DE2018549A1 - Process for the preparation of diaminodiarylmethanes - Google Patents

Description

MTENTANWJUTt DR.-INQ, H. FINCKE β μΟνοηιν β, J η ^ DO 1070 DIPL.-INQ, H. BOHR Meitar * 31 DIPL-INa. 8.STAEQER 20185Λ9 ·

Cap 22237 - Dr.K / H. ΙΟΙ OASS D.21832

ΒΒ8 OHREIB UHG for patent application by

Firs «IMPERIAL CHEMICAL IKDUBIErBS LIKITEI), London S.V. 1 / BKGLAIfD,

concerning ι

"Process for the production of IfcLaainodiarvl- ■ ethanes"

PEIORITiT: April 17, 1969 - GROSSBHITAIiNIEII.

The invention relates to the manufacture of JDiaaino » diarylaethanaü and anti-oren related methylene bridges on the value of polyarylaaJn ^ n higher functional quality through coruiencation of aroaatiaohen alaines with formaldehyde.

The manufacture of ethylane bridges eluting polynrjTaail ntsn by Kon-lennatijn τοη arylamlneii old foraldehyde in the presence of 8äur3, known as ? >> B * hydrochloric acid. Here

009848 / $ 194

condensates obtained * the diamines, and polyamines feissiine hülierer functionality include _e For example, when aniline is used as the primary Arylamiii, then contain the methyl formed enbrüclse "comprising 011 Polyarylaiaine
2,4'- and 4 »4 ¹ ™ 3) iaiiainodiplienyliHethan der Pormel

CH ₂ -M y ™

and

-TV-OH

Bra ₉

Iriarnin, 2,4-B; L £] "(p-aiaiiiobGHSjrl) -> aniline der

ÜH,

BRA,

OH,

EfII,

ORIGINAL

0098Α6 / 1945

and related. Connects a lioixorer isaiiafimlctioBalitiit «If ■ öäe Arylajsi «is aniline, then have .εί.β flies allgciaeine

formula ^!

™ 2

■ -%

where η 1 or mine? is"

Ss mir de miuiseui * goft '^ dea ,, that α is' Horstellmig τοα bridges on ¥ - <2: Lseüö.öi ⁵ Poi ^ a ^ yliisiinsn in successreioliei? V / else la Abweseiilieit OCE usual: ßaiir <m Katal.ysatorea listed tiQrden & ann "and that- one-neutraleni Hetallsals in • iron isugeeetster Satire one aiisKciicliende liaüaljse fler aation gives the Korroalaneprobleiae, the wii. SMisren ver" linked öiiiä, imö äie Hotvfenäigliioit, after testing the probe Batloii a 'Heutralißation: Hit AlMiIi Toysmielimen, werclea öoait avoided «

Thus the invention is a method geaiäfi CDCR Heretel- = lung of Methylonbrüoken atifweiaeKden Pol ^ arjXaminen before gesolilGgen, welßlissj dadurcli executed n irö _ΰ äaß.aian a pri-Haeres arylamine with Forüialdeliyd elevated box Seaiperatur in Gögcmv! / Art a neutral iielißllsalses- and in the absence siaer augeeetsrf; eii Sliure condensed ;,

Ea can ^ edeu-priraäre Axylamiu od © 3? Geiuisrjh from primary ijeira -orfindimgngenjäßu "V0 ?? i'aiirGn vervjöKclei become _f

O O 9 8 A 6/1 9 A 5

weXelies see, beaonders can be applied to primary arylsjaine * which contain a single aromatic nucleus, which in the par & -position sur'Aminogruppe unsubstituted 1st · am before augt.es Arylßiain is aniline *

Examples of primary arylamines * the methods are used M> xmeft _r are aniline, ortho = 3! Oluiäini parä-Soluäin, meta · =? ortho = and paralthylsniline and similar isolators of propylaniline, butyl aniline iraö OctylsjiiliBg -ostho «, säete, υηά para =» anisifline -Ehsnetidln, 2,3,5-lEifflethylenilin, a-laphthylamine, 2,4- and 2,6 -XyUaImIiSJaInJ, 2,4 ° and 2 _a 6-diethyleniline _> 2-kethyl-6-iithylsniline, meta = B © nsylaniliHj ortho- and. caiiliiij, para «= ·» meta = irafl ortho «nitroanilln ₉ 2} 4« "and 2,6» 2olylenäiaaiin »!, S ^ aphthylenediiaHin and ortho

Dar SOnaaldehyd is in iswecksaäßiger way erfindyngs helmet proper procedures in Poesj © iner aqueous Lösiang used The commercial LSswngen sait a Eonaentration of dangerous 35 to 40 $ MJsmen used _c Se is pointed _s that even materials »DI® in · situ! Farsi & ldöhyd bil = "The ₉ Vfie a" Β * Paraforxnaldehyde and Srioxaiij, was used.

Ss 2cann jeoes neutral metals as foeiai ei'indiinggeiacestver driving can be used.

Examples fite neutral metal salts * which can be verweiidet 3 are Itetriusichlorid, latriiuabroiaid _t Hatri \ _p -iiafluorid sodium iodate, HatuJLuiBsulfatr Hatriumbenzolsulfonat Liehe tsnd LithluiE · = ·, Kaiitäsa "rubidium _p K &lzlma" ·, Bariiim-, beryllium, _MEgnesiiam-? Alnminiuin- »Manganese, % ± nk ~ and

ORIGINAL

009846/1945

Halides of alkali and alkaline earth metals are the preferred neutral strings.

The neutral "SaIs is used in comparatively small amounts" such as 0.1 to 10% by weight, based on the total weight of amine and formaldehyde, but amounts outside this range can also be used.

An essential feature of the process according to the invention is that neither organic nor inorganic acids of the condensation agent have to be added.

It is preferred that the condensation is carried out at a pH below 10, in particular below 8.0, where a small amount of alkali can be used if necessary » Bring the pH to the preferred range. This Alkali is added to the formaldehyde solution in a water-like manner. ~

The ingredients of arylamine x formaldehyde that can be used in the invention are used of the kind "as they are known in the art" For example, lrylaaln / Poriialdthyd-KolTerhMltnieee from about 1> 5/1 to 13/1 can be used. Me invention is particularly brewable with molar proportions of arylaein / iormaldehyde of 1.6 / 1 to 6/1,

The initial dimensions of Tarfahran are carried out as αa-j arylmin and the formulas to be used are uul ύ & η i * »lioh» abbt. Bas »autrala Salat kaim, Bweckmllo-In fora a% iäiielgen W) * uug, oinam the Beak» ^ r in front of the MUnhau or gugen Hndo there? ίIiachi ₄ Jf! "" tit Murden. ^{Wöf}} i} the mix "viril da" ι nah viM '& ügewfriiie on alna fooperatur from aislir ale ¹¹

HO to 35O ° ö,

0 098AS / 194 5

Bb is preferred to take a jerk? atiäo spherical
use during the Erhitauiigsatiife,

Me duration ü & v Erhlisaung bit out? The extent of the condensation depends to a certain extent on the "Eiatalyaator" used, his? Quantity and then i'smperatar = »and pressure conditions under which the reaction is carried out wjl.rd, from»

Let use of iron parts in the
Only from 150 to 200 ⁰ G does the reaction run in Weuigan

to the end * Dießs 2eit kmm especially by working
at higher iSeaaperatiix-sn vsrringsi ^ t

The ancestor kaim aBtwsdej? Step by step or continuously added before · It is particularly suitable for a fconti "! luiorliulie ilrarbeitswsiss, vobai dis components koatlnuier" I..3U11 ßniiilsciit νωύ damn ilurel "oine Erhitaungassonö with the tfttv .njoh ?? abii2 'mid daai gswünechben Druok hindairchgerdliri; Vövdon and v / oboi the Terweilseib in tier Brliitsiingeaon bo «ing ©? I>-l; slit wii'dj <1εα5 diö Heakbion at the respective
to Earlö la «« ft *

U in «Toriich bung i'iix · the .Dwi'cliführirng des örfinciungsgeaisame Voirfahrsna in kontimiiörliaUiij. ¹ way is shown in the attached iSüichmmg tiar

ι ti doi * ^ oichnung akillen on: ι

1 -mil 2 Jalntribfcd fiiv asylsinine and IP

öin-3 pump,

'■> DvuoltWBfisjai? want

7 i

3 ..w \ |; cit ')! Mln inen mil Mi ?; ninoi ».öliilBoiilange M in oineia KUhlbe-

009846/1945

10 vertoumleru Jas. B? Oäi2ki; flows through; a continuiep 'Allowed an exit for 12 after 13'

the product on the isolation level «-

In the case of continuous operation, Arjlasiin, aldehyde imü, neuteaXes Salsi are continuously mixed in container 3 under vigorous Eühreia and then over it? the pressure 4 is pumped under a bridge of, for example, 70 atm through a stainless tubular steel reactor 9, which is kept at the desired temperature, with the residence time in the reactor determining the flow rate according to the figure. used temperature. is set- * When leaving the reactor, the mixture in 11 is approx. 60 ⁰ C cooled and then dttrch the continuous pressure reduction B "valve 12" drained. The end product fcaam can either "" be isolated "" neatly or at random "

An organic iSsungsaiit'feels can -Will run arfshren .da © erfiaöimgsi.geiaäßc · "^ ^ in the presence of which au" ßätslich or Ex'aats _f Depending on requirements ₀ The presence of organic IiöBungssit = einee rope of water Torliegt te3.n _{however, β} is not a preventive feature of the invention

The product can be isolated in the titeliciien else titeliciien for such condensations. WoIiI ₅ aüderß than Lall © a traversing ens _f eng at SalsB = · acid -Uses vfirö, there is no need ₉ an alkali aur ITeutralisation ö © b 'BauroS Atal ^ ^ crystallizer admit _o Bas. Heaktionageisch the distillation can be subjected to those who «■■■ the _s ^ nd swar preferred -under reduced * .Brück, -am water." Iittsungfisiitrtel imd. prisiäsee ArFleaiB su eliminate. Mo Xso ~ 1stion may include a filtration, to solid substances promoters sy üien beseitigen5 if necessary.

laugh at the removal of Hasser ₉ solvent and arylaiaine

0 Q 9 8 A 6/19 A 5

know fi & s. Product as such for 'oils BxossgeniK'img can be used in a polyisocyaaatisaffisieiisetung or Gg can also be subjected to distillation ¹ ' from sneezing boiling products 'such as sB' M. & irinoäiarjlmetii & üe _ff hersußteile _e

The erfindungggesaäße method is suitable for the production of DiaMnodiaryimethanenc Bas is aleoj © e meowing verliältniemäßig liolie Arylaiain / Porinaläehjil ^ erliältnisse Torwendet werdaiij "nope, the product can weräen distilled _s uk a purified Biaminodia ^ ylmerbiiaTü h © 2, * s? Uiätellen _not like SoB «. a BiamiiodiphenjlSBötliSHi & n & © ieli for clio XJiwaKcllirag in DiisocyaoatocliphenyliietME.! suitable, the wleü.ei? i \ m tihs Si © Her et ellung von Polsrarethaaelastoffieres. etc verwenööt advertising can ü®n. Alternatively, through the lf © EVi © nöung of the lower aryljaiaiiv ^ oiaBialäohyd-Ve the process for the production το », mixed on bridges up © iß © nö @ n Polyarylssiiiiea ¥ © mfeniet χίΘΓοο? Ι ₀ .the KUtaätfilieh au Marinen _Various proportions of aJriaBiße and Folyarylamine of higher functionality can be used © Such products can otoe Deetill & tion phosgeniört U3B mixed PolyisooyanatsusaMBensetBiingon her to share »the bösondßrß in the production of foamed poloI urethanes are particularly useful from polyurethane.

The invention is further illustrated by following examples ül & _p in <äeti © above all © ropes MiÄ Srossentangaben eind expressed in weight _p aofern nothing anöeree indicated *

. “AD ORfGINAL

009846/19 45

2018 5Λ9

9 «■■; ... ■

Bsi a 15 1 © 1 1

Sn 774 Seilon one. well gerttlirtea aniline would be vareenä tra · = 20 Mmrfcen 162., 2 files 37 jusiger, watery i'ossjalüeliyd

' The reaction proceeded exotaepä, and aio iüesaperatur deo Sesjisclia ßieg'wäln? © next output from 20 to 50 ⁰ C *

Zum-Gemis-oh vmröen then 7.5 ropes HatrinBaohlorifl train © eetas * ii and Sas Gesjiscli became -after another 15 Miirateia don KÜiiren in a red- free S ^r baliliatai3okla.v © ia

iiröe- then, lanter Eüfcrea ia eiB © sa ¥ s5? scb.los © en «m ^ 6. 'For hours at 194 to 200 ° 0

deia AblteUlilsB became the. Autoclave emptied _g und.¥as-a@'jf country something aniline äinrcti Bostillation at 15 saia Hg entferntj wobai were hitst to a lunentemperator of 84 ¹

EüOkstand isrurcle um filtered , 'on ®iiQX% iin ± BQh® Salss remove ₉ iraä absoMießfmd was © öer Heat ä & B gen' aniline by distillation in a 33ü

Bas -fe'oiJutetj fjin lclareB teauoea viscous Oi ₃ . us? gave

x'ialö beatEmä i "« essential & about Metürflen - '■' hifd «-xan miXwoise> K! eii roiyarylD ^ ioem 'on des? Baoie tob Ainilin, η <· .Ά- ψμάϊ> .hauptaächlloh ana ^f friamtn,' and «nfehlelt smaller --- M '.-. n.-. ^Ä Jii? ο1; /; χϊίΐ1η0 K? 3h9i? -93i« funct ionall t * -31j.

0 ()! JB ', 8 / I94B

In the case of Paoegöiaier question, the product resulted in one γ ©! Αθ

OTigj you 31 ₉ 6 $ Isöogfanat nai 0, -49 COilor contained «,

B © i game 2

Zw 372 α, 'οϋβα efcies gut gd »Ü2i3? I; en iAllins% / m.'ilen waiarenö tin = -

7 Jllmitea 81.1 ropes of a 37 aqueous figs ütoxrnalda J3ng give © © n> CISR Tox-lier 2.3 iPeils an east _S 4- plgen SIMG srngesetst wordea were "manufacturing pH d © 8

Mq B'oKsaMaiiydsä'agafe © ran sxotiaerii \ mü eile · 'Ses> i @ s © eiaischöis rose wüirenü öer Stigebe you S2

Dan G-iJiäieejb. mirdsti "tlami 3-75 3? © il © latritsia ymri Ü33 © 53m:!. bcI3. littrow aaoli id.Bi> m 'KOita« röB ± n ein i? oatfreiun Stalila ^ atokla ^^ m übe ^ ftihrt »Ss

to 190 to 200 ^C) il o ^ i ^ at.

Üf & oh aera AMdllilsm wtufie der /-.Btoklss^ emptied, iaM ■ a'teis Aiiillti wvt £ üt-m üvtfQ'k Ds? -Jt: illatioii at 15 sin! R ■ {V / i.tBsesstrBiilp'iinii} © ·) l: ssr.i) ^ .- i; 1gt _? yofe © i to atif sima ■ iitDiipsr ^ -feHi? Tone 82 ⁰ Ci gii ^ m ^ sn m'.iifl © e of the Büe &filte.isi-1; » vw ö-: is ü-noi / ^ a-itih Γ! 1 üt

.Llation; i.n il

c? yiskoosö oil, orgab 'bsi

■ '4,.' ii _? 4th

. ;; i ifai "» - ^v ii. * J. ^! -i 5j.},. ihu.i »l:? ni Vi, i -)« nl; lj.rt.! i u \ aa.a Methyl one- " ^a ""Ο 0 9 8 A 6/1 9 4 5 ^ ₀ . _0RtG1NAL

together with kl & ± n & Ten Mengst Allerer fis-ßktioii®ller amine *.

Product gave bsi PIioogenier-iiBg a role si2 © aimüeiiB © t ^: äg _? the 31- »25 * ^c ß
aiorbaren Olilor delilor »

B ice ρ. i © 1 3

53β5? Tferstell tob Example 2 was wieöeriioXt, with jeöocli 81 y. 1 ropes 37 solid water? Por-Eiaidehyä Te «/ eB pH. by dropwise addition of a 0.4

g has been set to 6 ₉ 3

-JSsss product ^ a tCriMisaiines Tisfeoaes oil _s en-üiiielt

The older remainder consisted of polyaryl ajüinen ^ liatiptßllolilioh ^ isaia .wnä containing methjleabrUeken. Polyamino, liölaersr punk = "- 'tionality".

The production of external material produced a polyocyanate which was 3.0 _P 9.1 5§ iso "cyanate" and 0 ₅ 6> hydrolyzable olilor

B ei a ρ i e 1

The Yerf3iacli von Böißpiel 2 vrarde wiedö2? 3ioXt, whereby however 81,1 ~ afeilö 37 S ^ lgea? ■ aqueous % mm & 3, ü®} x $ & it is used ₉

00984B / 19AE

its pH Ütecb. gugsibe τοη 2 _g '2 rope of a 4 * 0 $ ige: a wäßr gea Fs-feHdtsiSltjaror / illösiuig air £ 1O ₅ -O eliagosed wcEilen was «

The product, a brown viscous © ® oil, contained a? Analysis: "

7 »5 $ 2 _f 2 ⁱ

23 »5 # 2,4'-DieintnoaiplieayliBe1ihaa ₅
36 $ 4 »4 ^l

x ¹ remainder feßstasö from MethTrleafexMieikös raifweiseiaänen '

hanpteäolilicli Sfrieaain © susarisaen ssil t ioality *

At HxoEigeniertsBg © ine neuseteuiag "oils 29" 94 $ leocysaat imfl 1.2 f> chlorine

Example 5

f Ti * tfXfSTTU Tt rfPV illTl ■ ΓΉΓ ^ ΐ "« i μ ^ "■ '■■ Ά *' T % ι r ίΙΆΧ *** 'B -Λ ^ ί" Γgr ttVΤ &.Τ-' ti «Jt ΰ £ Λ;

Of? Yevsacb. ψοη ! © iepiel 2 was repeated _f where 81 ρ 1! ropes a @ & 5? word iäigen aqueous Forisialdeliyds veswendot mirden _t whose pH dnreh Stigabe τοώ 5.1! Sight © iiter ö "4 ^ r vrfiBrigen liatriiaiailydrosydlösiing aiii 9 * set 1 em

lfao Pz ^j odt2kt _s a brown ice _f Yifl ^ oöes oil ₉ contained according to an analysis «

7 $ 2, -2 ⁹
25 i> 2 ₉ 4 "

The H € iö5; bsstanrl © .υπ Hethylenbrüoken auftfeieenden aajinen »mainly ffiriaiain and. l? oljtim ± ne Mih3. * c3r litasst ·

009846/1945 t * ₀ pR, _{G (NAi}

13 ~ '.

The product resulted in Phosgenie ^ mBg ©: hse raenaetsung ,. the -30.65 $ iBOöjanat xnnü (VFSi $ ■ rsss contained chlorine *

B e is ρ i e 1

The Yereucii of Example 2 * rai? Cls wisd © riiolt _? ^r being 81.1 ropes. 37 ^ igör aqueous SOrsalde ^ jii Terweadet whose pH dtiroh. 'Adding you 2, & ropes a 0 _? 4 #igQB gen liatri-urahyclroxyalSsnug was set to 8-, 1 Bingct

The "product" contained a blue-black viscose oil Analysis:

24 JS 2 _s 4 ⁹ -] 0iaiainoäip3! Ie'nylsnethan, 58 ^ 4j4 ⁹ = 'Dia! Ninodiphenylnietlian »

The best beabaad ans methylene bridges aiHlnen, Mainly Xrisiain u "M Polyaxßine higher funk

functionality «/

example

Tersuoh from Boiopiel 2 wurflo repeated, but v / ob © i 81.1! Peile 37 # watery formaldehyde was used, its pH by adding 1.5 rope weight a 0.4 # igön Jj? Jsung of-HatriumihyaroKyö was set to 4 »25-.

Product contained

23 fi 2,4'-Diajuinodiphei3yIaiethan ₉ 38 ^ 4,4 '"J3iö} iiiiiodiphenyl?} Iethane _e

009846/1945

ty -r ιι-ιψ-ητχ

The experiment of Example 2 was wisd@riie3.t ₅ using 81.1 ropes of 37% aqueous formaldehyde of 3.75. labriui ach chloride

The PK'odüJct had the following analysis

7 $ 2,2'-Ι) 1βΒΐ1ηοα1ρ1ιβη3ΓΐΐΒβί1ιβη,
25 ^ 2 _t 4 ⁿ -DiaaiiQodiplien3rlmetl2ian,

36 # 4 ₇ 4 ⁿ

The ß © at consisted of methyl teÜGksn aiaiVeisendeB amines, liauptsäclilicli friasain miä polyeiaine functionalitjKi: · ¹

] L JLiL JLJL L · Λ ---— _ %

The experiment of Example 2 repeated vrarde been however 81.1 ropes 37 $ aqueous formaldehyde Terweisdet ^ furden whose pH was adjusted to 6.3 "mi with 0.4 part fiatriumclilorid instead of 3" hone 75 irarden used *

The product resulted in the following © Analyzes

4 $ » 2,2 '«]> iaminodiphenylfflethane,
21 i » 2,4 '« Biaminodiplienylmethane,
45 5 »4 p 4"

The Resfe consisted hub Metlijlenbrüclcen aufveiaenden polyaryl "amines j heuptsäohlioh. Teiaiiin and Polyaminet higher functionality.

HAD ORiQfNAL 009846 / 1945-

^; ": - - 15 V ■. ■■■. ■■ ^:

Example 10

.Bor experiment τοη Example 2 ifarde tfiederüolts where _e 1ecioch 81.1. _{Ropes of 37% aqueous formaldehyde were used, the pH of which had been adjusted to 5 S} 2 by the addition of 2.1 ropes of a 0.4% aqueous Hstr: U! IB3nyäroxjälsung

The product resulted in the following

6 $> 2 _Ρ 2 ⁹
23 $ 2 _f 4 ^s
40 ^ 4.4 *

The older hefiite consisted of lietliyl © backing axifescent and polyallyl naiiptsäciiliüfe SrlamiB saiesssaeia uit Polyssainen

Htm product resulted in "at 13hGsgen ± e £% mg a ßammKsetgiiiig iait a ßelialt of 31,4 ^ isoeyamat vinä 0,59 ί ^ 33ydroi2rsieKlie2.'es chlorine *

& ^R f ^ G Sueli of Example 2. vmräe tilederftolt wherein _F 81 s 1 ropes 37 ^ aqueous ForaaMeliyd Tex & vmi et been "fow pH eiagestellt 6 ^ 5 was been \% nä further wherein 3tl5 ieile I2anganoiilfat-teti'al2ydrst instead of 3.75 parts

-were used".

The product resulted in the following © analysis:

20 % g ^
4-5 / ^ ^ »^ {■ '

Her Heat beutend- aias Methyleateüofeeri ripping open

009846/1945

amines mainly triamine and polyamines with higher functionalities

B ο i £ 3 ρ i e 1 12

Was the experiment of Example 2 was repeated "However vfobei 81 _r 1 parts oiner 37 ^ aqueous & LORM ldehydlösung ver" · w were et end your * pH at 6 * set 4, and wherein 3.75 'Sell® Ifognesiumsulfat ^ heptahydrate instead of 3ι75! Rush sodium chloride were used _e

The product gave the following analysis:

18 ^& J> 2,4 "^ MarainodiphenylKiG than, 41 ρ 3 $> 4s 4 '-Diaminod ipheiiy! Methane _o

The remainder consisted essentially of polyarylamines with higher functionality _{or the like containing Ilethylene bridges}

The experiment of Example 2 was repeated _r but with 81 j, 1 ropes of a 37 J aqueous Forraaldehyds ₉ were used whose pH was adjusted to 7.1 "and wherein 3 _f 75 parts potassium bromide instead of 3 * 75 parts of sodium chloride were used,"

The product gave the following analysis:

4 ^C A 2 ₉ 2 ° "DiaminodiphenyliDethan, 23 # 2,4 '-Diatuinod iphenylraethan" 41 ρ5 * /> 4 »4'-DiaminodiphenyliDethan _o

The remainder was imported mainly of Hethyletibrücken aufwei send polyarylene! Amines higher functionality ₀

^ '\ J 009846/1946 »AD

17 «■;

B e i β p.i e 1 14

The experiment of Example 2 was repeated, but with 81p 1 part 37 # aqueous iOraialdahyd would be used, whose pH had been adjusted to 6. ^ 5 and-where 3> 75 parts Bariureal chloride anateile of sodium chloride were used *

The product resulted in the following analysis:

3 ° h 2.2 ^B -Diaininodlphenyliaethan, 21 ^e ß> 2.4 ⁱ ~ BiamAnodiphenylmethan, $ 4j4'-Ilia, Biinodiphen5 ^r lmethano

The reed of the material was made up of methylene bridges having polyaryleraineii of higher amino functionalities

Example 15

The experiment of Example 2 was repeated ₉ except that 81.1 parts of 37 irerwendet 5 »aqueous Porinaldehyd» whose pH was readjusted to 6/15 © and were dissolved in the 3 3 75 ropes potassium chloride v / orden. No sodium chloride was added after the formaldehyde reaction had proceeded

J) Extraordinary product gave the following analysis:

6 <4 2.2 ⁸ -Majü.inocliphenylniethan9 28 j «2 ₅ 4 ³ -Diarainodipheiiylraebhan, 5ö '^ 4» 4'-Maiaiiiocliphenyliiiöthano

The Rent bootond in weaentllchen auö IiathylonbrUcken aufwei i ^J ol / arylaniinen higher / Iminfunktionalltäto

The product was a crude polyisocyanate at Phoaiienieriing

0Q9Ö46 / T945

- ίο -.

with a (life of 92, 1 $ (calculated with MoieJailargöwIeht τοπ 2f? 0 as Diiaooyanatodlplienylinethan) »tie contained a hydrolyzable chlorine content of 0.4 ^ ₀

Example iü

The experiment of Example 15 was carried out by Lederholt _ρ , but 302.5 ropes of ortho-chloroaniline were used instead of 372 ropes of aniline and after transferring the reaction mixture into the autoclave this 6 "hours to 220 ⁰ C anateile of 6 hours , was heated to 19O ⁰ C ₀

The process was determined by gas / liquid chromatography analyzed »Me analysis revealed;

2 ρ 0 ic 2.2 »-diamino» 3.3 * -d iohlord iphenylmethane,

55 S *> 4 y 4 '"» Diamlno-3,3 "« d iolilorä lphenylaiethan »

Dor host beejtand: 1ns v / esentliohen. on? Having ethylene bridges Polyarylamines of higher Aain functionality on the Base of ortho- ^ chloranllinο

ti

The experiment of Example 15 was repeated, but 4SS ₉ 6 parts of ortho-lOluidin instead of 372 parts of aniline were used, and wherein after the transfer of the start loan lleaktionogeaiischea into the autoclave this ö hours at 220 ⁰ O and 'niolrfr 6 hours at 19O ⁰ C heated

The product was determined by Gan / Plttssisslcöits-Ohrroiiiatographie analyzedο The analysis resulted in ι

tAO ORIGINAL

- ■: .. ■ -.... 009846/1945

- 19 -. '■ - ■:' ■

Dei? Heat the product consisted Ih wg seat union of methylene * bridge comprising polyaryl & mines higher on the Basia of _orthc-e Soluiäin

B_e l_ap i ^ el 18

The experiment of Example 1 was repeated, however, was _p being performed after transfer of the initial aniline / PoriBaldehyd · = Reaktionsgemiacha in the autoclave the Erhitsungsstufe 6 hours at 16O ° C instead of 6 hours at 190 G ^0.

The product resulted in the following analysis:

1.5 ° / ° S ^ 15 ^C A 2 _f 4 ^l
43 ^c p 4f4 '

The remainder of the product consisted essentially of methylene bridges with polyacrylates of higher AI functionalities .

Be is P i e 1

The preliminary test of Example 1 was repeated, however, 162.2 parts of 37 aqueous ponsal hydrate and 4 cells Sodium chloride instead of 81.1 parts of formaldehyde and 3 »75 parts of sodium chloride were used o

The analysis of the product showed

009846/1948

2j 5 i » 2.2 * ~ diaminodiphenylmethane _s 17 ⁰ Z * ' 2.4 ^s -diaainodiphenylmethane, 28 id 4,4 ·' -Sianinodiphenylmethan _β

The rest of the product consisted of the weeentlielien atis methylene = bridging polyarylaraines of higher amine functionality.

PAIDBNT CLAIMS:

009846/1 9A5

Claims (1)

PA 3? E If 3? A N B P R Ü G H E s A process for preparing MethylenbrüGken having polyarylene! Amines by condensation of a primary Arylaniins with formaldehyde at elevated temperature ₉ characterized in that it is carried out in the presence of a neutral metal salt and in the absence of added acid. Process according to claim 1 _9, characterized in that the primary arylamine contains an aromatic nucleus which is unsub · = etituieri in the para «position on the amino group; is, 3. The method according to claim 2, characterized in that aniline is used as the primary arylajaine, 4 »A method according to, any one of the preceding claims, characterized in that an alkali metal or alkaline earth metal used as a neutral Metallsais a halide v / ird _e 5ο Method according to one of the preceding claims, characterized in that " ^r ^ ß the neutral metal ace in a volume of 0.1 to 10 Gow _o - $, based on the total""weight on arylamines and formaldehyde, is used ο 6 ο method NaOH öinora the vorhorgeheiid en claims, üuduirah gel -. «I / jnsäeichnot, - Dafi the .KonrtüHiöation.-boei oinem pH below Hj 009846/1945 7o method according to claim 6, characterized in that the pH of _{p p} is less than 8 0 » 8a Method according to one of the preceding claims, characterized in that the ratio of arylamine to
Formaldehyde 1.6: 1 to 6: 1 is _e 9 ο method according to one of the preceding claims _β characterized in that Sas Kondansationsgemisck on
a temperature of 140 to 35O ° C will be «, ¹ IΟ «, method according to one of the preceding claims, characterized in that the Erbitzimgsstufe in einia
higher than atmospheric pressure » Ho method according to one of the preceding claims, characterized in that © s in a continuous manner
is performed. 009846/1945