DE1593905A1 - Process for the production of polyether polyols - Google Patents

Description

PATENT LAWYERS
DR.-ING. H. FINCKE

DiPL-IN G-. n. cÖHR Feb. 23, 1967

DIPL.-LN3.5-. STAEGER

MUNICH _<Ρ . _Λ ^ _ΛΛ , -

MO: ^ sT ^ .3i 1593905

Folder 21148 - Dr.K ₀
Case Do 19098

description to the patent application of

Imperial Chemical Industries Ltd., London S.W.1,

Great Britain

concerning ■ processes for the production of polyether polyols.

Priorities: 28 * 2.1966 and 20 “2.1967 - Great Britain

The invention relates to polymeric materials and in particular on polyether polyols and processes for their production.

Bs has already been proposed to make polyether polyols produce that one alkylene oxides with primary or secondary Amines which contain two or more active water

BAD ORiGfNAL

109808/2 1 36

contain s-coffatome

The uncatalized reaction usually proceeds as far as » that all of the hydrogen atoms bound to the uninitrogen be replaced by alkylene oxide, tertiary hydroxyalkylamines being obtained.

However, if these tertiary amines are not strongly basic, then the reaction proceeds without the addition of a catalyst Promotion of the reaction of the hydroxyl end groups with the alkylene oxide does not easily further the most suitable catalysts for the reaction are alkaline materials such as potassium hydroxide, but in many cases result Difficulty finding the catalyst in AmIr. to dissolve before the addition of alkylene oxide. If the catalyst doesn't is completely dissolved, then it can perform its function of accelerating the reaction between the alkylene oxide and the reaction product from the hydroxyl capped Do not exercise amine and alkylene oxide; in addition, the reaction product can cause undesirable by-products as a result of a Reaction that takes place between the catalyst and the alkylene oxide alone may be contaminated. Procedure that to remedy this difficulty have been proposed » usually require a more complicated oxyalkylation procedure.

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Thus, according to the present invention, a process for the preparation of a polyether polyol is proposed, which is carried out by mixing an alkylene oxide with a mixture of a primary or secondary amine containing at least two active hydrogen atoms in the molecule and a simple polyvalent ^{amine which is liquid at 12O 0 O} Aiko «get implemented».

It has been found that the method of the present invention largely eliminates the above-mentioned difficulties "and that the oxyalkylation reaction very much runs smoothly ο In addition, it has been found in many cases that the products are easier to handle than the products obtained by oxyalkylation of the amines alone * In particular, those products have the oxyalkylation of mixtures of aromatic amines and simple Polyhydric alcohols are usually much lower viscosities than oxyalkylated aromatic ones Amines alone with a similar hydrocyclic value. This lower viscosity can be achieved by having a polyether based amine with a polyether polyhydric alcohol based, but it is generally preferred to use the mixed polyethers . from mixed initiators, thereby also taking advantage of the improved manufacturing conditions specified above to use α

. BATH ORIGINAL

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The alkylene oxides that can be used in the present process, ethylene oxide include propylene oxide and styrene oxide, t Butylenoxyde and mixtures thereof. Optionally, the alkylene oxide can be incorporated into the reaction mixture in more than one stage, a different oxide being used in each stage. For example, the mixture of the polyhydric alcohol and the amino compound can be reacted first with propylene oxide and then with ethylene oxide.

The one that has at least two active hydrogen atoms in the molecule primary or secondary amine can be a compound that has at least one primary amino group or at least has two secondary amino groups, or it may be a compound in which the two such groups are present.

Examples of amines produced by the process according to the invention can be oxyalkylated are aliphatic amines such as butylamine, benzylamine, cyclohexylamine, piperazine, Ethylenediamine, hexamethylenediamine, diaminocyclohexane, diethylenetriamine and triethylenetetramine. The procedure however, it is particularly useful for the oxyalkylation of aromatic amines, which term is compounds are meant in which at least one of the amino groups is linked directly to an aromatic nucleus.

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Suitable compounds are, for example, aromatic amines which contain only two active hydrogen atoms, such as aniline, toluidine, the misidines and the phenitidines, but a particular advantage is achieved in the process according to the invention when aromatic amines are used, the three or contain more active hydrogen atoms, as these amines give products with very high viscosities . Examples of such amines are o ~, s ~ and p-phenylenediamine, 2,4- and 2,6-tolylenediamine, the diaminoxylenes, 2,4- and 2,5-diaminoanisole, the chlorophenylenediamines, o- and p-aminobenzylaain, 4-aminodiphenylamine, 2,6-Diaroinopyridin, 4, 4 '-Diaminodiphe nylmethan, t, 5- and 1,8-Diaminonaphthelin, 2,4,6-Traminotö hydroxytoluene, 4,4'-diaminodiphenylamine, 2,4,4 ^> -Triaminodiphenylethane, 2,4 »4'-triaminodiphenyl ether and 4,4 ', 4" -Triaminotriphenylinethane.

It is particularly expedient certain commercial mixtures of aromatic amines to be used, such as mixtures of 2,4- and 2,6-Tolylendi airrt η obtained by reducing the Dinitrierungeprodukte of toluene. Other suitable mixtures are, for example, the crude reaction products of aniline with formaldehyde. These reaction products contain diamine dipheny! Methanes and also polyphenyl polyamines with more than two amino groups, in particular triamine but also hotter molecular polyamines. The proportions in which the various polyamines are present in atm crude product »

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largely depend on the initial ratio of aniline to formaldehyde. "To obtain a crude diaminodiphenylmethane suitable for use in the process according to the invention it is preferred that the molar ratio of aniline to formaldehyde be between 4: 1 and 1.2: 1 and is preferably between 2.5: 1 and 1.5: 1. The most suitable crude diaminodiphenylmethanes contain 50-90 GeWo-? E diaminodiphenylmethane, the remainder being triamines and higher molecular weight polyamines.

As used in the present specification, the term "simple polyhydric alcohol" refers to monomeric polyhydric alcohols containing only carbon, hydrogen and oxygen atoms. Examples of such liquid polyhydric at 120 ⁰ C are Athylenglycol alcohols, propylene glycol, trimethylene glycol, diethylene glycol, dipropylene glycol, 1,2-, 1,3-, 1,4- and 2,3-butanediol, glycerol, 1,2,3- , 1,2,4- and 1,3,3-butanetriol, 1,1,1-trimethylolpropane, 1,2,6-hexanetriol and other hexanetriols, sorbitol and iditol. Mixtures of suitable polyhydric alcohols can optionally be used. It is generally preferred to use 20-70% polyhydric alcohol based on the total weight of Amia and polyhydric alcohol,

even

but higher ratios, / up to 9θ £ *, are in certain cases useful.

109808/2136 bathroom cmiaiNAL

The selection of the in conjunction with a special Amln Higher value alcohol to be used is largely dependent on the Determines properties that the desired reaction product should have. So it is when the hydroxyl function onality of the product is insignificant or if the production of a polyol with the lowest possible viscosity is desired, it is advantageous to use a cheap glycol, such as. Ethylene glycol, to be used. In such cases, in which it is desired that the product be complete consists of materials with a functionality of 3 or more, glycerine is suitable.

A method of making suitable mixtures for the Reaction with the alkylene oxide consists in daa primary and / or secondary amine with the polyhydric alcohol in the presence of water and an alkaline catalyst to mix and then remove the water by heating under reduced pressure before carrying out the reaction with the To remove alkylene oxide »If necessary, the catalyst can be dissolved in the polyhydric alcohol before the latter is mixed with the amine.

The general reaction conditions between the alkylene oxide and the mixture of the polyhydric alcohol and of the amino compounds are of the type described in the literature for the reaction of alkylene oxides with active ones

109808/2136

Hydrogen-containing compounds "are described. For example, temperatures" of 50-15O ⁰ C, preferably 90-120 ⁰ C, rad pressures up to 5-6 at can be used. Alkali catalysts, such as, for example, potassium hydroxide, sodium hydroxide or barium hydroxide, can advantageously be used. The amount of alkylene oxide used in the reaction should be sufficient to produce a polyether polyol composition having the desired average molecular weight and / or hydroxyl value.

After the reaction has ended, the polyether polyol can if necessary 7om the catalyst freed by known processes like a.Bo by neutralization with an acid or by treatment with carbon or natural or synthetic absorbent soils or © © mix from it and subsequent filtration »It is beneficial in that Polyether polyol at some point during its manufacture or

Cleaning an antioxidant, see B. sterically hindered Phenols.

The polyether polyol produced by the process of the present invention e are highly reactive towards isocyanates and are particularly useful in the production of cellular or non-cellular polyurethane materials are useful, for example the general ones described in the literature Methods can be used »For example, the polyether polyols, optionally in a mixture with others

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Polyols, with organic polyisocyanates, if necessary in Presence of other materials, such as ζ »Β. gas generants and other conventional additives.

Because of their responsiveness, they're after this here Specified manner produced polyether polyols especially for use in the production of foamed polyurethanes using conventional techniques such as the one-shot method and the different on prepolymer processes. The ordinary ones can do it gas generating agents such as water and / or fluorinated Hydrocarbons. Those polyether polyols that have a relatively high average Molecular weight and low hydroxyl value can be used in the manufacture of flexible foams used, while polyols with high hydroxyl values, such as «200-800 mg K0H / & in the production of hard foams can be used. Polyether polyols with hydroxyl values are particularly suitable for this purpose in the range of 400-600 Ωg KOH / g, the combination high reactivity and high hydroxyl functionality, which is found in the polyether polyols, derived from primary or secondary amines with four or more active hydrogen atoms make them special as starting materials for the manufacture of hard Foaming brewable. Those polyethers of the present Brfin-

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that differ from aromatic amines such as tolylenediamines derive, have advantageously low compared to the oxyalkylated amines with the same Hydroxyl value Viscosities. The viscosity properties of polyether polyols are extremely important in the manufacture of polyurethane foams where the various components are must be mixed together quickly and evenly.

The common tolylene diisocyanates or diphenylmethane " Diisocyanates in essentially pure or in raw form can be used in the polyurethane process, but other organic polyisocyanates can also be used come to use. The raw ones are particularly suitable Diphenylmethane diisocyanate compositions containing 30-90 Gewo- # contain diphenylmethane diisocyanate, with the remainder from polyisocyanates with a functionality of more than two consists. Such compositions can be obtained by phosgenating crude diaminodiphenylmethane.

Suitable catalysts are, for example, the tertiary amines and organic compounds of metals such as tin. In some cases, however, it has been found that the reactivity of the polyether polyol to isocyanates is such that the use of catalysts with a high activity is unnecessary »Surface-active agents that can be used are e.g. siloxane / oxyalkylene copolymers, oxy- / ethylated alkylphenols, oxyethylated fatty alcohols and

109808/2136 ~ ¹¹ "

BATH ORIGINAL

BXoeloaisehpolymere from ethylene and propylene oxide »

Xn most conventional Polyuröthanaartscnaumayfflteiften foaming begins approximately 10 seconds after dea Additives food ζ of the polyisocyanates to the polyol and the Hilfebeßtaafiteilen and the foam "takes about 1 minute to Stelgen and is shortly thereafter tack-free at Rade the rise time or, and this means that a very short periods of time for mixing and pouring of the foam components are available, but attempts to extend this time considerably, "for example by lowering the catalyst concentrations, have a disproportionate increase in the time it takes for the foam to rise, and particularly the time that he needs to become tack-free. An unexpected benefit of using the polyether polyols of the present invention in the formulation of polyurethane foams is that the time available for mixing and pouring can be significantly increased with only a slight increase in the time the foam takes needed to rise and sun to clear the sieve

The invention is explained in more detail by the following examples » However, the examples are not to be taken in a limiting sense, all parts and percentages are expressed in weight.

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example 1

Typical polyethers according to the invention are produced in a stainless steel pressure vessel equipped with heating coils, a stirrer, an alkylene oxide duct and a thermometer pocket. The initiator components are introduced together with the potassium hydroxide catalyst, dissolved in an appropriate amount of water (in such an amount that O _t y / o KOH results in the finished polyether). The water is heated by heating for 1 hour at 100 ^° C. under 15 mm Hg pressure removed. Pro pylenoxyd is then introduced "The temperature is maintained at 100 to 110 ⁰ C, and pressures are applied at up to 2.8" After the Propylenoxydzugabe another hour to complete the reaction is heated, after which Y2 hour under a pressure of Holds 15 mm Hg.

The amount of remaining potassium hydroxide is determined by acid titration. An equivalent amount of acetic acid plus a ÜberBchluß of tojs is stirred at 100 ⁰ C during YZ hour, after 1 hour at 15 mm pressure is maintained ,,

A series of polyether polyols, the details of which can be found in Tables given is made from glycerin and a crude aniline / formaldehyde- ^ condensate, which is made from approximately equal amounts of diaminodiphenylmethane and higher polyamines, Table 1 shows the proportions of the used

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BATH ORIGINAL

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Components; Table 2 gives the analytical values of the products _o

Table 1

Glycerin Amine Prop.vlenoxyd 1 300 700 t690 2 500 500 1960 3 700 300 . 2240 4th 500 500 1650 5 500 500 2360 Table 2

Hydroxyl acid viscous
worth worth doing
(mg _Ä KOH / g) (mg.KOH / g) 25 ⁰ C
(Stoke) 0.16 3430 Equivalent to-
consecrated 1 484 0.13 186 363 2 493 0.17 29 566 3 496 0.20 275 973 4th 564 0.43 108 504 5 458 598

A polyurethane foam is made up of the following components

manufactured:

Polyether (2) 100

Trichlorofluoromethane, 40

Water 2

Tin (II) octoate 0.5

109.808 / 2136

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Siloxane / oxyalkylene copolymer 0.5

crude diphenylmethane diisocyanate
with “a salary of about $ 55
Diisocyanate, with the remainder off

Polyisoeyanate with higher functionality consists of 160

The rigid foam obtained has a very fine, uniform texture, is not brittle and has a density of 0 _v 026 g / cn?

Example 2

Using the procedure of Example 1, polyethers are prepared from glycerol and commercially available tolylenediamine (approximately 80-20 mixture of the 2,4- and 2,6-isomers) «Table 1 shows the proportions of the components used; Table 2 gives the analytical values of the products »

Glycerine amine

1 700 300 2660

2 500 500 2680

3 300 700 2700

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Table 2

Hydroxyl Acid Viekoöi Equivalent

worth worth doing by weight

(mg.KOH / g) (ogoKOH / g) 25 ⁰ C

(Poise)

1 461 0.16 29 746 2 485 0.15 80 464 3 498 0.31 398 328

The polyether (3) becomes using the following Components made of a foam:

Polyether (3) 100

Trichlorofluoromethane 40

Water 2

Tin (II) octoate. 0.5

Siloxane / oxyalkylene copolymer 0.5

crude diphenylmethane diisocyanate

(as in example 1) 152

The product is a fine, evenly textured rigid foam that is not brittle and has a density of 0.029 g / cnr o "

Example 3

The table explains the extended Miech / pouring time, resulting from the use of the polyethers of the invention results in «The relevant approach consists of:

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Polyether

oxypropylated triethanolamine (molecular weight 166)

Ethylene oxide / propylene oxide block copolymer (which under the trademark "Pluronic" L61 im Is commercially available)

Dimethylcyclohexylamine siloxane / oxyalkylene mixture polymer Trichlorfluormethaii Tris (ß-chloroethyl) phosphate crude diphenyl diisocyanate (as in example 1)

Parts 15 parts

4 parts 2 parts

2 parts 55 parts 30 parts

Parts (105 NCO index)

As a comparison substance, a polyether was used which by oxypropylation of a 2: 1 mixture of triethanolamine and tolylenediamine to a hydroxyl value of 500 mg KOH / g had been produced and at which due to the higher reactivity of this polyether dimethyleyclohexylamine has been omitted.

Tabel

Polyether Ver
same at
game
1 kr. 2 at
game
1 No. 3 at
game
2 No. 1 at
game
2 number 2 at
game
2 No. 3 1) Mixing / pouring time
Seconds 11 20th 28 17th 20th 14th 2) rise time
Seconds 50 80 75 72 65 70 3) time to glue
to become free
Seconds 50 90 75 82 75 85

1) From the addition of the isocyanate at the beginning of the stalk,

2) From the beginning of the climb to the end of the climb.

3) From the beginning of the ascent to the non-stickiness of the foam

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Claims (1)

Claims ο process for producing a polyether polyol, characterized in that an alkylene oxide with a mixture of at least two active Wassarstoffatome in the molecule having primary or secondary amine and a simple polyhydric, at 120 ⁰ C
converts liquid alcohol. ο Method according to Claim 1, characterized in that propylene oxide is used as alkylene oxide. 3 «, method according to claim 1 or 2, characterized in that the amine used is a compound in which
at least one amino group is directly bound to an aromatic nucleus «, 4. The method according to claim 3 »characterized in that an aromatic amine having three or more active hydrogen atoms in the molecule is used as the amine. 5. The method according to claim 4 »characterized in that the amine is a mixture of 2,4- and 2,6-tolylenediamine
is used. 6 "Method according to claim 4" characterized in that as amine a crude diaminodiphenylmethane with a -18- 109808/2136 ~ 18 - holds 50-90 wt _o - # Diaminodiphenylmethanen, whereby the. The remainder consists of triamines and higher molecular weight polyamines, is used, 7ο Method according to one of the preceding claims, characterized characterized in that the polyhydric alcohol in an amount of 20-70 wt .- ^, based on the total weight made of amine and polyhydric alcohol 8ο Method according to one of the preceding claims, characterized in that the polyhydric alcohol Glycerin is used «. 9ο Method according to one of the preceding claims, characterized characterized in that a polyether polyol having a hydroxyl value in the range of 200-800 mg KOH / g, preferably 400-600 mg KOH / g, is produced MiMmNMlMl MHNS H FiNCKt OIPI.IM · Λ · ΟΗβ DIPL-INO. »ITA» « 109808/2136