DE1568844A1 - Process for the production of organic polyisocyanates - Google Patents

Description

PATE NTAN WALTE

DR.-ING. H. FiNCKE DIPL.-ING. H. BOHR DIPL ..! NG. S. STAEGER

Telephone: 22 49 41

8 MUNICH 5, Müllerstrasse 31

-3. June '66

Folder 20 754

Case D.18419 / D.19072

description

for patent also

from Imperial Chemical Industries Limited

London ₉ Sun U. 1 / England

concerning

"Process for the production of organic polyisocyanates"

PRIORITIES i 3 * June 1965 and 18 February 196δ - Great Britain -

The invention relates to the division of organic isocyanates, in particular organic polyisocyanates.

009829/1670

The production of organic mono * and polyisocyanates by means of phosgeneic alloys and polyamine hydrochlorides has been described. The present invention relates to the phosgenation of Auinhydroohlorldsn in an improved physical form, which is particularly suitable for τ * - see conversion of phosgene.

Aminhydrochloride, especially polyamine hydrochloride, dl By using known methods, they are all in the form of coarse particles, and they require one prolonged treatment with phosgene, generally with siemlioh high temperatures, sur conversion into isocyanates. Sine Prolonged treatment of this type is not only detrimental to the production speed standpoint, but leads also see unwanted lifting reactions which cause a loss of yield.

Amine and polyamine hydrochlorides, which are close to the known Methods are established, are not only available in rough physical form and are therefore difficult to generate, but are also often obtained under such precipitation conditions that they result in products which do not • Contain tOohiometrisohe amount of hydrogen chloride and have a proportion of free amino groups · During

009829/1670 BAOORiG ₁ NAt

the subsequent treatment of this rough H with Phoegen at elevated levels. Temperatures can free the ice Amino groups in unexpected lifting reactions, such as formation Clay ureas »with simultaneous loss of yield» participate ·

For these reasons, the production of isocyanates, in particular polyisocyanates, by phosgenation of amine hydrocarbons is not carried out to any extent, although it might seem economically attractive at first glance.

In the production of * -'-- ■ ■ -viecHen isocyanates, eloh their brewing proved extremely difficult and true because of the slow rate at which aliphatic amines or their salts can be phosgenated.

The reaction of an amine and hydrogen chloride to form The hydrochloride is a highly exothermic reaction. In order to obtain a hydrochloride of satisfactory physical form, excessively high temperatures are required be avoided.

009829/1670

It has now been found that amine hydrocarbons are satisfactory and reproducible in the fine state of the physical Subdivision, which is extremely suitable for phosgenation, by treating a thin film of a solution of the Amines can be generated in an inert solvent with hydrogen chloride. The essence of the present invention consists in the fact that the hydrochloride is produced » by brewing a solution of the amine in an inert solvent, this solution being in the form of a thin film with a constantly changing surface, in contact with hydrogen chloride. The heat of reaction of the amine and the hydrogen chloride is conveniently removed by the thin Film of the solution is cooled. If a very dilute solution of the amine is used, refrigeration may not be required. When the amine hydrochloride catfish is generated, it is in the form of a slurry or suspension of very fine particles dee hydrochloride with high Surface obtained in the inert solvent. This slurry or suspension is particularly suitable for the Conversion into the isoyanate, and through their use, the disadvantages which accompany the previous hydrochlorides are avoided or considerably reduced

009829/1670

BATH ORIGINAL

-s- .1588844

The application dee erfizidungsgeajäßen Vsrfaiiröns' mi Bias preparing isocyanates insbeeo & wider Fo * are unexpectedly high yields and short footnote th.

In the case of isocyanates which contain at least one aliphatic sofc bonded isoyanate group ^ 1st dia "at the hiosgenation stage duroh the inventive method reaction rate particularly surprising in H on the known difficulty and slowness of the phosgenation of the corresponding amines and their" salsse at? Eh known methods "the application of erfini3ungagemi * 8§" Experienced allows generation eoleM? isooyanav *? iiwöli Bin. continuous Verfaiiren "what ei oh so far NTCH% a" Lf pÄ "tikabel has proven"

The inventive method for the production of organic Isocyanates by phosgenation of an amine hydrochloride therefore consists in «forming an amine hydrochloride» by a solution of this amine in an inert solvent, which is in the form of a thin film with sioh constantly changing Surface is present, treated with hydrogen chloride and the amine hydrochloride thus formed reacted with phosgene

009829/1670

The method according to the invention is extremely valuable to me Production of organic polyisocyanates from polyamines via the hydrochlorides of the same and, in particular, only production of organic polyisocyanates from polyamines, dl containing at least one aliphatically bonded amino group

The inert solvent used in the process of the invention can be any of those solvents such as however, they were proposed for use in phosgene generation reactions. The term "inert" means inert among the reaction conditions so that the solvent is obviously inert to hydrogen chloride, phosgene and the amine the reaction conditions used be au0.

In advance, the inert solvent used in the process according to the invention is an oil-free solvent, in which hydrogen chloride is present at low temperatures, β.B. Room temperature, is somewhat soluble; Suitable solvents include ester solvents such as n-butyl acetate, n-hexyl acetate, Dimethyl carbonate and dietary carbonate, hydrocarbons, such as Toluene and xylene, and halogenated hydrocarbons, such as Mono-, di- and trichlorobenzenes, chlorotoluenes, carbon tetrachloride and triochlorofluoromethane.

009829/1670

1568044

ir ^ tU-Vi the \ ö ^ means »Gi ti» jfaU'1,0 can in v * <n if * tu ^ *. . ^v > solution ve?> t - :. ade is the ^ i;

ν -

The thin © i'jln cior Amlnü.iiciunüi άατ old Ciil is , feami by verBohiedeue Ii den, and elfraeo kaim fts? Would you like some peas with a changing surface on different veins? hev

be

So can ras;. «In a thin file -3er cooled surface to flow or In βίηβιυ V:», «,. ,, ·. , ,,,. ·. ■■ ■

native kmns der düiin * *:,! & «to be braced around f talen OberfXöohe.»

ü ^r - "r a fe-

The surface of the thin oil becomes duroh the mere flow of the film is constantly changing, but the surface can be further disturbed and re-sucked by moving or Turbulent! Generated in the atmosphere Above this surface.

inner surface of a cylinder tube has just one Proven suitable surface on which the thin film of the

009829/1670

Amine solution can be formed. Since «pipe can be vertical» horizontally or at an * angle. The initiation can be inserted into the cylindrical tube at a point and placed on the inner wall of the tubes «and the The usual thin Vlin can be kept flowing along the entire length of the inner walls of the tubes by moving or turbulence within the tube. So can an eloh • without rotating shaft, which is located in the tube near the bottom centrally on geriohtet let, open leaves, Arne or Wlooher, welohe the surface of the thin film is constantly like and while she turns the leaves around the central shaft, Arne or Vieoher can, however, be set to do so • ie actually the surface of the thin liquid film Do not touch, but only stubbornly stubbornly pass the surface by walking close to the surface. Alternatively, IMn Let the leaves touch the wall of the tube, and break up the particles of the hydrochloride as they are formed will improve. The centrifugal force exerted by such a rapidly rotating arrangement throws uutonatieoh all Particles of the solution or slurry exiting the thin powder are directed towards the pipe wall.

The cylindrical tube can be provided with a jacket which contains a coolant in order to cool the thin film and to allow the dissipation of the heat of reaction of the amine and hydrogen chloride »

009829/1670

_BATH ORIGINAL

« U « ⁵ S: » i . ·; Ϊ ΐΐ λ /

For the Küi'sxhr '/ ΰΐι üiilr ^ viM the SuspOE.aiöa des Ky,:,; ", C; 1-desj entrance § i> i.Lnki: ie:; - / "^' .-- 'AusleS vorgeea ^ aiii. . "The S-br ^ eatwednr Ie Gisi
solution take place 5

Das ^ y lind smell β Zohz gzivstgt o-ler the Affiiiilösiuag isit the help of the C ^ ijwerfe-uf that Bohr is in a horizontal I-Hge "is in a hurry and dtn: Beecl ^ clr turns around the dllr-aan ^ i ': .ji d.an Πο

Uae pipe needs g /

that can be approaching Seilüm haoan υ>]. · 1 ΐ weleeru

Some kind of device ^ dia s-iQh zw? l ^ vohfUhmmg de ^ formation dea Polyarainhydrochlor! ds., the ^ nig ^ t 5, ta is generally called "DUnneohichtverdampfer or I> Uar.ßoMciiiiT? .- yworkers is called ^ any of the large number of different dinschloht vaporizers or "processors" which are bio-oil or are accessible to industry, the amine hydrochloride can be used in the preparation of the oil, whereby the "initial requirement is that _?" while the dilime sole

ORIGINAL BATHROOM 009829/1 670

-ίο- 1588844

the amine solution along the processor or evaporator moved and into a fine slurry of amine hydrochloride is transferred, eie the hydrogen chloride gas, daa the Reet de Volume of the thin film evaporator or processor fills, presents a continuously changing surface. A cooling medium, usually water, can be passed through the jacket of the evaporator β

It is assumed that the improvement achieved by the method according to the invention is partly due to the low degree of curl in such a thin-film evaporator let, the formation consistency of the Hydrochloride if the reaction components through the thin film evaporator flow, the delay between the formation of the hydrochloride and the phosgenation of the hydrochloride on Minimum brings.

The attached drawing shows a device that can be calibrated has proven suitable for carrying out the process according to the invention on a small scale.

91g. 1 of the newspaper 1st a. axial section of a device the sloh to carry out the formation of the amine hydrochloride suitable.

009829/1870 bad original

In FIG. 1, the device consists of a reaction vessel containing a cylindrical tube A, hollowed out at both ends, which is provided with a four-blade stirrer B at a height of about 1 mm from the inner surface of the tube A, which is located on A shaft C is located centrally in the cylindrical tube and in which the stopper D and TQB is held at the end bearing. The cylindrical tube A is surrounded by an annular dumbbell Ϊ, which has an inlet Q and an outlet B for cooling liquid and a thermometer K but Measurement of the temperature of the coolant in the ring-shaped jacket. The indissoluble tube is provided with an inlet L for hydrogen chloride, an inlet M for the amine solution and an outlet H for the slurry or suspension of the hydrochloride .:. & The outlet H is provided with a thermometer 0 in order to determine the temperature of the suspension of amine hydrochloride leaving the reaction vessel.

flg. 2 is a perspective view of a four-leaf Stirrer which is suitable for use in the device according to FIG.

If the device shown in FIG. 1 is manufactured from Amine hydrochloride is used, becomes hydrogen chloride gas

BAD ORJGlNAl

009829/1670

Introduced at the L inlet and amine solution at the M inlet. Coolant is applied to the 'annular cooler as required. The stirrer B is rotated at about 1000 rpm, and the effect of Rührere together with the pressure dee at M entering Flüssigkeitestromee causes the amine solution, the tube A along in the form of flows of a thin Flüeeigkeltefilmes on the inner surface "The reaction of Aain and hydrogen chloride is carried out to form the Amlnhydrochloride while the liquid flows along pipe, and the FIi eB geschwindlgkeit and the like "is set to DAFL up to the time at which the slurry from the Auelafi N iierausfließt, the G & nze AmI _n I _n the hydrochloride transferred 1st · causes the rapid rotation of the Rührero that the thin film has an exposed to the hydrogen chloride gas has surface "which varies continuously.

Figo 5 is an axial section of another type of thin film device, which is suitable for the formation of Amlnhydrochlorldee in the process according to the invention.

In FIG. 5, the device consists of a cylindrical tube A, which is closed at both ends and is disposed in a vertical position and provided with a drehbaren- centrally aligned shaft G _f that is held in the stuffing box D ". The shaft C carries a coil spring «! Q that through

0 0 9 8 2 9/1670 'BAD ORIGINAL

the arms are held P of the cylindrical tube A in extreme vicinity of the inner surface provided "The cylindrical tube A with 1st Sinlässen L and M are hydrogen chloride and Aminlöaung and an outlet for ΪΓ amine hydrochloride. A circular jacket F _s which is provided with an inlet G and outlet H for cooling liquid and thermometers for measuring the temperature of the liquid surrounds the pipe A ₀

Using the device of Figure 5, the shaft and the springs attached to it are rotated at high speed and a thin layer of amine solution flows down the inner surface of the cylindrical tube and the surface of the thin layer is exposed by the passage of the coil springs through the thin layer continuously broken and moved. The shaft and the rotatable springs are expediently rotated at speeds in the order of magnitude of 500 rpm to 1500 rpm

The apparatus shown in Figure 5 may include _a two helical springs, which are mounted on arms on the rotatable shaft, or it may be mounted as two springs so more? that they act in close proximity to the inner surface of the pipe ₀

Other types of thin film evaporation! or processors are also used in the production of AminUydrochlor! da im Ancestors ο

BATH ORIGINAL

009829/1670

Thin-film evaporator, which are suitable SiOH door operation in the production of the NaOH Aminhydroohlorids erfindungegeaäfien method are already commercially erhältIioh, and the following are typical for solohe devices: the vertical ⁿ Sambay "-and the vertical and horizontal" Sako "evaporator, manufactured by Samesreuther-MUller-Schuss, Butzbaoh / Germany, the horizontal "Kontrofilm" evaporator manufactured by Artisan Industries Inc., Waltham / USA, and the vertical "Luwa" evaporator manufactured by Luwa A.Gr., Zurich / Switzerland.

The amine hydrochloride may be at any temperature within the range of from ⁰ C to 10O ⁰ C are prepared, but is preferably carried out at temperatures of from 1O ⁰ O to 65 ⁰ C if desired, the operation can be carried out at a pressure above atmospheric pressure to increase the solubility of hydrogen chloride to increase in the solvent. In order to stay within the above preferred temperature limits, the thin film is preferably cooled.

The amine hydrochloride slurry or suspension, whichever flows from the thin film device contains amine hydrochloride, in which virtually all amine groups are converted to hydrochloride, and can then by any of the

009829/1670 ^BAD o ^RIGINAL

d · :: Ό: it > » ... ö or αο.λ ;; Γ; '·' ,. e Art af »i"? ■ ο Γ-: '

λ * re

tion level: -> el «" t.,, .:

Ftg, 3 I »·., ^ Lλ V'lieöe ^ kontlnuieriiöhe .. · ;. E «; r ts« lluii ^ vci; after erri: i, ^a:: z3 ^ ege2 äaeii?

In the in Fig ₃ ; The type of procedure shown flows in the DUnnachichtreaictor I produced? Amine hydrocarbyl to a usual I-ilhrre ·. ":"? τ II- -? 9τ ίίΐηerhalb dee Berelclia von 75 1) 1 ρ 190 ⁰ O operated and; .n 'plead Tncögen a directed

0 9 8 2 9/1670

The work in the higher areas of the temperature ranges is not necessary, but is often mentioned if the process is used for the production of organic polyoxyanates, the aliphatically bound Ieooyanatgrup ~ group contained the overflow goes to a further reactor III of similar construction to II, operating the beiepieleweiee in the range of 12O ⁰ C to 200 ⁰ C {during Here division of aromatic isocyanates temperatures up to 16O ⁰ C is normally sufficient, but it may be advantageous in Pail polyisocyanates with aliphatically bound isocyanate Manoh-BaI, in the higher Part of this' temperature range to work.

Depending on the desired rate and the size of the reactor, If you want to use, further reactors can be added to the series in order to allow sufficient residence time for one provide safe termination of the response eu. Further phosgene can be added to the rear reactors as required However, sufficient phosgene often remains in the solvent released from the earlier stages to allow for more encores in the to make later reactors unnecessary.

Fig. 4 (Figo 3 the provisional speolfioatlon of the British Patent application 7276/66) is a flow sheet of a typical

009829/1670

_BA0

1 ξ ii \ ü *>: 4

Verfahr.- ^ u * j,; · - ·.; ■■ · .: ■ ^ \., -, ν, :: - ^^ ellim ^ roa i-jf ^ Äs gt slAimg a;.; wel ^ jrsr; .j V

DünneoidcirfcTeräaispfer ait üh- i.ioä ^ a Kerlonalsr; wi «ä * r finished Pkvc & eiixv-rv ... ■ _. .ν: .. ^ - ,: ο.ί ·; e ^^ a ;, -. iie IiI ¹ S ^,

ι & Α vvi, n

BATH ORIGINAL

To organic isocyanates, which according to the invention Methods that can be made include aromatic, aliphatic, cycloaliphatic, and araliphatic isocyanates. These include, for example, phenyl isocyanates, tolyl isocyanates, chlorophenyl isocyanates, lolylendilsooyanatt, in particular mixtures of the 2,4- and 2,6-isomers, diphenylethane-4,4'-diisooyanate and mixtures thereof, the polyisocyanates contain higher functionality, 3-methyldiphenyl * ethane-4,4 * ~ diisocyanate, m- and p-phenylene diisocyanate, diphenyl 4,4'-diisocyanate, haphthalin-1,5-diisocyanate, chlorophenylene-2,4-diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Haxaoethylene diisocyanate, heptamethylene dileooyanate, Octamethylene diisooyanate, nonanethylene diisooyanate, lecafflethylene " diieocyanate,. ^ odee & methylendlieocyanat, m-xylylenedieooyanat, p-Xylylenöiiisocy & nat, Cyclohexau-1,4-DiissCoyanat »Oyolohexane-1,3-Diieocyajiat- Methylcyclohexan-2,4- und 2,6-Diisooyanat,

6oeyan & tofflethyl) ~ oyclQhexan, Dlieooyanato-2-oIaocyanatoätäylphenylisocyanat, οι _{-Ieooyanatobsn.iyli B ^ ,; yai). & U e} Methylisooyanat, Ethylisocyanat, Propy .1.1 secy ana t _r laopropylisocyanat; Butylieocyanatobsn.iyli B ^ ,; yai). & U e Methylisooyanat, Ethylisocyanat, Propy. n'oxylisooyauat, heptylisooyanat, octyl isocyanate, Nony.l: LBoc./iy »at · Decyliaocyanafc, dodecylisooyariat, Cyclohexylüh lorhejcy L i uocy um fc _c

BATH ORIGINAL

8 o "ban ~ · ■■■ * ■■: * lead * .- '' - ^: -""U". in the-.

bar on the Heretellui'i * :,. '■■; :: orgszii achen Poljia wciil aromatic old auo': i alipr * atidcher nature, whereby it results in unexpectedly high yields and short rides «

Which achieved the method according to the invention geeoh Speed let beoondpre surprisingly in terms of the polyisocyanates, the aliphatiach bound leooyanai: - groups contain »in view of the known difficulties and the slowness of the phosgenation of aliphatic amines by the known methods. The present Ae Invention is also particularly advantageous »since it has the durσ» allow implementation of a continuous process for the production of aliphatic isocyanates, which was previously not possible in general.

The following examples illustrate the invention without restricting it to SU. All parts and percentages are based on weight, unless otherwise stated _c

009829/1670

■ Belepiel 1

A # 8 cent (w "/ wt.) Solution in o-tolylenediamine yon Diohlorbeneol at 65 ⁰ C in a thin-film reactor of the type shown in Fig. 1 at a rate γοη 8.0 / min inserted g. At the same time, dry hydrogen chloride is introduced into the reaction vessel at a rate of 1.6 g / min. Dae diamine is a Gemieoh you isomer which contains about 80 $ 2,4- »19,6 ^ 2,6- and 0,4jfc 3» 4-tolylenedlamine.

Water at 10 ⁰ C is passed through the ringförmigen'Mantel of Dünnsohlohtreaktors in the circuit to remove the exothermic heat of reaction. The reactor used in the above amounts has a length τοη 30 om and a radius of 5 om. The temperature of the reactor effluent is 24 ^° C.

From the thin film reactor, the suspension of PoIyaminhydroohlorid flows into a stirred reactor II (Pig. 3) üblioher type, which is kept at 9O ⁰ C and in a welohen FhOBgenetrom is continuously introduced at a rate of 2.0 g / min. The working volume of the "wide reaction vessel II" is about 1500 com.

009829/1670 _BAD ORIGINAL

From the Köaktop Il Hi ^ Zt -. ·.,. ■. L ■ '-. ■ -..- ^? On ltdyleMiisciy; and Tolyler * l? lsearbaiayi - l'J ^fc ^ i '- i3 ä.rltten. Reactoy III (Fig. ^{Of the 1} UBi 12O ⁰ C content «» vira ^.:> E, a Product which overflows from the reactor runs into an Aafaahae vessel (Fig. 3} * ee © material vird. Degassed, iir; in Lörang ver ^ Xi.sbenen O w & eööTstoff UR-C remained canöö Awageu to entiBZ'i ^ solution emit t el v / is removed vaxä da »Proaiüct in üfelienas ¹ white distilled * vas a ^ * 5 '& ge · Aus ^ eut ^ ail cyan eats results »

IÄ Ϊ «

e «} Example ViiU'd in« u ^ -Hv - '^^ lici ^

(2.0 g / rain) in dea Büiiiiec'ils ^ iiraaii ^ oj? ^ in ^ sf ^ üirta Sin further 3troci ναι · * KiDSgOM (v? 5 ^ / ";.: f; ':.) v.'ri ■. j ·. iia.9 s ^ ei.te 5k: ali · «

where; ί ** ί1οο * 'i * ahtc' üoiy IwV ·; ^ iJi '"i'v'i-rla: .-; irfi _f d> iii atwa

BATH ORIGINAL

009829/1670

186 * 844

After distillation a yield of 89% of a total amount of tolylene-2,4- and 2,6-diisooyanate.

Example 4

A 10 ^ ige (w / w) solution of technical "4" 4 * -Diajd.nodipheny! Methane in monochlorobenzene at 50 ⁰ O is in a vertical thin-film reactor of the kind shown in Pig-5 bit at a rate of 8.0 g / min introduced. At the same time, dry hydrogen chloride is introduced into the reactor at a rate of 0.9 g / min. Dlaninodiphenyl methane is produced by condensing aniline with foraaldehyde . Ke contains mainly 4,4'-diaminodiphenylethane together with some 2,4'-diaminodiphenylmethane and polyasin of higher punctuality,

Water at 5O ⁰ C is circulated through the annular Han tel d &s> vertical Dünnechi chtreaktors to control inter alia the exo autothermal & Raaktionevfäri e. The thin JPiIm is made continuous by a set of four stainless steel spiral springs; Wiped steel, which are mounted on cross-pieces at a point of boredom, as shown in Fig. 5, which are wired with a wire . The Heaktionsgei'äfi has a length of about 25.4 cm and one. Diameter of 4.6 cm and a wiping surface of about 365 ca ", the temperature of the reactor effluent is 50 to 55 ⁰ G,

9/1670 BAD ORIGINAL

from the DuxmeGhicirtreaktionsgelag flit: Lι «ν *> ν.ίϊρβη:? ία; ί d @ e Hydrochloric, .. η -5« τ * stirred reactor IX (Fig »V v> vi usual construction ,,« f be. ·. r '-' C is held wv .; ■ - ^ "'" hsr continuously with an O * ^ -: cohesion - »/ on. g />' Ui s? ^x !, - PtwOpenr-itrom we introduce» Das Arbeitavoluineii the Healrtor's Xl is about 1500 com,

Aue the reactor II flows daa product zwa Heaktor III (iMgrJ), which is maintained at 125 ⁰ O, The aue this reactor overflowing product fliefit in a AufnahmegeföQ (Fig, 3) * The Mate · "rial" the eioh In this QetäQ gathers , treated ana at 2 whites in the following way!

The material is heated under normal pressure and half of the monochlorobenzene it contains is removed. Then, the pressure is gradually decreased and the temperature is raised to 16O ⁰ C, at which value it is maintained for 3 hours. The curable solvent is distilled off while heating, and after cooling, the product is obtained as a viscous, dark brown liquid. Its main component is 4.4 ^l -DiphenylmethandiisooyEnat _! However, it contains isomeric diisocyanates and polyisocyanates of higher functionality together with other impurities

009829/1670

The analysis ze J ^ t ₁ that the Iaocyanatgehalt dea product 91? 6 / i (au3gedrtickt ale diphenylmethane diisocyanate, corresponds yuierbaren with a hydro] chlorine content of 0 ₉ 18ji. It is suitable calibration au0erordontlj.cn for producing rigid Sohäume using conventional working method ^ Z ₀ B ₀ from hydroxylated polyethers, catalyst and blowing agents, such as halogenated hydrocarbons.

example 5 A

A 5 ige (wt / wt) solution of hexamethylenediamine in trichlorobenzene at about 25 ⁰ C is at a rate of 8.0 ml / min in a thin-layer reactor, which in Pig. 1, introduced with a length of 30 cm and a radius of 5 om. Simultaneously dry hydrogen chloride is introduced _f min to the reactor at a rate of 1.0 g / 10 ⁰ C and WaBBer at will by the annular shell dee reactor out in Kreidlauf to the heat of the exothermic reaction dissipate.

From the thin film reactor, the suspension of polyamines hydrothlorid strömο in a stirred reactor of conventional Bauartj, which is maintained at Ι4θ ° ΰ _f and in which a phosgene continuously at a rate 1 / min we initiated g de. When 1OCC ml of reaction product formed as an intermediate

0 0 9829/1670

BATH ORIGINAL

155S8U

in this reactor $ ■ * ■ $ & u \ 2 * rl t '■;"<!, vf-yaeii dia / iufy ^

The feaperaöur dee inter & eülä- ^ n. BeaktionsprcdukiJds gut within 1 stool ^{increased to * co u} O and with diesel * Se ^ pcratuTi still under Au.frech'teriia.VvUii ^ des glelalif- ^ i? H ^ sgeii «Strom, held for 2 hours-rrij am ϋ, ιάβ this?. · time has the total suspended Feet ^ Osijrmz gelüsiij imd ss Tsr - = remains a lclarea ^ oraxige-lTfum ^ s iToüukt * Bie yield «· λ Hexametnylendiisöiiyaiiat i« dio-3em Eoiiprod ^ in oeerda-aii; clur ^ ä complete decitillaticn s ^! i, s? .2, i Foakstä'rlö.rf ,; amounts to. 99 ^^

The following
k & iüite Verfaiirtii !. sur E ^ rattLlv ,. 15B miss 5C represent awai vereö-äii and 3D a ^tf carb

t: .c - .; ißS8iten ui

above shows the advantages of the ^ r

5Bj> 0 uj.iü "; 3) ^ ejg

h the

, ΐ example

B β I a

pooiil'jrid will Jisrg-äscsllt? IMeEi a solution of 116 g Hexaiaet-h ^ ?. e # di £ inii ^r .. ii ⁵ - w ^ thani ?! langeam under Hüiiren au eüier Löauii, «. from. 233 3 ti-gukensm CJil-crivaeßS substance in Metiia'iiol added v / :: ^s i _e Ti-If precipitated hydrochloride vira filtered off and; ö uuici. ^ t urid goaiahlcn, uad

009829/1870

BATH ORIGINAL

- 26 - "68844

90 g are suspended in 510 g of trichlorobenzene in a flask equipped with a stirrer, condenser and gas inlet tube. The solution is saturated at 100 ⁰ C with phosgene, "and then the temperature is increased and at 185 to 19O ⁰ C maintained at this value while a phosgene at a rate of about 0.4 g / min is durohgeleitet. After 6 hours the phosgene flow is stopped and the mixture is degassed with a flow of dry nitrogen.

Example 5C

49 g of hexamethylenediamine and 650 g of trichlorobenzene are placed in a flask equipped with a stirrer, condenser and gas inlet tube. Dry hydrogen chloride gas is at 20 ⁰ C 30 bie initiated, until the formation of the hydrochlorides terminated. The hydrogen chloride is then replaced with egg nen slow phosgene stream and the temperature was raised as quickly as possible to 19O ⁰ C. This requires about 1 1/2

Hours, as the mixture is very charged at medium temperatures

o • fclnöa and becomes difficult to stir »When the temperature is 180 C reached »the phosgene rate is about 1/2 g each Minute increased and the mixture finally with the same

0S82S / 1670 _BAD ORIGINAL

Phoogenßtroin bul 19O ⁰ C ^ dmH-aüf lii β ι; μ - :: - i ^ · 3 rd, Ήί »te Phosgenl ^: - u-) g;> ^ ⁿ it jji der ) Ut?, a bp'.vir / ' ! ·"' / 2 i * t: «: D and the yield Qi,! Lexiiriethylondäi nnc *;>; ·: ι: -

Example 51)

66 g of hexamethylenediamine and 459 g of o-dichlorobenzene are placed in a flask which is equipped with a stirrer, cooler and gas inlet. and heated to 80 to 88 ⁰ C * Dry carbon dioxide is eingeleitt-t is "terminated until the Garbonierung" DIEA requires about 1 3/4 hours * Dae mixture is then cooled within 1 hour at O ⁰ O "and 90 g of phosgene is 1 initiated hour, while the temperature is kept below 5 ⁰ C ,, DaH mixture is bit 2 1/2 hours while passing eineo langoamen Pho at 150 1Ö0 ° C. and then 11 hours with a Phoe genzugabegeschwindig & elt of 0 _f 25 g / min geriüirte reflux end dieeer time most of the Feeteub * Atana disappeared and the Außbeute ic \ hexamethyl "ndiiac oyanat is in Rohprodulrt *

B ο ie ρ i β 1

A 7f5 ^ ige (Gev ^ / Gey ») Löaunf: an D ^ '^ eajietliylenäituniii in o« J) ichlo.rbeii2o! L at about 25 ° C \ dr <\ ^ i: a ^ oochvdndi ^ r'j of 10 l ^v i: ~ \ 5 rV / zdi-- in tizjn VAhmzvY · .: '.: iv; "?; ^: ^J ^ r« "- ^? : ^s ir

BATH ORIGINAL

009829/1670

Example 1 introduced the type used., Simultaneously is

Dried · Ohlorv / aseerstoff into the reactor at a rate of 1 _f lg / min introduced, and water at 1O ⁰ C is through the annular jacket of the Reaktlonegefäßes "circulates around the heat of the exothermic reaction dissipate ₀

Wirdo from the DünnecMchtreaktor the suspension of polyamine "hydrochlcrid flows into a stirred reactor of conventional design, which is maintained at 140 ⁰ C and in which a Phoegenstrom continuously introduced at a rate of 0 _f 8 g / min Wenr · to 1500 ml of the intermediate reaction product in this reactor have geBammelt, the supply of diamine and hydrogen chloride is intra = is then semi increased 1 1/2 hours at 170 ⁰ C and at this temperature, still maintaining the same Phosgenstrome, 1 3 / to the thin-film reactor aborted the temperature of the intermediate reaction product "held for 4 hours at the end of this period, the gam.e suspended solids are dissolved _t and there remains behind a clear, yellow product, the yield of Dodeoamethylendiisoevanat in this crude, determined by complete distillation of the residues is 99

BeL β ρ 1 ο 3. 7

3inc "', /, / iev iige (Gev _f; solution of la-xylylenediamine in trichloro-" be.' · Ι ":. b" i etva 25 ⁰ C v.ird with a C-esohv / indißkei t? from 9 ^ 0 ml /

U 0 9 8 2 9/1 670

_BA D ORIGINAL

kysToohlorid ir. ilruiti H .-: I / ■ εhai i-

BATH ORIGINAL

»30» 156B844

When prepared by a conventional procedure, the yield is only $ 88 after 4 hours phosgenation in the heat at 19O ⁰ Cc

Example 8

Sine! Fig (Gewo / wt.) Solution of p-xylylenediamine in o-dichloro benzene at about 25 · ⁰ C is introduced at a rate of 10.0 ml / min in a thin-film reactor of the type used in Example 1. "Simultaneously dry hydrogen chloride is introduced into the reactor at a rate of 1.1 g / min, and water at 10 ^° C. is passed through the circular jacket of the reactor in order to remove the heat of the exothermic reaction.

From the thin-film reactor, the suspension of polyamine hydrochloride flows into a stirred reactor of conventional design, which at i. ^r > 0 ° 0 is maintained, and in which a reverse current conti · = nuXerlLoh with normal speed of 0 _? 8 g / min introduced v / ird,?) When 1000 atl of the intermediate reaction product Li, üi, ^ iuii liH7 \ k'sov are melted »the feeds of Diüt ηί> -. 'I-'iii urul ^; hl.orva; 3 3 material passed to the thin tube reactor i ~>. · ::: · ■:. ·: ij. - ': i: "ua> ^ ι at \ -ν de. ü int8rnied: l £ ireii H. ,, nk tion y products η .-' ■: ■ ι ^; ■■ '. ·. ... : ^Λ ·. '. R.' ■ .. ';u'.ui'i-j on ^: 70'"(- i.,. O ;; i; uriti, still under

vj ,: 3> 3 ' ^u--: .i> η o,:. i di3 «er

BATH ORIGINAL

w 0 3 S 7 ^3/1 6 7 0

© rap »ι * a ν * '..-. : ■■: α al-, '' 'ν, "ä Dn ά ο

: "■ '■ * ψ β ^ m> ΐ ■.

3 e 1 e ρ ά, e _i 1

Solution yr:; ⁱ r, affleti ^ _; "i cniii amrn

ahiorbeneol at about 25 ⁰ C becomes Jr; a

At the same time, dry GhlorwaBeeretoff is introduced into <ien Beektor nt * at a rate of 1.0 g / sin, which is similar to that shown in Fig. 1. Vr · ser>"i about 10 ⁰ C is passed through the ring-shaped dumbbell of the reactor g in order to dissipate the heat of the exothermic reaction"

The Suepenelon dee ΙΗρι & Ιτι-hydrochloride flows from the thin-film reactor into a stirred reactor II (Pig «4) of conventional construction tri. the held at 18O ⁰ C, "and in which a phosgene stream is continuously at a rate of 1 g / sin eingelei tet, Oae Arbeitevoluemen of r.xeiten Heaktore is about 1500 ml.

After the reactor II, the intermediate reaction product flows into a third reactor III with an Arboitevoliraen of

BATH 009829/1670

about 850 ml, which is kept at 190 ^° C. Phosgene is fed into this reactor at a rate of 1 g / min . From this reactor the reaction product flows over into a final reactor IV with similar features to reactor III , where the phosgenation is terminated. The overflow from reactor IV is raw Solution of hexamethylene diisocyanate in trichlorobenzene with only a little suspended solids · The yield θχι hexamethylene diisocyanate in this crude product is

009829/1670

Claims (1)

• υ » ■ 'Psteataaspyüciie' 1β Y © r £ ®hren aw HeristelXiaiag of organic isocyanates Through the Bhosgeni yield of an AfflisshydrGehlori & Ss thereby keaa «- · be without “ that one forms the _{amine hyeb? © Chloride 9} by men a solution of this amine in an inert I> ösimgemitt®l ₉ di © in the form of a dümiexi Sohioiit isit constantly changing r OTserfläöh © is present »treated with oleohydrate and the aminäjdroahlorid formed in this way with phosgene conversion * Procedure according to Ansprusia I ₉ dadurefe gete organic- Isoejanat is an -orgajaisckee Püljisosjsaat and a polyamine is used as ß 3 _β Terfahren according to claim 2 _r öadu? 'Gli characterized that the organic © Folyieocyanat is aiii aromatic organic PolyisoüyanEt and aan used as a polyamine an aromatic p © 2.y «amine 4 <s Yerfahrsn according to claims 5 _S characterized ₉ that the organic polyisocyanate is @ in i'olylene diisocyanate or isomers thereof " 5 ο Yerfahren according to claim 2 _D characterized, that £ the organic polyisocyanate and the polyaEiin used contain aisidestesis- © in © aliphatic cli gsbundens isesyanate group _o BATH ORIGINAL 00982-9 / 1 67-0 6o method according to claim 5 »characterized in that dad since organic polyoxyanate is hexamethylene diisooyanate. 7ο method according to one of the preceding claims} thereby characterized in that the solution of the amine in the inert solvent contains 4 to 16 (Jew.Ji AmIn. 8. The method according to any one of the preceding claims, characterized characterized in that treating a solution of AmIn in an inert solvent, the solution being in the form of a thin layer with a constantly changing surface, with hydrogen chloride in a thin film evaporator or processor is carried out. Process according to one of the preceding claims, characterized in that the amine hydrochloride is formed by allowing a thin layer of a solution of amine in an inert solvent to flow down the inner walls of a cylindrical tube which contains hydrogen chloride gas and the thin layer continuously is moved by stirring blades ₉ arms or wipers, which are arranged on a rapidly rotating shaft which is centered in the tube. / 1Oo method according to claim 9 s characterized in that Coolant around the outer walls of the cylindrical tube is circulated » BATH ORIGINAL 003829/1870 ms / M eiaea ö © s? v ^ ¥ © m ^ Με 'ί & ΰ ΐ? ί £ öqä, Qiaos? fee = Ε € ε! Ί »5? € Λ sisefe, mh 1I ei © tasi? f t ₁ , ösß IQ Μ © βϋ ^@ 0 gs == by, gekemaseielawätg that eöt koatiauierlisli di ^ shgefülir ^ and the Hyäs * oeiilörid nof the formation feoatiauierlisfe su continuous phosgenationumgSTorricihtuiig 14o Yei 'go to one of the previous Anspirtlohep because it is characterized in that the phosgenation is carried out at a pressure above atmospheric exit temperature « 15e method m && h one of the preceding claims da «· characterized by && Q phosgene zueamraen with chlorinated oxygen while * the formation of the aisine hydrochloride © is introduced , 16 ", Organic Ißoejanate _f produced by a method according to one of the preceding claims" WTWAN "". " Da.-IHG H FINCK6 BlM.-WS. R BOHl 009829/1670 Blank page