight of polystyrene,

6 parts by weight of styrene,

1 part by weight of 1-allyl-phospholine oxide (1-allyl-1-phospha-2 and 3-cyclopentene-1-oxide), produced from equivalent parts of 1-chloro-phospholine oxide (1-chloro-i-phospha-2 and 3-cyclopentene-1-oxide) and allyl magnesium iodide in tetrahydrofuran, 0.6 parts by weight divinylbenzene and

0.008 part by weight of dibenzoyl peroxide

is filled into a bomb tube under nitrogen. After 30 days at 32 ° C, the solid product is rasped and toluene and Chloroform freed from residual soluble components. The phosphorus content of the product is 0.3 percent by weight.

Under the action of the catalyst, toluene diisocyanate changes into the carbodiimide at 75.degree.

Example 10

9 parts by weight of styrene and 0.1 part by weight of divinylbenzene are mixed with 1 part by weight of 1-methyl-1-phospha-2 and 3-cyclopentene-i-oxide

mixed and with 0.3 parts by weight of benzoyl peroxide as Initiator polymerized at 110 ° C. The product has after washing with toluene and chloroform a phosphorus content of 1 percent by weight

Example 11

To 2 parts by weight of a polyvinyl alcohol (molecular weight 15,000) are 6.8 parts by weight of 1-chlorine at room temperature

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1-phospha-2 and 3-cyclopentene (US Patent 3723520) dissolved in 2O parts by weight of dichlorobenzene, 4 parts by weight of pyridine were added dropwise, 0.1 parts by weight of ethyl iodide was added and the mixture was heated to 110 ⁰ C. The resulting solid product is filtered off with suction, washed with water, then with ether and dried over phosphorus pentoxide.

The product is a good carbodiimidization catalyst for 2,4- and 2,6-tolylene diisocyanate at a temperature of 150 ° C. From 70 parts by weight of a mixture of 2,4- and 2,6-tolylene diisocyanate (80:20), 3 liters of carbon dioxide develop within 10 minutes at 170 ° C. under the action of 2 parts by weight of catalyst. ^; .

Example 12

160 g of Malonsäurediäthy lester with 106 g of diethylene glycol and 1 ml of 10% sulfuric acid in 100 ml of toluene under reflux for 24 hours heated and then the toluene slowly distilled off. 240 g of this product are mixed with 240 g of an unsaturated polyester from equivalent amounts of maleic anhydride and diethylene glycol (acid number 8) mixed, 206 g of 1-methyl-1-phospha-2 and 3-cyclopentene-1-oxide and 10 g of benzoyl peroxide were added and the mixture was heated to 150.degree. The resulting crumbly product had after Extract with toluene and chloroform a phosphorus content of 1% .. '■

^{If 1 g of the catalyst is heated to 85 ° C.} with 34.8 g of a mixture of 2,4- and 2,6-tolylene diisocyanate (80:20), 4 liters of carbon dioxide are evolved over the course of 3 hours.

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Example 13

350 g of an unsaturated polyester with an acid number of 9 from equivalents Amounts of maleic anhydride and tetraethylene glycol are mixed with 150 g of 1-methyl-2 and 3-allyloxy-i-phospha-cyclopentane ioxide mixed, then slowly heated with 7.5 g of benzoyl peroxide with stirring to 150 ° C and stirred for 1/2 hour The crumbly product is extracted with toluene for 2 days and with chloroform for 2 days.

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Example i4

* dd.

133 g of o-tolyl isocyanate are insoluble with 5 g of a solid Catalyst according to Example 1a heated to 180 ° C. with stirring. After that, within 1.5 hours, 12.3 liters of carbon dioxide have developed, the catalyst is suctioned off and the filtrate is distilled. 95.3 g of di-o-tolyl-carbodiimide are obtained with a boiling point of 135-137 ° C./0.1 Torr (87% of theory).

Example 15

133 g of o-tolyl isocyanate are heated to 140 ° C. with 5 g of a solid, insoluble catalyst according to Example 2a with stirring. After developing 12.1 liters of carbon dioxide within 2 hours the catalyst is suctioned off and the filtrate is distilled. 103.5 g of di-o-tolylcarbodiimide with a boiling point of 130 132 ° C./0.1 are obtained Torr (94% of theory)

Example 16

203 g of 2,6-diisopropyl-phenyl isocyanate are mixed with 5 g of a catalyst according to example 1a heated to 200 ° C. with stirring. After that 8.9 liters of carbon dioxide within 12 hours have developed, the catalyst is suctioned off and the filtrate (177 g) is distilled. 132 g of bis (2,6-diisopropyl phenyl) carbodiimide with a boiling point of 165-168 ° C / 0.1 Torr (71% of theory).

Example 17

1500 g of a mixture of 2,4- and 2,6 tolylene diisocyanate (80/20) are mixed with 50 g of a catalyst according to Example 2a

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heated to 100 ° C. After 38 liters of carbon dioxide have evolved, the product is filtered. It has a viscosity = 14 cP and an NCO content of 39%.

Example 18

300 g of diphenylmethane-4,4'-diisocyanate are heated at 80-100 ° C. with a catalyst according to Example 1a. After 3 liters of carbon dioxide have evolved, a product is obtained which is liquid at room temperature and has an NCO content of 2996 and a viscosity η _{o /} , = 46 cP.

Example 19

168 g of 1,6-hexamethylene diisocyanate are heated to 150 ° C. with 5 g of a catalyst according to Example 1a. After 14 liters of carbon dioxide have formed, the product is filtered and thinly layered. It then has a viscosity η _. = 580 cP and an NCO content of 23%.

When applied to a glass plate, the product forms a scratch-resistant, elastic film.

Example 20

A mixture of 111 parts by weight of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and 84 parts by weight of 1,6-hexamethylene diisocyanate is heated to 160 ° C. and mixed with 5 g of a catalyst according to the example 1a offset. After 7.3 liters of carbon dioxide have evolved, the product (viscosity η = 170 cP)

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filtered and thinly layered at 80 C / 0.12 Torr, with monomeric isocyanate being stripped off. In addition to carbodiimides, the thin-layer product has a high content of isocyanatouretonimines. ⁽ Ί 24 ^{= 916 CP; NC0} ~ ^{salary = 23} ' ^9%)

Example 21

500 g (2 mol) of diphenylmethane-4,4'-diisocyanate are heated to 140 ° C. with 20 g of the catalyst from Example 1a. After liters of carbon dioxide are released which is uretoniHiIj ₁ - group-containing Isocyanatocarbodiimid freed by filtration from the catalyst.

The product is used in proportions of 10, 30 and 50 percent (a; b; c;) stirred into melted diphenylmethane-4,4'-diisocyanate, storage-stable products that are liquid at room temperature are formed.

a) NCO content = 31% '^ ₂ 4 ^{= 22 cP}

b) NCO content = 28% <n _. = 140 cP

c) NCO content = 25.2% r? ο * = 130OcP

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Claims (5)

Patent claims: 1) High molecular weight compounds that are insoluble in polyisocyanates, which the formation of carbodiimide groups from isocyanate groups catalyze, consisting of a high molecular weight matrix and bound to or in this matrix via covalent bonds low molecular weight carbodiimidization catalysts. 2) High molecular weight Carbodiimidisierungskatalysatoren according to claim 1, consisting of a polyester resin matrix, which catalytically effective groups of the general formula 4 \ O R .R ₃ (A) R, (B) or contains in which R _{1 is} an alkyl, aryl or aralkyl radical with 1 to 14 C atoms and R-JR ₃ , R ₄ , R ₅ hydrogen, halogen, C ₁ - to O ^ -alkyl, aryl or? - aralkyl radicals, alkoxycarbonyl, phosphonic acid ester or C ₁ - bis C.-Qxyalkylreste or Mercaptoalkylreste or HO- mean, the catalytically active groups (A), (B) or (C) via at least one of the radicals R ₁ to R through an ester group, an ether group or a CC bond or the phospholane ring directly via CC bonds or into the matrix are bound. 3) High molecular weight Carbodiimidexerungskatalysatoren according to claim 1, consisting of an optionally crosslinked via divinylbenzene Polystyrene matrix, which catalytically active groups Le A 16 592 - 32 - 709822/0854 ORIGINAL INSPECTED the general formulas (B) or ^ 4 MR- contains, in which R an alkyl, aryl or aralkyl radical with 1 to 14 carbon atoms and
R ^, R, R, R ₅ hydrogen, halogen, C.- to C ₁₄ -AIJCyI-, aryl- or aralkyl radicals, alkoxycarbonyl, phosphonic acid ester or C ₁ - to C ₄ -Qxyalkylreste or alkyl mercapto radicals or HO- mean, where the catalytically active groups (A), (B) or (C) are _{bound to or in the matrix via at least one of the radicals R 1} to R ₅ by an ether group, a CC bond or the phospholane ring directly via a CC bond are. 4) High molecular weight carbodiimidization catalysts according to claim 1, consisting of a polyvinyl alcohol matrix, which catalytically active groups of the general formulas R ₄ H * " O R. (A) R, contains, R, O R • Η R, (B) or r MR, Le A 16 592 - 33 - 709822/0854 in which 3 R _{1 stands} for the polyvinyl alcohol matrix and R ₂ / R, R ^ and R _{5 have} the meaning given above. 5) Process for the production of high molecular weight carbodiimides ierungskatalys ators according to claim 1, characterized in that a functional group containing high molecular weight Matrix or monomers suitable for building up a high molecular weight matrix with low molecular weight carbodiimidization catalysts or brings their precursors to a reaction which oppose the functional groups of the matrix or the monomers contain reactive groups, and in the case of the use of precursors of low molecular weight carbodiimidization catalysts these are converted into the catalytically active form after incorporation into the matrix. Le A 16 592 - 34 - 709822 / 08S4