DE2034713A1 - Production of methylene bridges on pointing polyarylams - Google Patents

Description

Imperial Chemical Industries Ltd, London, Great Britain

Production of polyarylamines containing methylene bridges Priority: July 11, 1969 - Great Britain

The invention relates to the production of diaminodiarylmethanes and other related methylene bridges containing polyarylamines with higher functionality Condensation of aromatic amines and formaldehyde »

The production of methylene bridges containing polyarylamines by condensation of arylamines with formaldehyde in the presence of acids such as hydrochloric acid, with condensates being obtained, the diamines, triamines and polyamines contain higher functionality is well known. If aniline is used as a prlmäraa arylanine, then the polyarylamines containing methylene bridges contain 2,4'- and 4,4'-diaminodiphenylmethanes of the formula

f \ -. OH ₂

NH,

009884/2264

and

GH.

NH,

the triamine 2 _t 4-bis (p-aminobenzyl) aniline of the formula

1L ₅

HH,

and related compounds with higher amine functionality » If the arylamine is an aniline, then you have them all mean formula

NH <

Ί ²

n-1

where η is 1 or mohr _o

009884/2264

Through a suitable setting of the aniline / formaldehyde ratio it is possible to manufacture products that contain the most varied proportions of diamines and higher polyamines contain. So it is possible to manufacture products that contain a large proportion of diamine or the one low proportion of diamine and increased proportion of triamine or contain polyamines of higher functionality. Goose generally can be said to be the amount of diamine in the product, the higher the ratio of Aniline is to formaldehyde «,

Polyarylamines containing methylene bridges, which are prepared by this condensation reaction, are used in large quantities to polyisocyanates by phosgenation ^v in an inert solvent such as a halogenated benzene, to produce. Polyarylamines, especially those. which are produced by known processes using smaller amounts of amine, often contain materials which are insoluble in such halogenated benzenes even at low concentrations, which is why they are not particularly suitable for phosgenation. It has now been found that improved products which contain fewer insoluble substances can be produced by the process according to the invention.

Thus, according to the invention, there is a method of manufacture of polyarylamines containing methylene bridges by condensation of primary arylamines and formaldehyde proposed, which is characterized by the initial mixing of the primary arylamines and formaldehyde carries out in the absence of a catalyst for the reaction by these two reactants in introduces certain proportions into a mixing tank, in which also a stream of already mixed and partially converted formaldehyde and primary arylamine from

009884/2254

a first Heaktionsbehälter is introduced, which is from Mixing tank is fed.

Any primary arylamines or any mixture of primary arylamines "an inventive method" can be used, which is particularly applicable to primary arylamines, the single. aromatic nucleus, © athalten, which zäp aminogropp © in the para position. ian substituted.

A preferred arylamine is aniline «

Examples of primary arylamines which can be used in the process according to the invention are aniline, meta-toluidine, ortho-, poluidine, ₉ meta- "" orthomalic isomers of eropylanilime ", butylaniline wad ethaniline, ortho- and aeta-anisidine raad -Phenetidia, 2,5 ^ 5-trimethylaniline, A »laphthylaain ,. 2,4- wad S ^ ö-Dimetöylanilin, 2,4- and 2,6-Dietharlanllin ₉ . 2-Met * yl-6-äthy.X-anllin _t meta-Benzyianllin, ortho- and meta-Chloroanilia.,. meta- and ortho-hitroaniline, meta-bromoaniline ,. 2.,. 4- and 2 _? 6 ~ tolylenediamine, 1,5-naphthylenediamine ", and ortho-" and meta-phenylenediamine "

In the present process, formaldehyde is preferred used in the form of an aqueous solution wagon »Ss can the commercial solutions with an eonsentration of 35 to 40% are used «It should be noted that formaldehyde formers such as a # B · Paraform and trioxane, which generate formaldehyde in situ can be used.

The ratios of arylamine to formaldehyde which can be used in the process according to the invention are as follows as is the case with the known methods. Example games

009884/2254

wise arylamine / formaldehyde molar ratios of about 1.5 / 1 to 12/1 can be used. The invention is especially at arylamine / formaldehyde molar ratios from 1.6 / 1 to 6/1 usable.

The first stage of the present process, i.e. the stage with which the present invention is concerned, is carried out in two containers arranged one behind the other. The first of these containers is a mixing container, in which of the formaldehyde and the primary arylamine are brought into contact, these two materials be measured into the mixing container in predetermined proportions * The mixing container can be measured with an effective Be equipped with a stirrer. This Eührer preferably consists of a turbo mixer or a commercially available high-performance mixer to create a turbulent mixture.

An overflow outlet from the first mixing vessel leads to a first reactor, which has a further connection with the mixing vessel, through which material from the first Reactor? Ium can be returned to the mixing tank. material ■ from the first reactor to the mixing tank by means of a recirculation pump returned, which is set so that the return of the material at a predetermined speed he follows. The formaldehyde and primary arylamine that are metered into the mixing vessel are thus mixed in a stream of already mixed and partially converted formaldehyde and primary arylamine, the is returned from the first reactor to the mixing tank.

The reaction between primary arylamine and formaldehyde takes place to some extent immediately upon mixing; the temperature of the first reactor is adjusted so that a further reaction takes place therein.

009884/2254

The return speed is set according to the Rate of addition of the reactants and accordingly the degree of diminution of the Heaktioa participants, required for mixing in the mixing tank.

The mixing container kaaa at any temp © ratiar "to operate, but it is not ewilnsekfe ₉ DAB is at a temperature of 80 ° 0 üb © raciö? Itt © a Amo There wia? & ~ B®ror Trains t that the temperature twe 20 until Ψ3®® § €> becomes talt @ a. It is pointed out to it <§a ₉ ^^ $ & ® T®m $ ® && ia2 & of the ash container weltgelieaä dme ¹ © !, © Li © f © sp © s? ati! S? d © s © raten reactor »is regulated,} dm the BlielsfiM-iiasigsaatdrial from the first Healrbor ¥ eiiBg © h, © iid the 3! @ Hg © smtOT of the l-Üsch» container «.

The first fieactor is kept at a temperature of 20 "to 80®C _s forsmgsiigis® 35" to.

The mixing container can be heated as needed or, but this is samiadest with smaller ones Attachments, usually alobt aofelg ^ da the ffickführungfliisaigkeit from the first reactor amsaiiiiea with who by 'graying the Heaktioast © ilaelMier © atstand © n Warm the contents of the container to the point you are looking at Keeps temperature «.

The mix of primary »Irylaein partially converted state that is present la is only partially sun glue container guided. The bed flows through a bucket outlet in ®rstea · Heaktor from which the transformation into Mai ^ l®absrüolsan exhibiting Poljarylaain «diirefe lAItsn®g ia § © § © ®υ ^^ ΐ eiats Catalyst ssueiid® is performed. Bi © Böfeaadltag ä®s Abetroms from the first Healt © r with dom. catalyst "and through

Heating to thereby bring the reaction to an end be carried out by the most varied of procedures «. In the method according to the invention, it is not necessary that a special procedure is used

At. an embodiment of the method according to the invention wM the Abstroa from the first reactor in a second Introduced into the reactor, where a strong acid is added to the mixture and the mixture with the added catalyst is heated in order to bring the conversion into polyacylamines instructing ethylene bridges to completion. Xm second reactor another implementation takes place and the reaction becomes expediently brought to an end by the fact that the mixture is allowed to flow into a third reactor, in to which it is heated to bring the reaction to completion. When the reaction is complete, the product becomes isolated in an expedient manner by methods known per se. In this way the sturgeon is neutralized and the organic material is separated from an aqueous layer and washed with water. Excess primary arylamine and traces of water are removed by distillation.

In the above embodiment of the process, the residence time in the various reactors can be according to ! Temperature at which the reactors are to be kept, can be set.

The second reactor in which the Reaktionsteikiehmern acid is added, is ⁰ to 70 C, held in an expedient manner to a temperature of 40 to 100 ° 0, preferably 50th

The abstroa from the second reactor is then heated to to bring the reaction largely to an end, whereby the

009884/2254

heat in an expedient manner at a temperature of 85 to 150 ° C is carried out. The use of high ! Temperatures above 1O5 ° C resulted in water distilled off or that work must be carried out under pressure »

The acid catalyst "in this embodiment of the Process according to the invention is used, an organic acid, a mineral acid or a Lewis acid be. Usually these are acids that have a strong acidity or a strong Lewis acid activity demonstrate.

Examples of acids that can be used are Benzene and homologous sulfonic acids, difluoroacetic acid, Dichloroacetic acid, heptafluorobufferic acid, gxalic acid, Trifluoroacetic acid, trichloroacetic acid, hydrochloric acid, Sulfuric acid, nitric acid, iodic acid, perchloric acid, Fluorosulfonic acid, fyrophosphoric acid, hydrobromic acid, hypophosphorous acid., phosphonic acid, phosphoric acid, Boron trifliorid, Phoaphortrichloricu (Ehioxiylchlorid, Aluminum trichloride and benzoylchloride ^,

The amount of acid used in this embodiment of the process can vary widely, such as in the known processes; Appropriate amounts are 0.01 mol to 1.1 mol, preferably 0.1 mol to 0.5 mol, Acid per mole of primary arylamine.

The final isolation can of course be carried out using continuous neutralization and con continuous separation can be carried out, fio that the process is generally good for a continuous one Operation suitable. Alternatively, the initial stages. d @ s Process to be carried out continuously, wtfb «i das Product for the third stage then for a batch

009884/2254

is collected.

The reactors, especially those in which mixing takes place, are normally equipped with a Agitator aligned

The accompanying drawing is a schematic illustration which explains a type of device that is used for the implementation the embodiment of the invention described above Procedure can be used.

In this drawing, A represents a mixing vessel which is equipped with inlet pipes B and 0 for formaldehyde and amine, respectively. The mixing container also has an overflow pipe D which is connected to a first reactor X. The first reactor X is equipped with an immersed pipe E which is connected to the mixing tank A via pipes F and a circulation pump G. In the drawing, the drill F is inserted into the tube C, which is used to introduce the amine into the mixing container A »In another construction, the tube F can lead directly into the mixing container A. The first reactor X is equipped with an overflow tube J. equipped, which is connected to the second reactor Y, which is also equipped with an inlet pipe K for the introduction of acid and with an overflow pipe L, the latter leading to a third reactor Z, in which the reaction is largely brought to an end »The third Reactor 2 is equipped with an overflow pipe M, which is connected to a continuous neutralizer and separator, which are not shown in the figure. A ₉ X, Y and Z are all equipped with stirring devices.

When carrying out the process, formaldehyde and Amine in the desired proportions through tubes B or C introduced into container A. The mixture ana A

0 0 98 84/225 4

- ■ 10 -

flows naäiX over, and if there is enough material in X has accumulated, the circulation pump G is switched on and material returned from X to mixing tank A, from where it overflows back to X and takes freshly added participants with it «. A certain proportion of the material flows from X into the a wide. Reactor I over, with a certain amount of acid added to the Hohr K will. The reaction mixture from I generally flows through the reactor Z over, and after the end of the reaction in general this reactor the mixture flows to a continuous neutralizer and separator *

The proportion of the material X that is made available in the ratio to, "the portion that overflows complains of the feed speed of amine and formaldelayd and speed the pump 6 from · This koaa © a of course can be adjusted so that any desired throughput rate and refill visibility achieved. will·

The ¥ erweilaeit in each Seafctorea kasa © atsprechend the Durchsatzgeschwiadigkeit be adjusted mad & © τ te§B @ the reactor.

Typical working temperatures - in the d © a matiech dargeetelltea Beliältexm aiat container, 45 to & 5 ° G I © Heaktör X, and 80 M3 105 ⁰ C ia leoktor Z.

In a white! © i * © a MafutoiiHgsf ©! « &<Bw ^ © ^! © gQadoa invention came the ffl, s © teüg ans Äigrlaaia wu W @ s ^: iMil & Q '^ ü ₉ dl © worn first, laairt @ r alifHoBt ₅ with the f © s? 3 © MQä.Qsa ^ © a

0 Q ® i i 4 /

Reason for the amount used as "weak or trace catalysts" in contrast to the strong acids used in the case of the one described above Embodiment can be used in this further embodiment of the process of the invention using such weak catalysts is that heating required to complete the reaction more intense j, either in terms of time or temperature, than those described above stronger acid catalysts is necessary. With this further one. Embodiment of the method according to the invention can The effect of the catalyst can be increased by adding a neutral salt, if necessary. "

Examples of "weak or trace catalysts" are? weak acids, acidic salts, neutral ammonium salts and also strong acids, which come in relatively small Quantities are used.

Specific examples of weak acids are, for example; Acetic acid, acrylic acid, adipic acid, alpha-alanine, barbituric acid, benzoic acid, para-bromobenzoic acid, ortho-bromoplienylacetic acid, para-bromophenylacetic acid, butyric acid, n-butyric acid, meta-chlorobenzoic acid, para-chlorobenzoic acid, para-hydroxybenzoic acid, _9- meta-» -Ohlorophenylacetic acid, meta-chlorophenylacetic acid, para-Ohlorophenylacetic acid, beta-chloropropionic acid, citric acid, diethylmalonic acid, dimethylmalonic acid, di-n-propylmalonic acid, ethylmalonic acid, ethyl-n-propylmalonic acid, gluccolic acid, gluccolic acid, para-fluoro-benzoic acid , Hippuric acid, hydrazoic acid, para-iodophenylacetic acid, maleic acid, isobutyric acid, isovaleric acid, itaconic acid, lactic acid, malic acid, mandelic acid, para-IIethoxyphenyl

009884/2264

Λ2 ~

acetic acid, ethylethylmalonic acid, ethylmalomic acid, a3.pha-Nai> thoic acid, beta-haphthoic acid, nicotinic acid, phenylacetic acid, phenylamonic acid, orthophosphoric acid, pimelic acid, propionic acid, n-propy! malonic acid, Pyruvic acid, salicylic acid, suberic acid, Succinic acid, sulphanilene, tartaric acid, urea- « acid and

A wide variety of polybasic acids can be used as catalysts in the process according to the invention , for example. in the case of a dibasic acid that moiao metals are used, whereas in the case of etaslbased acids neither monometallic dihydsOg @ n-sals @ odes? Bimetallic diOg © n «» salae iswo to be refused konaea «Acid sals © from an®rgaai © eli © a © der organic ©» Sänrea uses nerd © »» It is also Q®miBaiw w & m. & @ ms®n ■ Salts entwined tierdoa., Boispl @ le for sarns? ® Salae ₉ die

Ealiusabifliaoside

Sodium trihydrogen naplithalin -1, 3 _? 5 »7-tetrasulphonic acid, Dinatplum-dihydrogen-naplitlialin-i, 3» 517-tetrasulphonic acid and similar acid salts and in particular those of; other alkali metals, of alkaline earth metals and of _: - ^ ^¥ ammoniaο Other acidic metal salts of the above acids and salts of hydroxy, amino, chloro and alkyl derivatives of the above acids can also be used »

The term neutral ammonium salt includes salts of one; basic and polybasic acids, in which all acidic hydrogen atoms have been replaced by the ammonium radical are, and also, those salts of polybasic acids in which some of the acidic hydrogen atoms are replaced by the ammonium radical and some have been replaced with a metal ion or with metal ions.

Examples of neutral ammonium salts that can be used in the process according to the invention are the neutral ammonium salts of the following mono-, di-, tri- and tetrabasic acids: formic acid, acetic acid, n-butyric acid, isobutyric acid, acrylic acid, methacrylic acid, oleoacetic acid, dichloroacetic acid, trichloroacetic acid , ß-chloropropionic acid, glycolic acid, n-valeric acid, isovaleric acid, mandelic acid, pelargonic acid, hexahydrobenzoic acid, benzoic acid, o-, m- and p ^ chloro ^ benzoic acid, o ~, m- and p ~ bromobenzoic acid, o-, m- and p -Fluorob®nzoic acid, o-, m- and p-methoxybenzoic acid, o-, m- and p ~. Toluic acid, suif anllsäure, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, ß-Ketoglu "tarsäure, dimethylmalonic acid, di-n-propylmalonsäure, -Ithylmalonsäure, diethylmalonic acid, J * _s iuiarsäure maleic acid, tartaric acid, pimelic acid, isocyanuric acid, lemons» acid, Aconitic acid, pyridine ~ 3 ~ carboxylic acid, campaereans _t o-, m- and p-benzenedieartoonic acid, <a <-. Iiad ß-lfaphtlioesäiire,

009884/2254

Phenylacetic acid, ο-, m-. and p-bromophenylacetic acid, o-, m- and p-chlorophenylacetic acid, 2,4-dichlorophenyl acetic acid, phenylamlocic acid, benzenesulphonic acids, methanesulphonic acid, trifluoromethanesulphonic acid, trichloromethanesulphonic acid, naphthalene-iC-sulphonic acid, naphthalene-iC-sulphonic acid ? -sulfonic acid, o-, m- and p-Toluolsulfonaäure, benzene-m-disulfonic acid, SuIfaminsäure, toluenesulfinic acid, o-, m 'and p ~ Hienolsulfonsäure, naphthalene-2 _{3 6-t} disulfoziaäure läaphthaiin-2,7-disulfonic acid, HaphthalizL-1,5-älsulfonic acid, ffaphtnalintrisulfQneäui? E _f laplitltoaliatats-aaiilfojisltire, hydrochloric acid, sulfuric acid, sulphurous saturation acid, phosphoric acid, alfegrlplioepliossliiipea® hydrobromic acid ,. Phosphorous acid, P ^ xopliosphorsaiM? ®, ElnBsaare ,, Pluoboric acid, iriuokieseleäiire, Chloroaiaa (I danic acid, Metapliospliorsaiare ₉
Hexafluophosphoric acid, Th.iopjb, © sp & © rsaii2 '© and

In the case of acids, old a Basiaitit foa 2 or more, the neutral salts can either be the most saline lamoniui salts or partly ammonium sala © and some rope metal salze, as has already been the case

Strong Sämreii, which is used in verlbältaisaiBIg Isleiaea Meagen .be iEonaen, are sJ »€ i © Jeslg © a Säissea, who in this description continues © Tben

It can

Di © "setoaelieB ®ä © T- Bp ^ ewkmtmljBm.t ^ iS'Qm ^^ dl ©

Jm toil Tje ice moGonctse A ^ lmai® / i ¹ @ 5? I3 © l (iQfe57d '== © OiQi ©~ fe, • fc P3 GO ± fm® "uoa lioico

extremely convenient to use them in the form of aqueous solutions e inworking.

In addition to "weak or trace catalyst ¹¹ , a neutral courtship of a metal can be incorporated" This promotes the reaction and in particular accelerates the last stages of the reaction "

Examples of neutral metal salts that are used can, are? Sodium chloride, potassium bromide, sodium fluo- rid, sodium iodate, sodium sulfate and similar potassium, Rubidium and cesium salts, magnesium chloride, bromide -3odide and fluoride, calcium chloride, bromide and sulfate, Sodium odide, lithium iodate and similar salts

The halides of alkali and alkaline earth metals are preferred »

The neutral metal is in "relatively small." Amounts used, for example from 0.1 to 10 wt <, «-%, based on the entire reaction mixture The neutral metal salt is expediently in the Solution together with the weak catalyst aingeax · » works.

The amount of "weak or trace catalyst" used in the method of the invention can vary widely. While it has been suggested that relatively large amounts can be used, small amounts have also been found to be sufficiently effective. When using weak acids, acidic salts, or neutral ammonium salts, it has been found to be appropriate, less than 0 To use 1 mole of such catalysts 4 ^{e Mo1} amine and preferably 0.01 to 0.00001 mole per mole of amine.

-009B84 / 2254

When using the strong acids mentioned earlier in this description, it was found to be expedient to use less than O ₅ OI moles per mole of Amia ""

This execution form of the process according to the invention is carried out by suspending the "weak or trace catalyst" and, if necessary, an atral salt in the effluent of the partially uagissetetea Jjeylaaia / tormalde- = hyd-GemiscJis from the ersfcaa reactor and then the combined mixture, zur Beenügüag eier H © a & tioa © rhitzt-o. The addition dee "weak - or Spisrenkatalysaters ⁵¹ is conveniently characterized amsgef ÜHS" t ₉ that raaa, d © n Abetrom fieskter in a second
or trace catalyst ¹ "« sad
neutral salt in aqueous IMm
Reactor ice leads. The Itüstaroa from dea. swe ± t @ a Eeafetör canoe then-amp Be © Bdlgung eier Eeaktioa © rfiitst ϊΐβΜθ3 & _ο ¥ eaa -. "Weak or Spsreakatalysiatorea" veseweadet tierdea, »as it is the case with this further ©» Aiaafllteaiigsföra des ¥ © rfakrens ₉ then the necessary increase «ag _? ■ the sur completion of the required fieaktion ₉ - vorangsweis® achieved DAB aaa the mixture uaatar DHiek to a temperature above 120 ⁰ C is heated, though optionally also a heating t> ei atmospharischdm pressure can be used "

The Erhltzungstemperatap is nDPsalerweiee liber 120 ⁰ G, and preferably in the range of 150 to 350®0.

The duration of heating required to achieve the Condensation sin "u bring" depends to a certain extent on the catalyst used, on its amount and on the conditions of temperature and pressure, under which the final award is carried out.

When using elevated temperatures in the size

009884/2254

The reaction is in the order of 150 to 200 ⁰ C in a few hours. This time can be reduced to a few minutes if you work at higher temperatures.

The process may be carried out either batchwise or continuously · It is particularly suitable for continuous operation, the components are continuously mixed and then passed through a Erhitzungezone with the desired pressure and the desired temperature and the residence time is set in the t heating zone so that the reaction is terminated at the respective temperature "

Each termination of the reaction can put the product in the for such condensation products can be isolated in the usual way, although of course there is no need for larger ones Add quantities of alkali to neutralize the acid »

So the reaction mixture of a distillation, vorzags ~ wisely under reduced pressure, in order to separate off water, solvent and primary arylamine «, The isolation process can be a filtration or a Include sieving to remove extraneous solids, if so desired.

After the water, solvent and aryl amine have been separated off, the product can be used as such for the phosgenation into a polyisocyanate composition or it can be subjected to distillation to obtain the lower-boiling .. products such as & »Bo Diamino -. diarylmethanes

In a further embodiment dee according to the invention .Procedure can be carried out on the first HeÄtep

; -009884/2284 = ■■ "■ '"' ■ '■ -

Heating in the presence of carbon dioxide in Msthylenbriicken won auÄB.lsendes Polyaiyiaain imgewaadelt _β wherein the carbon dioxide can be addressed as a catalyst in this case. " Possibly jfeaaa. ia connection with the carbon dioxide toeiiaadlisag © ia aomteales EaIs f © pw © a, d © t wer-r .--- den. This execution method Msa @ ate @ d © 5? discontinuously or continuously & ®ίη ΰ _iados d®ü exiting the © rate reactor Jfet @ 2? isil usafeDS ¹ Bssasls ia eiaar carbon dioxide atmosphere eÄitst wi ^ do Ia lall © @ia <lichen Yerfalreas kaaa äam Bb ^ is ^ SmI mnm dos tor through, eiaen S © el £ t © j? MaeLias'efeg © ^! ^ ® ^ w © ^ dea ₀ d © E "a Koiil © adi © 32iäiai3a @ iDpl8S (i nsafe © ^ " MmIi ^ © rnet & t is on a suitable SospQsa ^^? GQlalt®sa aisdo B © i @ ia © a

lutoclaves, elageibra © ^ ΈΜί heated in the sphere w © i? t © aQ Ba © I at a temperature w @ m -1 wise 140 liia Tbia 140 at measure of dei ^{1 of} the product i-iirä

from,

Ι2ΟΪ3.Θ

Loaaea nmä, © J TU γπΦιοΓ Lj τ- r7ln © "feka @ ,,

Such products can be phosgenated without being phosgenated it distills, with mixed polyisocyanate compositions obtained especially in the manufacture foamed polyurethanes, particularly of the hard types, are useful.

Products containing mixed methylene-bridged polyarylamines included and which by the erfindungsgeiaäß® te: e contain fewer substances insoluble in agents and fewer by methyl groups as similar products that are produced by the previously known processes »Biese Pro» products contain an increased proportion of "n 2,4 * -isomer" " Polyisocyanate compositions obtained from the mixed Polyarylamines which have methylene bridges and which have been produced by the process according to the invention have improved storage properties shafts at low temperature.

Because of the absence of acid in the first stages of the In the process, these stages are less corrosive and can be carried out in plants made from materials which do not necessarily have to be acid-resistant «

The invention is further illustrated by the following examples in which all parts and percentages are expressed by weight, unless otherwise stated is.

example 1

The production was carried out in a device similar to that shown in the accompanying drawing. executed.

009884/2254

203A713

Aniline was ironed at a rate of 5? 18 haste / min rapidly mixed with 5,976 parts / min 1 of oily aqueous formaldehyde in the mixing container A, a water-white mobile emulsion having a temperature of 45 to 50 ° 0 being obtained. The mixture ran over into the reactor X. When it had reached the point of overflow from -X to -Y, the circulation pump G was switched on ₉ and the mixture from X became A at a speed tob. 220 parts / min recirculated ο The material overflowing from X to T, treated with the addition of 0.915 ropes / min 36% (w / w) aqueous salic acid at a temperature of 62 to 64 ° G in reactor X, A pale orange emulsion was obtained. The mixture then passed through the oldest reactor, which was kept at 100 °. The size of the third reactor was such that the reaction in it largely came to an end Outflowing material was neutralized with 33% sodium hydroxide solution, continuously separated and mixed »Excess aniline and water were removed under vacuum, whereby a viscous clear red oil was obtained»

The product contained!

2,2'-Diaminodiphenylmethane 1.8 % " ^{: Λ}

2.4 - »7.5%

4.4 - "47.5 %

Triamine 25%

The rest of the material consisted of methylene-bridged polyamines with higher amine functionality »

The product was found at 8% concentration in monochlorobenzene a completely clear solution

009884/2254

Example 2

The procedure of Example 1 was repeated except that the following amounts of material have been grazed:

Aniline 51.8 parts / min

Formaldehyde (16%) 4.30 parts / min Hydrochloric acid (3656) 0.915 parts / min Return speed

speed 100 parts / min

The product contained in addition to the methylene bridges containing polyamines of higher amine functionality the following components:

2.2 ^l ~ diaminodiphenylmethane 2.4%

2,4'- «15 * 5 56

4.4 · - "■ 55.0%

! Priamine 20%

Example 5

The procedure of Example 1 was repeated using the following amounts of material:

Aniline 5.18 parts / min

Formaldehyde (16%) 5.76 ⁿ "Hydrochloric acid (36%) 2.74""Recycle rate 220""

The product contained 57% diaminodiphenylmethane and other higher polyamines containing methylene bridges Amine functionality.

009984/2254

Example 4

The procedure of Example 1 was followed with the following Amounts of material repeated;

Aniline 5.18 parts / min

Formaldehyde (28.1%) 3.25 " ⁿ Hydrochloric acid (56%) 1.59""

Return speed 220 ""

The product contained 51% diaminodiphenylmethane in Mixture with polyamines of higher amine functionality containing methylene bridges.

Example 5

The procedure of Example 1 was followed with the following Amounts of material used.

Aniline 5.18 parts / min.

Formaldehyde (36.2%) 2.33 " ^rt

Hydrochloric acid (36%) 1.59 " ⁿ

Return speed 220 ""

The product contained 52% diaminodiphenylmethanes in addition to polyamines having methylene bridges higher amine functionality

Example 6

The procedure of Example 1 was repeated, wherein the following amounts of material were used:

Aniline 5.18 parts / min

Jormaldehyde (36.2%) x 2.22 ""

Hydrochloric acid 1.59 ""

Return speed 220 ""

009884/2254

- 2? -: ■

The product contained 55 % diaminodiphenylmethanes in a mixture with polyamines having higher amine functionality and having methylene bridges.

Example 7

Aniline was fed at a speed of 5 »Ί8 ropes / min rapidly with 1.81 parts / min of 36% aqueous formaldehyde mixed, which had previously been neutralized to pH 6.5. The water-white mobile emulsion which formed in container A at a temperature of 45 to 50 ° C. ran into the Reactor X over »After you have passed the overflow point from Σ to

Y reached, the circulation pump G was turned on and the mixture of X was at a rate of 220 parts / min returned to A · That from X to

Material overflowing Y was brought together with 0.006 parts of 36.5% hydrochloric acid per 100 parts of 36% formaldehyde solution at a temperature of 60 to 65.degree stainless steel pumped, which was maintained at 260 ⁰ C, "the residence time of the reaction mixture in the heated tubular reactor was about 20 minutes" After leaving the reactor, the mixture was cooled to about 60 ° 0, and for the purpose of isolation of the product discharged through a continuous pressure reduction "valve · The mixture was combined with aqueous sodium bicarbonate to neutralize the acidic catalyst. After the aqueous phase had been separated off and washed with water, the excess aniline was removed under reduced pressure. The product, a dark brown viscous oil, contained 47 % diaminodiphenylmethane, the remainder essentially consisting of polyarylamines of higher functionality with methylene bridges »

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203471

The procedure of Example 7 was repeated, wherein the following amounts of material were used:

Aniline 5 * 18 parts / min

Formaldehyde (36%) 1.81 ""

previously to pH 6.4

neutralized

Return speed

That from X to. Y overflow was rated 2.0. Parts of sodium chloride per 100 parts of 36% formaldehyde solution and 0.014 · * parts 100% formic acid per 100 Tei le 36% formaldehyde solution at a temperature of 60 to 65 ° brought together 0th The effluent from the other reactor was treated in a manner similar to Example 7 »

The product, a brown, viscous oil, contained 60 % diaminodiphenylmethane, the heat of the product essentially consisting of polyarylamines with higher / jain functionality containing methylene bridges. "

Example ?

Aniline was rapidly mixed with 1.81 parts of 35 »2% aqueous formaldehyde in mixing container A at a rate of 5» ^ 8 parts / min, a water-white, mobile emulsion being obtained at a temperature of 45 to 50 °. The mixture overflowed into reactor X , and after it had reached the overflow point from X 'to Y, the circulation pump G was switched on and the mixture from X was returned to A at a rate of 220 parts / min. The material overflowing from X to Y was treated at a temperature of 65 ° C. in reactor Y by adding 0.2 parts of a 10% strength aqueous ammonium sulfate solution per 100 parts of 36% strength aqueous formaldehyde. The mixture exiting reactor Y was collected and treated in a batchwise manner by

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it is heated to 190 ° C for 6 hours at a pressure of 14 at was to bring the reaction to an end »

After the water had been separated off, the mixture was filtered to remove catalyst residues and then distilled under reduced pressure to remove excess aniline. The product contained 64.3 % diaminodiphenylmethanes and polyamines of higher amine functionality having methylene bridges.

BeiagielJlO

The procedure of Example 9 was repeated except that the the following amounts of material were used:

Aniline 5.18 parts / min

Formaldehyde (35%) 1.81 " ^M para-toluenesulfonic acid 0.014 parts / 100 parts

35.2% formaldehyde

Sodium chloride 2.0 parts / 100 parts

35.2% formaldehyde

Return flow

speed 220 parts / min

After neutralization and isolation, the product contained 66.5 % diaminodiphenylmethanes and polyamines of higher amine functionality containing methylene bridges.

Example 11

The procedure of Example 9 was repeated except that the the following amounts of material were used:

Aniline 5t18 parts / min

Formaldehyde (35.2 SO) 1.81 "" Trichlorooesige acid 0.05 "per 100 parts

35.2% aqueous form aldehyde

Return velocity

speed 220 parts / min

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After neutralization and isolation, the product contained 62.0% diaminodiphenylmethanes and polyamines containing methylene bridges higher amine functionality.

Example 12

The procedure of Example 9 was repeated using the following amounts of material · g

Aniline 5.18 parts / min

Formaldehyde (35.2%) 1.81 "" Recycle Rate 220 ■ ». »

The material overflowing from X to Y was treated by adding 2.0 parts of sodium chloride per 100 parts of 35.2% strength aqueous formaldehyde and saturated with a stream of carbon dioxide. The mixture leaving the reactor was collected and Y st treated batchwise by heating at 190 ⁰ C under a carbon dioxide atmosphere and pressurized during 6 to bring to an end the reaction. After the salt, water and excess aniline had been separated off, the product contained 59.8% diaminodiphenylmethanes and polyamines of higher amine functionality having methylene bridges.

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Claims (1)

- 27 - Claims . Process for the preparation of polyarylamines having methylene bridges by condensation of primary arylamines and formaldehyde, characterized in that there is the initial mixing of the primary arylamines and formaldehyde carries out in the absence of a catalyst for the reaction by these two reactants in introduces certain proportions into a mixing tank, in which also a stream of already mixed and partially converted formaldehyde and primary arylamine is introduced from a first reaction vessel, which is removed from the mixing vessel is fed " 2β method according to claim 1, characterized in that the primary arylamine contains a single aromatic nucleus which is unsubstituted in the para position to the amino group » Jo method according to claim 2, characterized in that the arylamine is aniline » 4ο Method according to one of the preceding claims, characterized in that the primary arylamine and the formaldehyde can be used in a molar ratio of 1.6 / 1 to 6/1 .- * 5. The method according to any one of the preceding claims, characterized in that the mixing container at a temperature operated from 20 to 75 ° 0. 6. The method according to any one of the preceding claims, characterized in that the first reactor is operated at a temperature of 35 to 70 ⁰ C. 7. The method according to any one of the preceding claims, characterized in that an effluent from the first reactor is fed to a second reactor that a catalyst consisting of a strong acid is added to the effluent 009.884 / 2254 and that the mixture with the added catalyst is heated in order to bring the conversion into polyarylamines having methylene bridges to an end. 8 * A method according to claim 7 »characterized in that the existing of a strong acid catalyst at a temperature won is added 50 to 7O ⁰ C." Process according to Claim 7 or 8, characterized in that the reaction is brought to an end at a temperature of 85 to 150 ⁰ . 10. The method according to claim 7% 8 or 9 »characterized · ^ · characterized in that the amount of catalyst used is 0.01 to 1.1 moles of acid per mole of primary aline. 11. The method according to any one of claims 1 to 6, characterized characterized in that the catalyst consists of a weak acid, an acid salt, a neutral ammonium salt or a small amount of strong acid is added to the effluent from the first reactor and the device aiah then to complete the conversion into methylene bridges containing polyarylamines is heated » 12. The method according to claim 11, characterized in that in addition to the catalyst, a neutral metal salt is incorporated. 13 «The method according to claim 12, characterized in that the neutral salt is a halide of an alkali or Alkaline earth metals is " 009884/2254 Method according to one of Claims 11 "bia 13» thereby characterized in that the catalyst is a weak acid ^; .. © in SaIa odor a neutral Ammoniuiaealz did, soft In ^ - "' an amount of 0.01 to 0.00001 moles per mole of eel who uses de: i, or that the catalyst is a strong acid, the. in an amount less than 0.01 mole per mole of amiri. yer ~ - we / jdet will * "■ 15 'method rcjaoh ainem of claims 11 to 14-, thereby characterized in that the reaction is carried out at a temperature of 1 * 0 to 550 ° O suend ©, 16 »Process according to one of claims 1 to 6, characterized in that the atom in the first reactor is heated to a temperature of 120 to 400 * 0 under pressure in the presence of carbon dioxide as a catalyst in order to bring about the conversion into polyarylamines having methylene bridges * 009884/2264 Blank page