DE1495693B2 - PROCESS FOR THE MANUFACTURING OF QUATERNAL POLYADDITION PRODUCTS - Google Patents

Description

It has been known for a very long time that low molecular weight dihalides can also combine with low molecular weight Let the diamines react while lengthening the chain. W. Kern and E. Brenneisen (J. Prakt. Chemie [2], p. 159, 193 [1941]) let in the context of experiments for the production of protein-like Polyelectrolytes e.g. B. Decamethylendibromid react with tetramethylethylenediamine and received glass-like, tough, very hygroscopic and completely water-soluble masses, which in addition to ether-soluble Monomers and dialyzable oligomers also contained non-dialyzable polymers. For the production Such polyelectrolytes have proven to be completely unsuitable for plastics.

Furthermore, a method for producing insoluble polyquaternary resins is known, which is a Quaternization polyaddition served (British Patent 652 830). For making such resins two low molecular weight substituted hydrocarbon compounds are reacted with one another, of one of which contains at least two reactive halogen atoms in the 1,4-position or further from one another are removed, and the other contains at least two tertiary amino groups, and wherein the one of the two compounds must have more than two such functional groups. After this Processes result in extremely highly branched and cross-linked, brittle resins that reduce the tightness according to their network, are insoluble in water. They consist of around 50 percent by weight

can be, in general, is not great. It was to be expected that higher molecular weight diamines or dihalides would react even more incompletely, which would result in a premature chain termination.

The invention now relates to a process for the preparation of quaternary polyadducts from A) ditert. Diamines or optionally polyethered. Polyamines with a pK value of at least 5 and B) organic compounds that

ίο have 2 or optionally more than 2 aliphatically bonded halogen atoms with an atomic weight of at least 35.5 or groups of esters of strong acids corresponding to the halogen atoms, at temperatures from 60 to 160 ^° C. in bulk or in a solvent. The process is characterized in that at least one of the components specified under A) or B) has a molecular weight of 500 to 5000 and at the same time contains a carbon chain of at least 18 carbon atoms which may be interrupted by heteroatoms.

The high molecular weight substances of greater interest in the context of the invention preferably have recurring substances Structural unit

IVi Λ. "

1 1

■ R - Ν - CH- R'- CH- Ν -
R ₄ R ₅ R ₆ R ₂

(2HaIe) _n

- N® - Br ^e groups

and are therefore suitable as ion exchangers. On the other hand, the salty character and cause the high degree of branching a very high brittleness of the materials obtained. You can do without Powder more in a mortar and do not have the strength and strength characteristic of plastics Extensibility. Their mechanical behavior can best be compared to that of an extremely networked one Compare Bakelite-type thermosets. The chain lengths of the network segments are only 5 to 12 atoms. High molecular chains are therefore not formed at all in this process.

The cited patent does not reveal the extent to which the quaternization polyaddition occurs takes place because even with a conversion of only 80% of theory due to the strong branching crosslinked resins are to be expected. Accordingly, the teaching of British patent specification 652 830 gives no indication of whether it is possible to use predominantly linear or only weakly crosslinked, high molecular weight Manufacture materials with a thermoplastic or elastic character through a quaternization polyaddition.

The use of a quaternization reaction to build high molecular weight substances with a plastic character or plastic-like behavior from low molecular weight building blocks was, however, unknown until now. The reason for this may be to be found in the fact that the quaternization of tertiary amines when using bromides and chlorides is often slow and sometimes incomplete, and the heat released during the reaction, which is approximately regarded as a measure of the driving force of the reaction. These high molecular weight substances of particular interest are obtained by polyaddition of diamines, possibly also polyamines, of the general formula I

N —R —N

R ₂

of dihalides, optionally also polyhalides or corresponding esters of strong acids of the general types Formula II

R ₅ - CH - R '- CH - R ₆
Hal Hal

obtain.

In the above formula I, R ₁ , R ₂ , R ₃ and R ₄ denote monovalent organic radicals, preferably aliphatic hydrocarbon radicals having 1 to 10 carbon atoms. In the event that the radical R 'of the formula II represents a radical containing at least 18 carbon atoms, R can mean a divalent or polyvalent organic radical having at least 2 carbon atoms, which may optionally also contain heteroatoms, can be branched and is either aliphatic, is cycloaliphatic or araliphatic in nature. In the event that the radical R 'of the formula II contains fewer than 18 carbon atoms, the radical R of the formula I should contain at least 18 carbon atoms. The radicals R ₁ together with R ₃ , R ₂ together with R ₄ , R ₁ together with R ₂ and R ₁ or R ₃ together with R can together form 5-, 6- or 7-membered ring systems. All of the

3 4

the aforementioned radicals, ie R ₁ , R ₂ , R ₃ , R ₄ and R The additional functional groups can

can optionally also carry substituents, both to influence the physico-chemical which does not degrade the basicity of the amine nitrogen- properties of the desired polymers as well set and are inert towards the amino groups. as starting points for later networking, e.g. B.

In the above formula II, 5 means sulfur, peroxides, metal oxides, form-R 'a di- or polyvalent organic radical aldehyde, polyisocyanates or polyols, polyamines, with one or more carbon atoms, which polyamides, ureas, polyepoxides, vinyl optionally also Heteroatoms contain bonds, polycarbodiimides are introduced. This can and aliphatic, araliphatic, aromatic applies to the divalent radical R 'is ent- or heterocyclic in nature. In the event that R is the io in principle also for the two one formula I a radical with less than 18 carbon radicals; R ₅ and R ₆ ; These radicals are preferably atoms, R 'should mean a radical containing at least 18 carbon but hydrogen or activating groups such as substance atoms. z. B. aromatic radicals, such as phenyl radicals. Preferential

The radicals R ₅ and R ₆ can be aliphatic or those di- or polyhalides of a cycloaliphatic nature, preferably they are, which are aliphatically bonded bromine or hydrogen atoms or aromatic radicals contain chlorine. Accordingly, in the case of dibromides, R 'preferably has a weight of at least 35.5 ° C, ie chlorine, bromine or an aliphatic, optionally branched di-iodine or a radical of 1 to 10 C equivalent to a halogen atom Atoms, while di-remainder of the ester of a strong acid, such as. B. Benzene 20 chloride preferably aromatic radicals R ', which can still carry sulfonate, tosylate, naphthalene sulfonate ^ trichloroacetate, additional substituents. contain. To understand alkyl sulfate, perfluoroacylate. Connections are also of particular importance

The invention also includes methods, at low vapor pressure, which are physiologically undeniable are tri-questionable through use or co-use. You will preferably go through or polyfunctional starting materials, the addition of bromoethanol to aliphatic or action directly to crosslinked elastomers or aromatic di- or polyisocyanates or through leads to hard, infusible resins. Addition of chloromethylphenyl isocyanates to ali-

It was surprising that with the choice of suitable phatic or araliphatic "diols, ether diols or Diamines and dihalides obtained high molecular weight linearly corresponding diamines, built-up substances with plastic character and with 30 The following examples show the extraordinary Molecular weights over 50,000 arise and these new possibilities of variation of the suitable di- or poly-types Polymers after deformation, optionally halides: 1,3-dibromobutane, 1,4-dibromobutane, 1,2, can be crosslinked by conventional methods. 3-trichloroisobutane (only two chlorine atoms are reactive), Such combinations of 1,6-dibromohexane, 1,3-dibromo-neopentane and methyl-diamines are particularly suitable and dihalides, their low molecular weight 35 hexanediol ditosylate, 1,3-bis-chloromethyl-4,6-dimethyl analogs When combined, benzene, 0-, m-, p-xylylene dichloride, bis-chloromethyl react very exothermic. naphthalene, bis-chloromethyl-diphenyl ether, bis-chlorine

In addition, it was particularly striking that methyl-duro ^ bis-chloromethyl-tetrachlorobenzene ^ -Disich the quaternization polyaddition even then is chlorobutene, 1,4-dichlorobutine, dichloromethyl ether, digut can be carried out if the starting components 40 are chloroethyl ether, dibromobutyl ether, dichlorodiethyl molar weights of over 4000. sulfide, dibromodiethyl disulfide, dichlorodiethyl sulfone,

In principle, all dihalides are all carbonic, 10-dichloroanthracene, cyanuric chloride, bis-chlorohexyl bonds which contain at least two aus- isocyanurate, adipic acid bis- /? - bromoethyl ester, sufficiently reactive halogen atoms or this stinic acid bis-β-chloroethyl ester ; halogen-acylated polyequivalents reactive ester residues of strong acids 45 amines such as bis-chloroacetylhydrazine, bis-chloroacetyl contain. The divalent radical R 'can be purely aliphatic Ν, Ν'-dimethylhydrazine, methylene-bis-bromoacetamide, table, cycloaliphatic, aromatic-aliphatic, hetero-bis-chloroacetyl-ethylenediamine.Bis-chloroacetyl-N.N'-dicyclic, saturated or partially unsaturated methylethylenediamine, bis-chloroacetylpiperazine, bissein. Aliphatic radicals can also heteroatoms bromoacetyltetramethylenediamine, bis-chloroacetylhexawie z. B. O, N, S, P in the main chain or in the 50 methylenediamine, bis-bromoacetylhexamethylenediamine, have side chains. From the above, bis-a-chloropropionylpiperazine; Bis-urethane from Dig shows that R 'also de-isocyanate functional groups and bromoethanol, such as. B. 4,4'-methylene, both those of the same bis-carbanilsäure-bis-bromoethyl ester, hexamethylene type, such as the groups Hai, as well as different bis-bromoäthylurethan, toluene-2,4-bis-bromoäthylure- Groups such as B. - OH, - COOH, - CN, 55 than, toluylene-2,6-bis-bromoethyl urethane, hexamethy- COOR, - SO ₂ R, - NCO, len-bis-chloromethylphenylcarbamic acid ester, tetra-

methylene-bis-chloromethylphenylurea etc.

Special dihalides that allow subsequent crosslinking reactions are: 1,3-dichloro

_, _, / -. / 60 propanol-2, l, 3-dibromopropanol-2, 2,2-bis-chlorme-

\ \ thylpropanediol, 1,3-dichloroacetone, 1,5-dichloroacetyl

R acetone, 1,4-dibromoadiponitrile, bis - (* - chlorobenzy-

liden) hydrazine, derivatives of nitrogen mustard such as

__ "" _N "j rf V N.N'-bis-chloroethylaniline.N.N'-bis-bromoethyltoIuidine,

\ X 65 bis-bromoethylalkenylphosphine oxide, e.g. B. oxethylated

R vinylphosphonic acid bromide, bisbromoacetyl-1,2-pheny-

and . Jendiamine carboxylic acid ^^ - Bis-ichloracetamidoi-anisole-

- CO - NH - R 4-sulfonic acid sodium, trichloropentaerythritol, di-

bromopentaerythritol, fumaric acid bis-ß-bromoethyl ester, Bis-chloromethyldiphenylmethane diisocyanate, 1,3-dibromopropanol (2) allyl ether, N, N'-bis- / I-bromoethylbenzenesulfonic acid amide.

Long-chain dihalides can usually in a simple manner from the corresponding diols after a Series of known methods can be produced. Among the long-chain ones that come into question for this Diols are in particular the various easily and cheaply accessible polyester diols, polyether diols, Poly thioether diols, polyester amide diols, polyacetal diols mentioned. The linear types come first in question, such as B. the polymerization products of ethylene oxide, propylene oxide and tetrahydrofuran and their mixed and graft polymers (e.g. polypropylene oxide-acrylonitrile); furthermore simple and mixed Ether, e.g. B. based on hexanediol, thioether z. B. based on thiodiglycol, polyester z. B. based on Adipic acid, sebancic acid, phthalic acid, tetrachlorophthalic acid, terephthalic acid, succinic acid, ethylene glycol, Propylene glycol, butylene glycol, 1,3-neopentyl glycol, hexanediol, oxethylhexanediol, dioxäthylhexanediol. Particular mention should be made of unsaturated polyesters which, for. B. maleic acid, fumaric acid, itaconic acid, Citraconic acid, mesaconic acid, tetrahydrophthalic acid, muconic acid, butenediol, butynediol, dioxäthylbutendiol included condensed.

The average molecular weights of the long-chain diols can vary between 200 and 20,000, depending on how far the specific salt-like character of the quaternary ammonium grouping in the end product should appear. Of the known methods for converting alcohols into the halides, the reaction with SOCl ₂ or SOBr ₂ in the presence of weak bases (e.g. pyridine, alkaline earth carbonates) is particularly suitable. The esterification with hydrohalic acids only works if the diol is stable to salt (e.g. decamethylene bromide from decanediol).

Other methods for converting diols into dihalides with molecular enlargement are named as an example:

1. The esterification with chlorine methyl or bromomethylcarboxylic acids, eg. B. chloroacetic acid, bromoacetic acid, Chformethylbenzoic acid, its simple esters or acid halides.

2. The reaction with halogen isocyanates, e.g. B. chloroalkyl isocyanates, chloromethyl aryl isocyanates with the formation of halo-urethanes.

3. The extension of diols with aliphatic or aromatic diisocyanates and reaction the terminal isocyanate groups with halohydrins, e.g. B. ethylene chlorohydrin, / J-bromoethanol and glycol mono-tosyl ester.

4. The reaction with acid halides of strong acids, such as benzenesulfonic acid, p-toluenesulfonic acid, Naphthalenesulfonic acid, trichloroacetic acid to the corresponding esters. Also from dicarboxylic acids, z. B. Polyester dicarboxylic acids can be used according to the invention to produce dihalides, what one z. B. by esterification with ß-halo alcohols or also via diisocyanates and halogen alcohols or halogen isocyanates. Extension via diisocyanate-haloalcohol or over halogen isocyanate has the advantage that it is also based on long-chain hydroxycarboxylic acids, such as they are often present in higher molecular weight polyesters, can be used.

Suitable diamines in the quaternization polyaddition are all di- or poly-tertiary amines, which strongly basic, d. H. those with a pK value of at least 5 and are not sterically hindered. Preferred diamines are bis-dimethylaminoalkyl compounds. In exceptional cases, weaker basic amines can also be used (pK value at least 9.5) if the steric conditions for the Quaternization are extremely cheap, e.g. B. with bispyridines and other basic nitrogen heterocycles.

The divalent, optionally branched radical R can be purely aliphatic, cycloaliphatic, aromatic-aliphatic, be heterocyclic, saturated or partially unsaturated. Aliphatic residues can also heteroatoms, preferably oxygen, nitrogen or sulfur in the main chain or in the side chains exhibit. Purely aromatic radicals R are generally unsuitable because the nucleophilicity of the Amine nitrogen is thereby reduced too much. Just like R ', R can also have functional groups included, provided that they are sufficiently inert towards the tertiary amino groups, z. B.

-OH-CN

SO ₂ R
R.

-n /

-NH

- COOR - Hal
-C = C

= CO
- COO -NHR

What has been said for the divalent radical R also applies in principle to the radicals R ₁ to R ₄ , but these radicals are preferably methyl groups or bridge members of a bicyclic system.

Low molecular weight ditertiary amines which can be used for the present process are obtained, for. B. by Methylation of the technically easily accessible α, ω-diaminoalkanes such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine means Formaldehyde / hydrogen or formaldehyde / formic acid, also from the corresponding halides or diols with dimethylamine (see. For example Houben - Weyl, Müller, XI / 1 p. 24ff.), From ketones, Diamides, ureas by Mannich reaction, from the bis-cyanoethylation products of Diols, amines and dimercaptans by hydrogenation and methylation, from diisocyanates by addition from dimethylaminoethanol, from diols and diamides by addition of ethyleneimine and then Methylation.

The following are examples of the large number of compounds that can be used:

1 ^ -Diaza-bicycloP ^^ joctan, tetramethylethylenediamine, Tetramethylpropylenediamine, tetramethyltetramethylenediamine, tetramethylhexamethylenediamine, Pentamethyldipropylenetriamine, hexamethyltriethylenetetramine, tetraethyltetramethylenediamine, 1,4-bis-di-

methylaminomethylbenzene, 4,4'-bis-dimethy] aminoperhydrodibenzyl, 4,4'-bis-dimethylaminodicyclohexylmethane, α, α'-dimethylaminoethylbenzyl cyanide, 1,3-bisdimethylaminobutane, hexamethylene-bis-carbamic acid-bis-dimethylaminoethyl-glycol, bis-dimethylaminoethyl-glycol , Bis-dimethylaminopropyl diethylene glycol ether, bis-dimethylaminomethylcyclohexanone, bis-diethylaminomethylcyclopentanone, 4- (ß- N-pyrrolidylethyl) pyridine, 2- (| e-dimethylaminoethylpyridine), bis - («- pyridylethyl) ', Νbenzylamine, , ίο N'-tetrakis- (dimethylaminopropyl) -p-phenylenediamine, N, N'-bis- (a-pyridylethyl) -m-phenylenediamine, N, N'-bis- (γ-pyridylethyl) -p-phenylenediamine, N , N'-bis- (dimethylaminopropyl) -m-phenylenediamine, bis-morpholino-methyl-urea, bis-piperidinomelhyl-biuret.

Examples of compounds that allow subsequent crosslinking are: 1,6-bis-dimethylaminohexanol - (2), 1,3-diethylaminopropanol - (2), 2,2-bis-dimethylaminomethylpropanediol-1,3, fumaric acid bis - ß- dimethylaminoethyl ester, dimethylallyl (3 _: dimethylamino-2-dimethylaminomethyl-2-hydroxy) propylammonium chloride, Ν, Ν-dimethylaminopropylaniline, Ν, Ν-dimethylaminopropyl-m-toluidine, N, N-dimethylaminopropylbenzenesulphonamide, N, N-dimethylaminopropylbenzenesulfonamide, N, p-toluenesulfonamide, bis- (methylallylaminoethanoO-hexamethylene-bis-urethane.

The long-chain ditertiary amines suitable for the process according to the invention are expedient also made from long-chain diols. For the types in question what has been said for the production of long-chain dihalides applies.

The following methods are exemplified for converting the diols into ditertiary amines:

35

1. Reaction with ammonia and methylation of the diamines formed.

2. Reaction with dimethylamine or other dialkylamines.

3. Conversion into dihalides z. B. according to the methods described and reaction with dialkylamines.

4. Reaction with aliphatic or aromatic diisocyanates and reaction of the terminal ones Isocyanate groups with dialkylamino alcohols, e.g. B. dimethylaminoethanol.

5. Reaction with 2 moles of acrylonitrile with subsequent hydrogenation and methylation.

6. Reaction with 2 moles of vinyl pyridine.

7. Esterification with dimethylaminobenzoic acid.

The embodiments described below are intended to be within the scope of the present invention explain without, however, the process according to the invention on the starting materials mentioned and reaction conditions would be limited. Rather, knowledge of these embodiments enables a person skilled in the art can readily work out analogous embodiments.

The process of the invention is generally used to prepare the polymers so that 1 mole of a diamine is mixed with 0.5 to 2.5 moles (preferably 0.8 to 1.5 moles) of a dihalide at elevated temperature (preferably 80 to 180 ° C) to react and then so after heating for a long time until the polymer formed reaches the desired degree of viscosity! Has. In a preferred Ausfülmingsform one component is selected to be short-chain, the other long-chain and the short-chain component at the desired reaction temperature in, the melt of the long-chain Component entered. After a short induction period, heat is generated and The reaction starts with a sharp increase in viscosity, with the melt usually becoming temporarily cloudy. Reheating on sheet metal or in molds at temperatures around 100 to 130 ° C leads to solid thermoplastic Plastics that may be at a high temperature can be processed or poured on the roller.

Both the diamine and the dihalide are long-chain and therefore both products are more waxy Texture, so they can be melted together. It is then heated until the mixture is homogeneous, and reheats at 80 to 160 ° C until the desired viscosity is reached.

If both reactants are relatively short-chain, careful temperature control must be ensured special care must be taken, since the reaction proceeds with considerable exothermicity and at the same time there is a very strong increase in viscosity. The higher melting point is expediently Component premelted and the other component gradually added. It can be advantageous here be to work in a solvent in which the polymer is soluble. For example in dimethylformamide or tetramethyl sulfone.

Polyquaternization occurs at temperatures below 60 ° C depending on the reactivity of the components only an imperfect one. In such cases it is possible to fuse diamines and dihalides with one another at correspondingly low temperatures and the to store solidified melt without a reaction occurring. The polyquaternization then takes place simply by baking out.

This fact is of particular importance for the production of crosslinked polymers in the casting process with the use of trifunctional or polyfunctional amines or halides. You melt in this If the components heat up, if necessary, heat until the start of the extension reaction, pour in Shapes and hardens through post-heating. After a few hours, the crosslinked high molecular weight Elastomers are taken.

Temperatures above 180 ¹ C favor cleavage of the polymers or degradation. To achieve very high molecular weights, it is more advantageous to keep the temperature at 80 to 160 ° C. for a longer period of time, optionally with the addition of a solvent, than to increase the temperature even further.

Of course, the polyquaternization reaction can also be followed directly to the preparation of a Connect the output connection without isolating it. For example, you put a long Polyester diol is added over 2 moles of diisocyanate with 2 moles of dimethylaminoethanol, then 1 mole of dihalide is added, such as dibromobutane, and leaves together until the desired viscosity is reached react.

Jc according to the raw materials used, z. B. purely bifunctional components, are the thermoplastic polymers with formaldehyde, Sulfur, peioxides, diisocyanates, etc. according to the usual Methods can be combined, either by the casting process or by those in the Gutniniindiistrie usual Vulkanisierunpsverfahrcn can be worked. With a suitable choice of components it is

109 551/491

Furthermore, it is also possible to obtain elastomers which, depending on the content of quaternary ammonium groups, more or less hydrophilic properties, but especially an antistatic character

point.

Presentation of the raw materials
Long chain diamines

IO

Al: 1 kg of the OH Polytetrahydrofuranäther be Zahl40 dehydrated at 120 ⁰ C in a vacuum, cooled to 80 ⁰ C and stirred in 167 g of 4,4-diphenylmethane diisocyanate at this temperature. It holds one-half to 1 hour at 80 to 100 ⁰ C, then stirred 60 g Ν, Ν-dimethylaminoethanol in one portion and holds a further 1 hour at 130 ° C. The resulting melt of the corresponding polyamine is poured onto metal sheets, where it solidifies to form a waxy product. Calculated Average Molecular Weight: 3700.

A 2: adipic acid-ethylene glycol polyester lkg of an OH number of 56 are dewatered at 13O ⁰ C in vacuo and stirred in 168 g of hexamethylene diisocyanate. Maintaining the melt for 1 hour at 13O ⁰ C, allowed to cool to 80 ° C and 89 g of dimethylaminoethanol is to. After it has been reheated at 130 ° C. for about an hour, it is poured onto metal sheets. A hard wax is obtained. Calculated average molar weight: 2500. K value in 1% dimethylformamide solution at 25 ° C: 22.

A 3: The batch was like A 2, but using 125 g of hexamethylene-1,6-diisocyanate and 44 g of dimethylaminoethanol carried out. A hard, tough wax is obtained. Calculated Average Molecular Weight: 4700. K value in 1% dimethylformamide solution at 25 ° C: 27.

A4: 900 g of polypropylene glycol with an OH number of 63 are dehydrated at 130 ° C., 250 g of 4,4'-diphenylmethane diisocyanate are stirred in and, after stirring for 1 hour at 130 to 140 ° C., 0.02 ml of dibiityl tin dilaurate are added. After cooling to 50 to 6O ⁰ C 89 g of dimethylaminoethanol is added in one portion, the temperature rising to 84 ° C. It is allowed Va hour at 130 ⁰ C to react further and poured into bottles. A viscous oil with a calculated average molecular weight of 2450 is obtained.

A 5: A polyester is made from 26 mol of adipic acid, 30 mol of oxethylhexanediol, 4 mol of maleic anhydride and 5 mol of dioxäthylbutenediol. H 2: produced, which has an OH number of 72.6 and an acid number of 1.6. 755 g of this polyester are with 174 g of 2,4-tolylene diisocyanate for 1 hour at 100 ° C under nitrogen for 3 H: transposed and 89 g of dimethylaminoethanol was added after cooling to 6O ⁰ C in one portion. The mixture is left for 1 hour at 100 ⁰ C under nitrogen to react for and obtains a brown-yellow oil from the calculated Durchschnittsmolgewicht 2040th

K value in 1% dimethylformamide solution at 25 ° C: 23.9.

A 6: The procedure is as for A 2, but using 117 g of diethylaminoethanol.

40

Short chain diamines

To 178 g of dimethylaminoethanol in 100 ml of toluene, 168 g of hexamethylene diisocyanate are added dropwise at 8O ⁰ C and then held still for 20 minutes at 9O ⁰ C. After cooling, it is diluted with 200 ml of mineral spirits and the precipitated crystals are filtered off with suction. 318 g (92% of theory) of hexamethylenedicarbamic acid bis-dimethylamine ethyl ester with a melting point of 63 to 64 ° C. are obtained.
To 178 g of dimethylaminoethanol in 100 ml of chlorobenzene, 250 g of 4,4'-diphenylmethane diisocyanate are added dropwise in 500 ml of chlorobenzene at 8O ⁰ C. After the chlorobenzene has been distilled off at 12 torr, a viscous flarz remains, which solidifies glassy.

According to JT Braunholtz and FG M a η η, Soc, 1953, p. 1817, m-toluidine is converted into N, N'-biscyanoethyl-m-toluidine. Of these, 180 g of melting point 82 ° to 83 ° C in 11 methanol and 150 ml of liquid ammonia with the addition of 50 g of Raney cobalt catalyst at 9O ⁰ C and 150 atm. Hydrogen pressure hydrogenated. 130 g (70% of theory) of N, N'-bis-aminopropyl-m-toluidine can be obtained from the residue freed from catalyst and solvent by distillation. Bp 165 to 168 ° C. To methylate the amino groups, 130 g of N, N'-bis-aminopropyl-m-toluidine are dissolved in 200 ml of methanol and, after addition of 25 g of Renay nickel, at 110 ° C. and 120 atm. Hydrogen pressure 180 ml of 40% formaldehyde solution are pumped in within 2 hours. After the catalyst and solvent have been removed, 117 g of bis (dimethylaminopropyl) m-toluidine are obtained by high vacuum distillation. Bp 139-147 ° C (0.08 torr).

Long chain dihalides

In 1 kg of adipic acid-ethylene glycol polyester of OH number 56, 168 g of hexamethylene diisocyanate were stirred after dehydration at 130 ⁰ C and added at the same temperature after 1 hour, 80.5 g of ethylene chlorohydrin. After a further hour, it is poured onto metal sheets, where the melt solidifies to a hard wax. Calculated Average Molecular Weight: 2500.
K value in 1% dimethylformamide solution at 25 ^° C.: 25.3.

The procedure is as under H 1, but instead of the ethylene chlorohydrin, 124 g / 3-bromoethanol added. Calculated Average Molecular Weight: 2540.

It is stirred for 1 kg of adipic acid-ethylene glycol polyester of OH number 56 after dehydration at 100 ° C and 250 g of diphenylmethane-diisocyanate react, cooled to 70 ⁰ C. and 125 g of .beta.-bromoethanol to. Thereafter, it is kept at 90 ^° C. for 0.5 hours and poured onto metal sheets. The result is a resinous wax that crystallizes very slowly. Calculated Average Molecular Weight: 2750.
K value in 1% dimethylformamide solution at 25 ^° C.: 22.

H 4: The procedure is as under H 3, as a diisocyanate however, 174 g of 2,4-tolylene diisocyanate are used. Calculated average mole weight 2540.

H 5: 1 kg of polytetrahydrofuran with an OH number of 40 are ^{dehydrated at 100 °} C. for 1 hour and 112 g of chloromethylphenyl isocyanate are introduced. The mixture is kept at 100 to HO ⁰ C for 30 minutes and the melt is then allowed to solidify. A hard wax with a calculated average molar weight of 3300 is obtained.

H 6: 300 g of polytetrahydrofuran with a molecular weight of 3000 are dissolved in 1 liter of toluene and mixed with 16 g of pyridine. Thereto is added dropwise 24 g of thionyl chloride at 5O ⁰ C and heated to 90 ⁰ C. It is neutralized with further pyridine, the precipitated pyridine hydrochloride is filtered off with suction and the solvent is drawn off in vacuo. The result is a hard wax with an OH number of 4 and a chlorine content of 2.2% (calculated 2.4%).

H 7: 1 kg of polypropylene glycol with an OH number of 63

-, are dehydrated at 13O ⁰ C and 195 g of toluene

) 2,4-diisocyanate stirred in. One holds ¹ _1/2 hours

at 130 ° C, cooled to 80 ° C., is 140 g / S-bromoethanol to and holding for 1 hour at 100 ⁰ C. This gives a viscous yellow oil from the calculated Durchschnittsmolgewicht 2400th

H 8: 200 g of polyethylene-propylene glycol mixture (ethylene oxide / propylene oxide = 1: 1) of an OH number of 57.6 are introduced slowly into 400 ml of 48% hydrobromic acid, keeping the temperature to rise to 5O ⁰ C. ^{The solution is kept at 70 °} C. for 10 to 11 hours, neutralized with sodium carbonate and extracted several times with benzene. After the benzene has been dried and distilled off, a light brown oil remains which has an OH number of 1.6 and a bromine content of 2.6%.

40 Short Chain Dihalides

H 9: To a solution of 161 g Glykolchlorhydrin in 500 ml of dry chlorobenzene is allowed after the addition of 0.1 ml of dibutyltin dilaurate /) 168 g hexamethylene diisocyanate at 8O ⁰ C to-

drops. The mixture is stirred for 1 hour, allowed to cool and filtered off with suction. Melting point 111 to

H 10: The procedure H 9, starting from 250 g Glykolbromhydrin.Schmelzpunkt 113bis 114 ⁰ C.

HH: To a solution of 125 g Äthylenbromhydrin in 50 ml of dry chlorobenzene was slowly added a solution of 125 g 4,4'-diphenylmethane diisocyanate in 400 ml of dry chlorobenzene at 8O ⁰ C. It is stirred for 30 minutes at 8O ⁰ C, cooled and filtered off. Melting point 155 to 156 ⁰ C.

H12: To a solution of 34 g m-Chlormethylphenylisocyanat in 100 ml of toluene is added dropwise at 8O ⁰ C a solution of 12 g of hexane in 50 ml of toluene.
Melting point 86 to 87 ⁰ C.

Example la

g of polyhexanediol ether with a molecular weight of 560 are dissolved in 250 ecm of toluene, and 35 g of pyridine are added. At 0 ° C, 102 g of thionyl bromide are added dropwise, then the reaction mixture is kept for 12 hours at 10 to 2O ⁰ C. The precipitate which separates out is centrifuged off and the toluene is drawn off in vacuo. The result is a hard wax with an OH number of 5 and a bromine content of 15% (calculated 23%).

34 g of the χ, ω-polyhexanediol ether dibromide from Molecular weight 690 are reacted with 6 g of hexamethyl-triethylenetetramine. At 80'C the reaction starts with turbidity and a sharp increase in viscosity. At 120 ° C it becomes tough, stringy Melt obtained, which finally solidifies to form a crosslinked polymer. The polymer cannot be pulverized, can be cut and is viscoplastic.

Example Ib

The same experiment is carried out with 6.8 g -dipropylentriamin pentamethyl wherein the mixture is heated for 6 hours at 12O ⁰ C in a mold. A solid, soft, tough, flexible plastic plate is obtained.

Comparative experiments

For comparison with la, 10 g of hexamethyltriethylenetriamine with 10 g of dibromobutane were used according to the example 2 of British Patent 652 830 implemented. A resin separates out of the thin reaction mixture, which is very strong after cooling is brittle and pulverizable after removal of water-soluble hydroscopic components.

The same result is obtained with pentamethyl-dipropylenetriamine as the amino component. It results In addition to water-soluble components, a powderable resin without plastic character.

B e i s ρ i e 1 Ic

An analog experiment for example 2 of British patent specification 652 830 with a higher molecular weight, branched amine (Al) instead of hexamethyltriethylenetetramine is shown in Example 10 (see d.). A rubber-elastic polymer is obtained, the properties of which are vulcanized natural rubber is equivalent to.

Example Id

320 g of a polytetrahydrofuran ether diol with a molecular weight of 3000 are dissolved in 900 ecm of toluene and the solution is distilled at atmospheric pressure until no more water passes over. Then 16 g of pyridine and 46 g of thionyl bromide are simultaneously added dropwise ^{at 0 ° C. from 2 drop funnels.} The mixture is subsequently stirred at ⁰ ° C. for 4 hours, then the reaction mixture is kept at 10 to 20 ° C. for 12 hours. The precipitate of pyridine hydrobromide which separates out is centrifuged off and the toluene is drawn off in vacuo. The result is a hard wax with an OH number of 3 and a bromine content of 4.1% (calculated 4.8%). 130 g of Λ, ω-polytetrahydrofuran of molecular weight 3120 dibromide are melted, 5.3 g pentamethyl dipropylenetriamine intimately mixed and the melt is heated in a mold for 24 hours at 12O ⁰ C. A soft, tough, rubber-elastic sheet is obtained.

Example Ie

An aliphatic paraffin of molecular weight 580 and the calculated on the basis of analysis data sum formula C "H ₈₁ is at 90 to 12O ⁰ C under the UV-

The lamp is brominated so that 2 bromine atoms per molecule occur.

150 g Dibromparaffin are mixed with 100 g pentamethyl dipropylenetriamine 4 hours at 80 ° C, then treated for 5 hours at 100 ⁰ C and drawn off the excess amine under vacuum. Then 45 g of dibromobutane are added and the melt is post-heated in a mold at 100 ^° C. for 24 hours. A hard plastic compound is obtained.

Example 2

25 g of diamine A 2 are ^{melted at 110 °} C. and 1.75 g of p-xylylene dichloride are stirred in. After a short time, a highly viscous, no longer pourable mass is formed, from which threads can be drawn, which are no longer hygroscopic.

Example 3

200 g of diamine A 2 are melted and 17 g of 1,4-dibromobutane are stirred ^{in at 100 ° C.} The melt is briefly evacuated and poured into a mold. After 20 minutes at 100 ^° C., a homogeneous, clear and soft plastic sheet has formed. A strip of this can be stretched to ten times its length and becomes extremely tensile strength in the process. After relaxation, the elongation goes back to 500% at room temperature. A strip stretched in this way does not crystallize, while unstretched pieces crystallize through after a few days, creating hard, elastic thermoplastics. Melting point at 19O ⁰ C. The water enters swelling, in dimethylformamide solution, a. K-value in l ° / cent dimethylformamide solution at 25 ⁰ C: 84th

Example 4

10.8 g of 1,4-dibromobutane are stirred into the melt of 235 g of diamine A 3 at 100 ^{° C.} The previously evacuated melt is reheated in a mold at 100 ° C. for 4 hours. This resulted in a thermoplastic with the properties described in Example 3, but which no longer swells in water. K-value in 1% 'ger dimethylformamide solution at 25 ^C C: 75.4.

Example 5

In the melt of 200 g of dihalide H 1, 9 g of 1,4-diazabicyclo [2,2,2] octane (triethylenediamine) are added at 100.degree. stirred in and the mass reheated at 100 ° C for 16 hours. After this time, the melt is become stringy. After cooling, it solidifies to a hard, brittle mass. K value in 1% Dimethylformamide solution at 25 ° C: 30.8.

Example 6

In the melt of 204 g of H 2 dihalide gl at 100 ⁰ C 9, 4-diazabicyclo [2,2,2] octane (triethylenediamine) are stirred in and the mass reheated 13.5 hours at 100 ⁰ C. A white, tough thermoplastic was created.
K-value in l ° / _o sodium dimethylformamide solution at 25 ⁰ C: 53.5. -

Example 7

14 g of p-xylylene dichloride are stirred into the melt of 205 g of diamine A 6 at 100 ^° C. and the mass poured into molds is reheated at 100 ^° C. for 3.5 hours. The result is a thermoplastic material that is broken down again when heated for a long time, with p-xylylene dichloride escaping.

Examples i

34.6 g of diamine A 7 are introduced into the melt of 254 g of dihalide H 2 at 80 ^° C. and the viscous liquid is poured into molds j after degassing in vacuo. After 5 hours, subsequently heating at 100 ⁰ C j has arisen a thermoplastic plate having high tensile strength and I hait after crystallization and is elastic.

ίο K value in 1% dimethylformamide solution at 25 ⁰ C: 35.4.

Example 9

126 g Dimain A 2 and 127 g H 2 dihalide are melted together at 40 ⁰ C. The solidified melt has a K value of 28 after 1 day and a K value of 38.9 after 2 weeks (measured in 1% strength dimethylformamide solution at 25 ° C.). If the melt is heated to 100 ^° C. for 24 hours, a solid thermoplastic material is produced. K value in 1% dimethylformamide solution at 25 ° C: 45.0.

Example 10

In the melt of 210 g of diamine A 1 at 9O ⁰ C 6.9 cc of 1,4-dibromobutane are stirred. After brief degassing of the melt, which is rapidly becoming more viscous, it is poured into a mold and post-heated at 100 ^° C. for 24 hours. The result is a cross-linked, rubber-elastic sheet with the following mechanical properties:

Strength 111 kg / cm ²

Elongation at break 610%

Module at 500% elongation 62 kp / cm ²

Hardness (Shore A) at 20 ° C 55

Rebound resilience in% 64

Structure (kg abs.) 16

Permanent elongation (l '/ l h) 18/7

Example 11

In the melt of 200 g of diamine Ä 2 are at

100 C ⁰ 13 g Tris-chlorohexyl isocyanurate and 8.5 g of 1,4-dibromobutane stirred. After 3 hours of post-heating, a crosslinkable plate with the following mechanical properties is created:

Strength 97 kg / cm ²

Elongation at break 645%

Module at 500% elongation 48

^s hardness (Shore A) at 20/75 ⁰ C 86/35

Rebound elasticity (20/75 ⁰ C) in% 36/50

Example 12

At 100 ° C., 21 g of 1,4-diazabicyclo [2,2,2) octane are introduced into the melt of 550 g of dihalide H 3. The viscous mass is poured into cans and post-heated at 100 ° C. for 4 hours. It results a thermoplastic material which is hard at room temperature and which can be crosslinked peroxide, whereby a slightly elastic, leather-like material is created.

Example 13

204 g of diamine A 5 and 254 g of dihalide H 4 are melted together, poured into cans and reheated at 100 ^° C. for 8 hours. The result is a soft, thermoplastic, rubber-like material that can be crosslinked peroxide.

Example 14

30 g of dihalide H 6 are melted and 1.1 gl, 4-diazabicyclo (2,2,2) octane is stirred in. Upon heating to 15O ⁰ C the reaction is carried out under viscosity increase. A tough resin results when it cools down.

B e i s ρ i e 1 15

500 g of Polybutylenglykoläther an OH number of 40 are dehydrated at 130 ⁰ C and stirred at 90 ° C 56 g of m-chloromethyl-phenyl isocyanate. After 30 minutes, 46 g of bis (dimethylaminopropyl) -m-toluidine are added, the mass becoming cloudy, viscous and stringy. After lstündigem reheating at 100 ⁰ C a rubber-like, thermoplastic material that absorbs moisture in the air under swelling and is strongly sticky is formed. It can be crosslinked with formaldehyde.

B e i s ρ i e 1 16;

2.8 g of diamine A 9 are stirred into the melt of 25.4 g of dihalide H 2 at 140 ^{° C.} While stirring the mass becomes highly viscous, in a nitrogen atmosphere to 16O ⁰ C heated. White, firm, weakly elastic threads can be peeled off from the melt without stickiness. The material can be crosslinked with formaldehyde.

The crosslinking takes place with 1% paraformaldehyde, 1% toluenesulfonic acid and 40 ° / ₀ highly active silica as the active filler. After 90 minutes of vulcanization at 121 ^° C., an elastomer with the following mechanical values is obtained:

Tensile strength 142 kgf / cm ²

Elongation at break 510%

Load at 300% elongation 72 kp / cm ²

Hardness (Shore A) 81

Rear-parallel elasticity 20 ° C 33%

Permanent elongation (l '/ l h) 32/22

Structure 26 kg abs.

Example 17

In 20.7 g of a Ν, Ν-tetramethyl-polyproypylenätherdiamins of molecular weight 2050, which is made from polypropylene glycol by amination with ammonia 'and subsequent methylation with formaldehyde / hydrogen was obtained in the usual way, 1.8 g of p-xylylene dichloride are stirred in at 100.degree. After 1 hour, a highly viscous, tough resin has formed, which in contrast to the starting components is completely soluble in water.

Example 18

IO

20 g of the N, N'-tetramethylpolypropylene ether diamine described in Example 17 ^{and having a molecular weight of 2050 are reacted with 3.5 g of p-xylylene dichloride at 100 °} C., an extended dichloride being formed. A further 12.8 g of N, N'-tetramethylpolypropylene ether diamine and 0.54 g of pentamethyldipropylene triamine are added and the mixture, which rapidly becomes viscous, is heated in a mold for 20 hours at 110 ° C. A clear, transparent, weakly crosslinked, water-swellable plastic is obtained .

Example 19

25 g of A 2 are reacted with 5.4 g of dibromobutane at 100 ° C., lengthening to a higher molecular weight dibromide taking place with an increase in viscosity. After 3 minutes, 1.7 g of triethylenediamine are added to the melt and the mixture is heated at 100 ^° C. for 2 hours. A hard, tough molded body is obtained.

Example 20

1 kg of poly tetrahydrofuran were reacted with 150 g of 2-vinylpyridine at 80 ° C. in the presence of 0.2 g of KOH. After the catalyst had been neutralized and the excess vinylpyridine had been distilled off, 129 gl, 3-dibiomopropanol (2) allyl ether were added and the mixture was heated to 120 to 130.degree. The polyquaternization reaction that sets in is noticeable through an increase in viscosity. This viscous melt is heated for 12 hours 12O ⁰ C. The thermoplastic, rubber-like mass obtained in this way can be vulcanized with sulfur.

Example 21

500 g of a polythioether with an OH number of 138 are converted into the ditosylate using p-toluenesulfonic chloride convicted.

200 g of the ditosylate (molecular weight 1120) were heated together with 30.5 g of diamine A 17 to 120 ⁰ C. The viscosity of the reaction mixture increases and a viscous melt is formed. A rubber-like thermoplastic material is obtained which can be vulcanized with polyisocyanates and polyepoxides.

Example 22

The procedure is as in Example 2, but using / S ^ '- dichlorodiethyl ether in place of p-xylylene dichloride. A viscous melt which solidifies at room temperature to form a thermoplastic composition is obtained after 4 hours reaction time at 15O ⁰ C. The same result is obtained with dichlorobutane.

Example 23

Starting from a hexanediol-neopentylglycol-adipic acid polyester, a diamine analogous to A 2 is produced. 160 g of this diamine are stirred with 8.7 ecm dibromobutane. The liquid mixture is post-heated in a mold at 100 ^° C. for 24 hours. The result is a clear, transparent, amber-colored elastomer with good strength and ductility, but low permanent elongation.

Example 24

254 g of dihalide H 2 are melted and at 80 ° C. rapidly with 43 g of melted Amine A 8 stirred. The melt, which becomes viscous very quickly, is poured into a mold where it becomes a strongly cross-linked, tear-resistant elastomer solidified.

Claims (2)

Patent claims: 1. Process for the preparation of quaternary polyadducts from A) ditert. Diamines or optionally polytrt. Polyamines with a pK value of at least 5 and B) organic Compounds containing 2 or, if appropriate, more than 2 aliphatically bonded halogen atoms from 109 551/491 Atomic weight of at least 35.5 or groups of esters corresponding to halogen atoms have strong acids, at temperatures from 60 to 160 ° C in bulk or in a solvent, characterized in that at least one of the specified under A) or B) Components has a molecular weight of 500 to 5000 and at the same time, if necessary, through Contains heteroatoms interrupted carbon chain of at least 18 carbon atoms. 2. The method according to claim 1, characterized in that diamines of the general formula I. N —R —N with dihalides of the general formula II Hal Hal where in formula IR ₁ , R ₂ , R ₃ and R ₄ aliphatically saturated or unsaturated hydrocarbon radicals with 1 to 10 carbon atoms and in formula II R ₅ and R ₆ hydrogen, an aliphatic, cycloaliphatic or aromatic radical and also R and / or R 'in the formulas I and II mean an aliphatic, cycloaliphatic or araliphatic divalent radical of at least 18 carbon atoms, optionally interrupted by heteroatoms, and at the same time the molecular weight of the relevant component of the formula I and / or II is a molecular weight of 500 to 5000 will. C C V;