DE1543704A1 - Process for the production of polyols - Google Patents

Description

A 92 366 dr. ι. M'aMaas

DR. W. G. PFEIFFER PATENTAN WÄ LT E 8 Mo NC H EN 2 3 UNGERERSTR. 25 - TEL. 333030

Jefferson Chemical Company, Inc., Houston, Texas, V.St.A.

SSSSSSSSSSSSSSSSSSSSS-SSSSSSSS'S'SSSSSSSSSSSSSSSSSSSSSSSaSSSSS

Process for the production of poly oils

sssssssssssssssssssssssssssssesssssssass

(Exclusion from patent application J 25 779 XVd / 39c)

The invention relates to the production of polyurethane sums. The invention particularly relates to Production of new nitrogen-containing poly oils, which for the production of improved rigid polyurethane foams suitable.

It is known that rigid polyurethane foams can be produced by reacting a polyisocyanate with a hydroxyl end group To produce polyester or polyoxyalkylene ethers with a hydroxyl number in the range from about 350 to 900 ", but no polyol has yet been found that meets all the requirements, and for various reasons, the polyurethane foams produced to date are not yet fully satisfactory

For example, the durability of polyurethane shank foams Much to be desired in relation to conditions of high temperature and high humidity. Furthermore it is for many applications of polyurethane foams

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necessary » 'Α %% ν « si-ßsa Söis & utistcfX au "dispose ,, ά®ν Sälb & tftuglääa & entl or p ^ aAiififÄ ftiok * hre * inbß ^ _v uia this BigensC'haftöB, - ku erais!« **,' aiisasn separate

erissd aur

Connections usually required in those that thereby the properties of the, manufacture

adversely affected.

With the kerfctelluKg of a satisfactory P. etoffe io% it also necessary »the relativea speed of travelea d # i · different alslayfeading reactions correctly to one another

This Alistimffiung is Gewöbüllch by eorg ~ · selection »Ines! Cä.t« ly * & tc »systems achieved- X» all. The catalyst is also used »a® tertllJMH Aaia _f da® tottwofler alone or ~ if necessary - in known« ? aitacgsn ^ aolien Zii'JivefbiÄdungön Töi "3» iaob.t is, Ü4e so

n tertiary aaiae give the finished ». Sohatutstoff ia d »ß! Prayed in cases a genuine acceptance

ϊ! 3 became now. gsfmiden that vielo the obe.n besohriebenen parts of Polyiirethaiieoh & uiBStoffeii by YerwenduBg το "new, etiokstoffhaltigen polyols ausgeöoh &lt" t be ketenes whose catalytic effect eats ao great that sat for Eer-η division of Hartechaujastoffea auwarden no g-asondertdr catalyst Surprisingly enough, they are with you

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BATH ORIGINAL

the erf indwgeseiaäCl · used. Polyethylene-made polyamide fabrics have the effect of making them easier to mac-hen. let ιχαά have good dimensional accuracy,

if specially admitted · Feusrhemmotoffe are vei-wend-et.

The new S'ehäiauss are outside of the north. from dsm Amin ^ eruch free, the often occurs in urethane rigid foams.,

The use of the polyols obtained according to the invention for the production of urethane foams is described in patent • .. · '... ·' ..... CPatenfcanmelduns J 25 779 IVd / 39c)

3 0 9022/1262

The erf indungsgemäß available polyol is prepared by adding an alkylene oxide to a Mannich condensation product of a Phenolverbindungj formaldehyde and an alkanolamine at a temperature of about 30 to 200 ° 0th These polyols have hydroxyl numbers of about 350 to 90O _9, preferably about 450 to 60O ₉ and a nitrogen content of about 1 to 15 weight = ^, preferably 4 to 8 weight = $ _p and the nitrogen is tertiary in the molecule Nitrogen in the form of 1 to 3 aminomethyl groups which are disubstituted on nitrogen and which are bonded to an aromatic ring on which at least one hydroxyalkyl group is also attached

Ethylene oxide ₉ propylene oxide,

At least styrene oxide, 1 "2-butylene oxide or glycid" originates one of the substituents on the nitrogen atom of the aminomethyl group contains 1 to 2 primary and secondary hydroxyl groups,

The Mannich reaction is a well-known reaction, wherein an active hydrogen-containing compound with formaldehyde and a primary or secondary amine to one

8AO ORIGINAL

9Q9822 / 1262

substituted aminome thy! derivative of the starting material containing the active hydrogen is converted Starting material for the production of the polyols according to of the invention to be used Mannich derivative is after usual method using a phenolic compound - as described below · »as the active ones Hydrogen-containing compound produced The ortho · = and para positions of these phenolic compounds are reactive enough to enter the Mannich reaction.

The Mannich reaction is carried out, for example, by first premixing the phenolic compound with the desired amount of the alkanolamine and then slowly adding formaldehyde to this mixture at a temperature which is below the temperature of the fovolecogenesis (a temperature which corresponds to the respective used phenolic compound varies and is less than about 35 ⁰ G "when phenol seibat is used) ', Haoh the end of the formaldehyde addition, the Reaktionsgeaisch iangs _a m with agitation-heated to a temperature Ton at least about 5O ⁰ G, for example in the range of about 80 to 150 ⁰ O is heated and held at this temperature until the formaldehyde content has fallen to at least about 1 weight9 = $. This takes about 2 to 4 hours at the elevated temperature.

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! times the end of the reaction, the reaction mixture is from Freed water and thereby a crude Mannich reaction product obtained crude reaction product by usual measures, in certain Components or fractions! Are broken down, but it is a special feature of the invention that you can use the whole raw Mannich reaction product can be used as such without isolating its individual components «According to the In the preferred embodiment of the invention, all of the crude Mannich reaction product is used as such, and when this happens "should special measures be used to obtain a product?" the contains less than about 1 weight = - ^ free! formaldehyde «

The phenolic compound to be used in the Mannich condensation is an aromatic compound which carries one or more hydroxyl groups directly on the aromatic ring and has a hydrogen atom in one or both ortho positions and / or in para position to the hydroxyl group and otherwise unsubstituted or through Is substituted radicals that do not react under the conditions of the Mannich reaction. Substituents of the latter type include u "a" Alkyl _v cycloalkyl, aryl, halo, nitro, carbalkoxy _P haloalkyl and HydroxyalkylοDie

preferably

phenolic compound is further / characterized by a molecular weight in the range from about 94 to 500 «

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'■■■ .. * 7: ■

Examples of useful phenolic compounds include "phenol, o = _s m- _e or p ^ cresolj lthyXphenol ₉ nonylphenol, p" phenylphenol ₉ S ^ -bisC ^ -hydroxyphenylO ^ propane, ^ "naphthol, P ""hydroxyanthracene, p-chlorophenol , o-bromophenol, 2,6-dichlorophenol, p-nitrophenol, 4 ~ Mtro ^ 6 ~ phenylphenol, 2 «ltitro-4« methy! phenol, ^ »S-diniethylphenol p-isopropylphenol, 2 = bromine» 4 ^ CyClOhBXyIPhCnOIf 2 = Me thyl ⁱ '"4 = ^j bromophenol, 2- (2-hydroxypropyl) phenol, 2 <=> (4 = hydroxyphenyl) -äthanolo

Daa alkanolamine for the conversion with the phenolic compound and formaldehyde in the context of the invention is a Alkanolamine of the formula

PHRCHR .HO- (GHH) -ir NH

3HR = GHR

or

HO- (CHR) _n --HR »

where R is hydrogen or an alkyl radical with 1 to 4 carbon atoms, R ^f ■ is hydrogen or an alkyl group with 1 to 4 carbon atoms or the group - (CHR) -OH and η is an integer from 2 to 5 «·.

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BATH

Examples of alkanolamines that can be used include monoethanolamine, diethanolamine, isopropanolamine, bis (2 = hydroxypropyl) - = amine _P Hyäro ^ ätiylmethyiamrin, N-Hydroxyäthyl · piperazine ₉ l ^ hydroxypropylpipera3in, 1T-hydroxybutyimethylpiperazine and N-hydroxyäthyiiper-2,5-4

In the ^ annich reaction, formaldehyde can be used in any of its usual forms, Z _n B, as an aqueous formalin solution, as an "inhibited" methanol solution, as pafaformaldehyde or trioxane »

The properties of the Mannich product and therefore also the Properties of the alkylene oxide adduct of the Mannich product can by appropriate choice of the phenolic compound used and the alkanolamine used as well as by Change in the molar ratios of the reactants can be modified within wide limits. For example, phenol, diethanolamine and formaldehyde are in a molar ratio of 1: 3: 3 used ^ then the product formed in the predominant amount contains seven hydroxyl groups each Molecule ,, Will the molar ratio of the-same reaction part = If the patient is set to 1 s 2: 2, then ala the product mainly formed is a pentol. Correspondingly, with a molar ratio of 1: 1: 1 the main product a triplet *

Used in the manufacture of the triol or pentol, formaldehyde Used in the overshoe, then runs alongside the Mannich reaction

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BATH ORIGINAL

secondary condensation of phenol with formaldehyde. This is the well-known novolak reaction that leads to polymethylene = · derivatives of phenol? If, for example, phenol, diethanolamine and formaldehyde are reacted in a molar ratio of 1: 2 ί, the normal Mannich reaction takes place at one of the three active positions of the phenol. This leaves two active positions on the phenol nucleus for condensation with the excess formaldehyde Ό the presence of the amino groups = _p sufficient to promote the phenol formaldehyde condensation by base- catalyzed = arises whereby a complex reaction product.

According to the invention, this will be a man! eh — reaction product reacted with an alkylene oxide to form the polyol. The catalytic effect of the nitrogen present in the Mannich condensate is sufficient to promote the reaction of one mole of alkylene oxide with each free amino hydrogen atom and each phenolic and primary hydroxyl group, which is why an additional catalyst is not necessary. Di-© alkoxylation is'bei "einer'Temperatur of about 30 to 200 ⁰ C performed" For example, adding 7 mol of propylene oxide to the phenol, diethanolamine and formaldehyde in a MolLve-rhältnis of 1 s 3 s 3 = Mannich prepared "Product to form a Hepfols, the theoretical structural formula of which is given below

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HIGH (CH

^ O-OiL ^ GH

HOCJH (CH,) -OH ₉ -O-OK

HOCHi CHjJ-

CH ₉ -CH (CBL-) OH ι 5

OH _o -CH _o -0-0H _o -CH (CH ») 0H

£ j £ Ä J

This compound can be the main constituent of the reaction mixture, but the device contains in practice known lines of tyrivolens, pentols. Heptoles

with imteraohieaiichom PrqföJgrlierungegr-id ,. Daa

obtained polyel
According to the invention / is a complex mixture, is defined, however, for the purpose of explaining the invention, as "alkyleneoxy adduct of Mannich treatment product from a piienolic compound with porous hydroxide and an alkanolamine".

Esj 1st oelbetverständlich possible, less than 1 mole _t per alkylene oxide free phenolic and primary hydroxyl group "in the Mannieh-Sondensationsprodükt siumsetsen. The very first swackräDiga!.! Close, -an alkylcnrxj'd is at one mole. Each free Äminowaaceratoffatos) and phanoliecher hydroxyl group r, In general, phenolic hydroxyl groups unbaseable TtrathanlSandungen <md oind -deshall; - vfo this Praktieoh

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BATH ORIGINAL

'Feasible' is - avoid this below. «2> a phenolic hydroxyl groups more reactive üinc! als'alkoholische hydroxyl _t react aio iuit duct alkylene oxide is first, thereby ensuring the implementation of the phenol see! hydroxyl groups when less al 'D 3e stöchlometriöolie amount. Alkyler.üxyd is used, In general, more than the minimum amount of AIky:! Enoxide is used to produce a product with a lower HydroxylBah3. and lower viscosity ". ' A well-suited "product is, for example, that by acidification of 5 mol of tropylene oxide (instead of the maximum amount of 7 mol or the minimum amount of 1 mol) to that in the Mannich condensation of phenol, formaldehyde and diethanolaain in a molar ratio of 1 s 3! 3 formed heptol product obtained ":

For the implementation of the method according to the invention » the preferred alkylene oxide is propylene oxide.

The following examples illustrate the invention Process for the preparation of the polyols described.

1.780 hg (14.4 Ib8. _C 20 mol ^'1 Phenol, 6.5 kg (i3,91bs _v, 60 mol) and Li.üthanolamin 802- "(1,77IbS.) Water' in a imrden

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1 §43704

Vessel with a capacity of 18.9 1 (5-gallon) was placed in the formaldehyde in the form of 4 »85 kg (10.7 lbs») of a 37 'point aqueous solution (60 KbI) slowly added with stirring, the reaction temperature at about 25 ⁰ O was held. "After the end of the addition dae reaction mixture was stirred for one hour at 35 ⁰ G and then for one hour at 83 ⁰ C heated« the reaction mixture was maintained at about 9O ⁰ C for about 5.5 hours from the What. freed water, using a nitrogen stream with a pressure of 300 mm. "Then 8.7 kg (19.2 lbSo _V 150 mol) propylene oxide were added at a temperature of about 90 to 12O ⁰ D over a period of about 4 hours" after the cessation of the reaction, unreacted propylene oxide from the reaction mixture was removed ₀ in this way a Manniehpolyol was obtained with a hydroxyl number of about 495 "

Example 2 "

About 1.89 kg (4.19 IbSo ₅ , 20.2 mol) of phenol and about 6.3 kg (13 »9 IbB., 60.0 mol) of diethanolamine were added to a reaction vessel with stirring with 4 * 85 kg (10 , 7 lbs ", 60.0 moles) of 37 # ~ strength by weight aqueous formaldehyde solution, the Reaktionetemperatur was maintained at about 35 ⁰ C" After complete addition of the formaldehyde, the reaction mixture was stirred for about 1 hour at 30 ° C and then

909822/1262 ^ _{0 0RIG} , _NAL

2.5 hours about 90 95 ⁰ O big heated »Bas reaction © · - was mixed by heating to 95 ⁰ O at a Brusquely won less than 1 mm from the water liberated. The Mannich base so obtained was heated to about 95 ⁰ O, was added followed by propylene oxide * "After the addition of about 1.36 kg (3 propylene oxide the temperature was srhblit to about 120 ⁰ O and continued Oxydzugabe" until there is no more pressure drop occurred "A total of about 6.02 kg (13.3 IbS ₀₉ 104 propylene oxide were added / of which about 290 g (0.64 11b) were not converted and removed by vacuum distillation." The product was an amber-colored, viscous liquid with a hydroxyl number of 570 and a viscosity ψοη 37650 eP at 25 ⁰ Co

Example 5

A 3-liter flask was charged with 564 g (6MoI) of phenol and 1260 g (12 mol) of diethanolamine, 974 g (12 mol) were added to this mixture 37 ^ -ig © FornaldehydlÖsung added with stirring, "the temperature at about 25 ⁰ C held

After the formaldehyde addition, the reaction mixture was stirred overnight at room temperature then IMD about 2 BIB 5 hours heated to 20 ⁰ C. Then the water was a pale yellow viscous oil was obtained by vacuum distillation at 100 ⁰ C and 0.25 mm from the product ", whereby 1971 g * Of this were 1772 g (5.41 mol) is heated in an autoclave at 9O ⁰ C, whereupon 1378 g (21.7 mol)

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Wurden- propylene oxide introduced, After complete addition, the reaction mixture was left for one hour at about 90 ⁰ C and through. Application of a vacuum cleaned "You got 3053 g of a golden yellow viscous material with a Hydroxylaahl -ψοη 508 and a viscosity of 45,000 cP

Example, 4

The beaehriebene in Example 1, catfish was repeated with the exception that the heating after Pormaidehydzu = · exist at 9O ⁰ C for 5 hours wurdeο carried out As a result, has been the free FormaXdehydgehalt the Mannich base of about O ₉ 6 fo to about O ₉ 12 $> reduced,

Example 5

A 3-liter flask was charged with 498 g (3.88 mol) of technically pure p-chlorophenol and 794 g of C? "36 mol) of diethanolamine" While stirring and maintaining a temperature of below 35 ^° C., 597 g (T, 36 moles) one 3? ^ »Igen formaldehyde solution added» The mixture was stirred for 3 Sbunde at room temperature and then heated to 90 to 110 ⁰ O for a total of ^{6 hours. Then it was freed from water at 11O 0} C and less than 1 mm pressure, whereby 1383 g

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BAD ORIGJNAL

Product love surückb., To a part of propylene oxide was added at 11O ⁰ G until no further pressure drop occurred more. Daa propoxylerte product was vacuum cleaning at 12O ⁰ C and. Ό, 5th on the subject, "whereby.a polyol with a hydr. Number of 508 was obtained.

Example 6

A 3 liter flask was filled with 941 g of C10.0 mol) phenol and 1051 g (10.0 moles) of diethanolamine contain * this mixture was cooled to 16 ° C using an ice bath, whereupon 1204 g (15.0 mol) of a 37% formaldehyde solution

This was introduced with stirring 16-25 ⁹ C _a The mixture was stirred for one hour at 30 ° 0 and then heated for 5 hours at 95 G., The Reaktionsgemisga was then heated a total of 9 hours in a vacuum at 95 to 100 ⁰ C, and finally The product obtained was cleaned at a pressure of less than 1 mm and yielded 2173 g of a very viscous material ο 2100 g of this product are reacted with 1314 g Proiaylenoxyii at 110 ° C. and 4.2 atmospheres (foO peig) ₀ to none Pressure drop occurred more. The Propylenozard was at 100 ⁰ G and less than? mm pressure cleaned and yielded a polyol with a hydroxyl number of 533 "'

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away

Example 7

A vessel having a capacity of 18.9 1 (~ 5 gallon) was added 4 ₉ 26 kg (9 * 41 Ibe, "45 * 3 = g * mole) of phenol and 4.77 kg (10.51 lbs," 45 , 3 g-Hol) diethanolamine charged "The mixture was slowly treated with 3 * 64 kg at a temperature of 35 ⁰ C under nitrogen atmosphere and with stirring (8 ₉ 04 IBSo ₉ 45 * 3 g-moles) of a 37? £ = formaldehyde solution added, After the addition of formaldehyde, the mixture was stirred at room temperature for 1 hour and then ^{heated to 95 °} C. for a further 2 hours. The reaction mixture was then ^{purified with gas at 95 °} C. and 3 mm kg (90.6 g-mol ₉ 11.6 lb8o) of p-propylene oxide given at 95 ⁰ C, whereupon the mixture O _{9 was} allowed to react for 5 hours at 110 ^{0 C} Hydroxyl number of 531 and a viscosity of 30,000 cP at 25 ⁰ C ₀

Example 8

A vessel with a capacity of 18 ₉ 9 1 was charged with 3.62 kg (8.0 IbSo ₁ , 38.5 mol) of phenol and 8.1 kg (17 _P 87 lbs _oe 77.1 mol) of diethanolamine o The vessel was evacuated and flushed with nitrogen before 6.18 kg (13 _P 64 IbSo ₉ 77.1 mol) of a 37% formaldehyde solution was drawn while stirring «,

^909822/1262 BADO _R , G, NAL

have always been - where one. the Reiaktionstemporatur not more than 35 ⁰ C rise ließ- Nash vollsitäiKliger Fonsaldehydzugabe the mixture was stirred for one hour at 35 ⁰ and Q for 4 hours at 90 ⁰ G heated Bie Mannich BAEE was vacuum-moor a nitrogen stream bai purified 90 ⁰ C. * Then -were 8 * 35 kg (18 ^ 4IbS. ,, '! 44 * 3 mole) of propylene oxide at 90 to 11O ⁰ C and 4 "2 atm poigj added (60"'. It purification of the propoxylated product gave 19 "31 kg (42.57 lba,) of a polyol ait ■ siner'Hy-droacylsahj. -van 56'l and a * viscosity raw "58-800 cF at 25 ⁰ C-.

2 / 12-62

Claims (1)

543704 - * r-4? Claims 1. A process for the preparation of a nitrogen-containing polyol with a hydroxyl number of about 350 to 900 and a nitrogen content of about 1 to 15 wt an aromatic nucleus are bound to which there is also at least one hydroxyalkoxy group which is derived from ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide or glycide, with at least one of the substituents on the nitrogen of these asinomethyl groups containing 1 to 2 primary and secondary hydroxyl groups, characterized in that at a temperature of about 30 to 200 ⁰ C (A) Ethylene oxide, propylene oxide, 1,2-butylene _{oxide, 4} styrene oxide, glycide or a mixture thereof with (B) a Mannieh condensation product (1) an unsubstituted or substituted one Mono- or polyhydroxyphenol with a hydrogen atom in at least one of the o- and p-positions to the hydroxyl group, which in the other positions by alkyl, cycloalkyl, aryl, jfitro, Ca & lkoxy, haloalkyl or hydroxyalkyl groups or can be substituted by halogen, 909822/1262 BATH ORIGINAL (2) formaldehyde and. (3) an alkaneclamin der ER-GHR HO- (CHR) _n ^ SH CBR-C / hR odar H - HO- (GHR) PNR ¹ where R is hydrogen or an alkyl group with 1 Ma 4 carbon at ο! Ben., R 'Wage er' stoff «an alkyX group with; 1 "to A carbon atoms or the group - (CHR) _n OH mid η a positive whole 7-ahl iron 2 to 5" mean, the Mannich condensation at a pin temperature below that of the JFovolakbildurig was carried out,
implements .. \ Terrahr3ii after .Ane-j-ruah ί _ν thereby! Let a K-.iiinieh-ioo-ienaationaproduicx be used, öae through Kottdeneajion ψηη phenol »formaldehyde and diethanolaadn in a molar ratio of 1 ι 1 t 1 fcia 1: 5 t 3 can be obtained. BAD ORIGWAL