DE1570885A1 - Process for the production of polyethers suitable for the synthesis of polyurethanes - Google Patents

Description

Process for the production of the structure of polyurethanes suitable polyethers.

The invention relates to the production of hydroxyl end groups containing polyethers and polyurethanes obtained therewith. "Polyurethanes" are the reaction products of these ethers with organic polyisocyanates or polyisothiocyariajites, and the reaction can take place in the presence of other components, usually organic components that contain more than one reactive hydrogen atom are made.

Polyurethanes are obtained in large quantities from toluene diisooyanate and Polyethers with two or three hydroxyl groups are shown. Examples of polyethers which have been used for this purpose are polyoxypropylenetriol based on glycerine with a molecular weight of> OOO to 4000, polyoxypropylenediol with a molecular weight from 1000 to 2000 or a mixture of two or more polyether alcohols, which are derived from Is2 propylene oxide.

Industrially produced polyurethanes are mostly in the form of pliable foam sold. Ss is known to be pliable

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Foam can be produced by having one or more of the aforementioned polyether compounds with a stoichiometric Excess of toluene diisocyanate and a sufficient amount of water reacts, usually 2-6 parts by weight, based to 100 parts of the polyether, which then reacts with the excess isocyanate, releasing carbon dioxide, and the mass foams up. It is also common to use a low boiling halogen hydrocarbon -Compound, preferably Trichi or fluorine than, to be installed as an additional propellant. There are numerous catalyst systems and foam stabilizers available for this reaction known. In one manufacturing process, the foam is in continuous Blocks often more than 0.6 m high and l, ö rn 3 width won. It is cut to suitable lengths and further brought into the desired shape with cutting and profiling tools. In another manufacturing process, the finished object molded in a container that can be closed with a movable lid. Such forms are often about 61 χ 61 χ 10 cm tall} they have a variety of shapes and contain only about 0.9 kg of foam when filled.

Polyurethanes made from copolymers of Is2 propylene oxide are also available and ethylene oxide with molecular weights of 2000 to 3000, in which the ethylene oxide residues have a terminal Form a block. Such products have only proven to be difficult can be produced, although the reaction is very rapid, and the elastomeric foams obtained from them, weren't very satisfying.

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In its application no. L kC jkj IVd / ^ yc ready "s, the applicant has proposed a process for the production of new polyether-alcohol Flexible foams which can be produced in one-step process produce flexible foams which can be processed in a simple manner, there being further latitude with regard to the catalyst to be used and improved physical properties being achieved terminal hydroxyl groups come from 1.:2 propylene oxide and consequently at least ⁵ 90 £ are secondary hydroxyl groups which all have the same reactive "! mix component, water, catalyst and foam stabilizer *,

There are numerous polyethers as intermediate products for production has been proposed by flexible polyurethane show, jed © eh had shown itself over and over again * that only a small from these PMyiJrethane ergföty, who the 'wtinsehteh phy-

N II ^ ce ^ pi ^ sen * in this small amount of money Boly ^ Kaer ^ i, the l% lyju # e * $ iaihe in BlocUEfofim mili geelg-

ikisenen MggSschaÄeif Ergebetti only finds mänt? weiaigeV- die slöte % im ^: Wü ^ M & mm ^ i ^ - fit «för ^ vei? fanfen v

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1570 p

Play-like upholstery for car seats and furniture, © t * g »fiiert very precise working conditions, since the surface of the moldings is large compared to the volume of the moldings. Di © heat capacity of the mold is compared with that of the Fornilli "GSS fgroßj the way of the rising foam is waae complicated 'besehränktj the foam is often subjected to pressure as a result of the outflow set resistance. If you want to make a good molding, the reaction components have to become foamy (rapid cream time), the flow properties have to

rough

foamed material must be good, and it must be formed which adheres well to the molding, but which is usually so hard that a molding results that is not exclusively soft and uncomfortable. The form should be free w & m. Crevices, voids or hard spots, such as those found in places containing colony and closed cells. If you use the expensive molds and curing ovens, the molding should be as easy as possible to remove from the mold.

It has been found that the so-called geicappteai &&& $ &&& * üäl «blook copolymers representaa ^ in deaaen that forms blocks, are too strongly reactive, as the only Bolyols in the P © rraling itrefweaiden te ^ LEi a sufficient amount aaa Istiaylpea ^ xx entto «l ^! t «ii» WH

derliche Oberfläehenaktlvitlib in € the i

possess properties, beatiagt the toöiie ®efasß & ■■ &&

Alcohol, which often increases tination reaction. On the other hand .

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to that of the applicant in the parallel application no. 46 747 TVd / 39e described methods are synthesized, the result in sufficient surface activity properties, which, however, since they are secondary alcohols, not fast enough for gelatinize all molding processes.

It has now been found that new polyoxyalkylene polyhydroxyl compounds can produce, from which polyurethane can be obtained let the copolymers of ethylene oxide and 1: 2 propylene oxide represent, in which only part of the ethylene oxide forms terminal blocks., ^

According to the invention, polyhydroxy polyethers can be produced with a molecular weight of 1000 to 6000, which contain three or more hydroxyl groups and which essentially consist of polyethylene oxide residues and 1: 2 propylene oxide residues, and which contain the residue of a polyhydric alcohol with three or more hydroxyl groups , where 4 - 20 wt. # of the alkylene oxide residues are ethylene oxide residues and in which at least 2 wt wherein 15 50 % of the hydroxyl groups present are primary hydroxyl groups · ...-, .. ■. . -. - .-. - -. '■, ---. ....- .. ·

The method according to the invention for the preparation of a polypropylene compound is characterized by the fact that one is an organic

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Polyisocyanate or polyisothiocyanate of the general formula R (NCX) _{n +} lt where R is an organic radical, X is an oxygen or sulfur atom and η is a positive integer, _{reacts with a polyhydroxyl polyether prepared according to the invention.} This process can be carried out in the presence of water, which is preferably present in a concentration of 1-3 % , if a foamed polyurethane is to be obtained. The polyurethane compounds produced by these processes are also encompassed by the present invention.

The invention also relates to a molding process in which the polyurethane foam obtained in accordance with the invention in a manner known per se is deformed, and the molded articles produced therefrom also belong to the present complex of the invention.

The polyhydroxypolyethers are advantageously obtained in such a way that ethylene oxide and Is2 propylene oxide are used with conventional initiators Molecular weight can react! for example, one can use the oxides with glycerol, trimethylolpropane or 1: 2: 6-hexanetriol convert to triplets; with pentaerythritol or ct-methylglucoside one produces tetra oils according to the invention, and with sorbitol one can Win hexols.

According to the invention, preference is given to preparing polyhydroxyglycol ethers which are triols and have a molecular weight between 2500 and 4500, in particular between 2700 and 4000. These products should expediently contain between 5 and 15% by weight of the alkylene oxide radicals as ethylene oxide radicals, and the non-terminal ethylene oxide blocks should contain between 2% and 7 % of the total

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Make up alkylene oxide residues? .Furthermore, the terminal ethylene oxide blocks should have such a dimension that between 20 and 45 of the hydroxyl groups present in the particularly advantageous ones Polyhydroxypolyethers produced according to the invention are primary hydroxyl groups.

Furthermore, it has proved advantageous if the total content of Sthylenoxydresten 6-12 wt.% Of Alkylenoxydreste located. If the content is on the order of 6 #, the non-terminal ethylene oxide blocks should preferably constitute two percent by weight of the total amount of alkylene oxide residues, and if the content is around 12 % , the terminal ethylene oxide blocks should be about 6 S of the total alkylene oxide residues present; and in addition between 20 % and 40 ^ of the hydroxyl groups present should be present as primary hydroxyl groups, '

The position OCE -Athylenoxydblocke may be considerably below differently "how can the reference to one of the particularly advantageous friole with a molecular weight of about 3500 iraranschaulichen * * Such triol built amf glycerol, LHAT the general-IPoranels

^ OH

where a, i> * »dc ifuljL oiler mean a positive integer \ m§. $ 0 e $ f * € * & * Aj d * * ». 1 represent positive whole choices;

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a + b + c = ρ; d + "'« τ + f ■ qj g + h + i = r and j + k + 1 = s

then the molecular weight of the triol M can be calculated as follows:

M β 92 + 44 (q + s) + 58 (p + r), and in the illustrated case it is J55OO.

The percentage by weight of ethylene oxide residues, based on the total content of alkylene oxide residues, can be calculated as follows Calculate equation:

4400 (q + s)

44 (q + s) + 58 (p + r);

the percentage by weight of terminal ethylene oxide residual groups is given by the following formula:

4400 Cs) ,

44 (q + s) + 50 (P + r)

and the amount of separated from the terminal groups Ethylene oxide residual groups can be determined according to the following formula:

4400 (q),

44 U + s) + 5Ö (P + r)

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For the individual case, the values for (p + r), q or s are determined by the molecular weight of the triol and the criteria given above. If the polyaddition of the alkylene oxide onto the alcohol component is carried out according to customary tests carried out in individual batches, the position and length of the alkylene oxide radical blocks can be varied in a simple manner; so you can for example. wise, in one embodiment of the process according to the invention, the block represented by ρ can be omitted and the first ethylene oxide and propylene oxide block units directly adjoining the ethylene oxide and propylene oxide block units directly following the terminal OH groups are closely connected to the initiator, so that this is hidden very deep in the molecule. Another extreme case is that in which the original propylene oxide residue block is relatively large and accounts for up to 90% of the alkylene oxide residue content. Preferably, according to which the terminal OH group following Äthylenoxydblock arranged Propylenoxydblock should not be more than 3 wt.% Of Alkylenoxydreste, however, if the the terminal OH group, the following Äthylenoxydrestblock ensure that 15 to 50% of the hydroxyl groups present as primary hydroxyl groups, then the blocks p, q, r can be divided or mixed in series of smaller blocks, and there can even be a random distribution in the manner of copolymer formation, by adding a mixture of ethylene oxide and propylene oxide in the desired ratio to the reaction vessel.

The amount of ethylene oxide that is required for the Such terminal blocks can be formed in the reaction which give the desired content of primary hydroxyl groups best described as the number of moles of ethylene oxide per hydroxyl group of the initial connections? Brought reaction

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must be, i.e. the polyhydric alcohol with which the alkylene oxides implemented. A guideline with regard to the quantities to be converted is given in the following table:

Moles of ethylene oxide per Hy % of primary hydroxyl groups droxyl group (in end in the product standing blocks) 0.2 0.3 20th 0.44 25th 0.58 30th 0.75 35 0.95 40 1.18 45 1.46 50

Sometimes there may be slight deviations from these results, depending on the reaction temperature, the pressure, the amount of catalyst used, the rate of ethylene oxide addition, the stirring intensity or the relative volume of the gas phase and liquid phase in the usual reaction vessel for batches Reaction. These deviations are probably due to an excessively high reactivity of the ethylene oxide in comparison with that of the Propylene oxide and are possibly also due to the fact that the vapor pressure of ethylene oxide is higher than that of propylene oxide at the same temperature. This is subdued are generally unimportant since a person skilled in the art can easily control and adjust the reaction conditions.

From the table above it can be seen that the amount of ethylene oxide which is required if you want to win terminal blocks with 15 % primary hydroxyl groups or 50 % primary hydroxyl groups in a triol with a molecular weight of 3500, 0.8 wt. # Or 5.7% by weight of all alkylene oxide present

matters. 0 0 9 8 1 1 / U 0 7 °

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The polycondensation of the alkylene oxide with the initiator is preferably carried out in the presence of an alkali metal catalyst. Such catalysts include sodium or potassium, which are present in the Initiator for sodium or potassium alkoxide, sodium or potassium methoxide, Sodium or potassium hydroxide are dissolved.

The new polyols prepared according to the invention can be used alone or in a mixture with other polyols in the process according to the invention use, or you can use mixtures with conventional polypropylene oxide based on polyols.

In the formation of the polyurethane compound, an aliphatic, aromatic or cycloaliphatic compound can be used as the organic isocyanate compound of the formula (RNCX) _n ^, and this can contain substituents, provided that the substituents do not interfere with the reaction. Isocyanates or thioisocyanates in which η is 1 or 2 are preferably used, and those in which η = 1 are particularly preferred. Examples of such compounds are polymethylene diisocyanate and dithioisocyanate, hexamethylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, 1-methyl-2: 4-phenylene diisocyanate mixed. isomers of l-methyl-2: 4-phenylene diisocyanate and l-methyl-2: 6-phenylene ^{diisocyanate, 4,4 t} -diisocyanate diphenylmethane. It is preferred to use products which are derived from aromatic diisocyanates, in particular those from toluene diisocyanate which contain about 80% of 2: 4-toluene diisocyanate and 20 % of 2-6-toluene diisocyanate. -

It should be mentioned again that the new according to the invention

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Polyhydroxypolyäther produced both an independent control allow their gelatinization properties as well as adjustment allow their surface activity and binding force for solvents, since the ratio of Äthylenoxydresten in the endstänv ■ digen block determines the content of primary alcohol groups (and consequently the gelatinization properties), while the total amount of ethylene oxide residues is decisive for the surface activity and the behavior towards solvents.

The surface activity properties and the absorption capacity for solvents can be determined by measuring the "Gloud Points" of the polyols. This method (sdfifce to be described in detail later) assists in measuring the temperature under standard conditions at which the polyol no longer dissolves in a mixture of isopropanol and water. Since the release handle of this type of polyol decreases with increasing temperature, the higher the surface activity of the polyol, the higher the cloud point. It has been found that the cloud point of the polyols prepared according to the invention depends on the molecular weight of the polyol and, in particular, on the amount of polyethylene oxide residues contained in the substance. The function of the position of the Äthylenoxydreste is less important compared to uer total existing amount of Äthylenoxydresten. The strength of fit for solvents depends on the solubility of the polyol in water, and it is usually about 30 times greater than the solubility of the polyol in water.

It is believed that in the particularly important first stage of the process in the reaction leading to urethane formation

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"■■ Polypi .. acts as a surface-active agent and the solvent absorbed by this forms a homogeneous solution or a dispersion with the water, the catalyst and the water-soluble silicone oil (foam stabilizer) in the essentially hydrophobic mixture of toluene diisocyanate, trichloromethane and polyol each desired minimum solubility limit of water in the polyol depends on the employed mixture whose water content and the initial temperature Although there is no absolute lower limit in this respect, it was found that with a polyol between 3 -. to 3.5 $ water is capable of dissolving, foaming is difficult to achieve at a temperature of 25 ° C - a polyol that is capable of dissolving between>, 5 and 4% water can be foamed under conditions that are reasonable for most commercial compositions without the need for special manual skills for the specialist carrying out the foaming would be rlich. However, a polyol that dissolves between about 4.5 and 7.5 percent water is preferred, and in particular, if optimal foaming results are expected, a polyol that dissolves between 5 and 7 percent water should be used.

Surface activity and mixing capability are more important properties in the formation and deformation of the Sohauras, and in the latter case, the gelatinizing is (duroh which is caused, the strength of the foam material) is of particular importance _t since by this the propagation of the foam is caused within the mold. If the speed of gelatinization is too great, cracks will appear in the foam, and if the speed of gelatinization is too slow

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is, the skin develops poorly and shows insufficient cohesion. If the polyols, for example a mixture of polyols, are not sufficiently homogeneous, then the catalyst balance is poorly balanced and the foaming temperature is extremely sensitive. The preferred content of primary alcohol is between 20 and 50 % of the alcohol groups present, and in particular between 20 and 4%. To illustrate these independent control measures, a group of polyols with an average holetailar weight of 3500 were prepared from glycerine. The results are presented in the table below and show how the cloud point, primary alcohol content and water solubility vary depending on the structure.

For comparison, control polyols are the same as the usual polyols under the test numbers 1 * 1, 1.2, 1.3, 1.4, 1.5, 1.8, 1.9 and 1.11 listed.

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Polyoxyalkylenetroles with one in end
ständi
gene
Blocks inner
half
of Mon
leküls Cloud
Point 7/15 C. J885: * Table I. 0 0 ⁰ C Molecular weight from 3500 ¹ "■ 11 Q 0.5 Ethylene oxide residual content
in parts by weight of alkylene
oxide residues 0 4th 40 solubility
in water
g / 100 ml & n Ver
search- in total
velvet 4th 0 16 Polyols
at 25 C % primary
Alcohol-
groups No. 0 6th 0 19th • 3.5 1.1 11 4th 2 28 100 5 1.2 ,. Λ * 2 4th 20th 4.4 63 1.3, 4th 0 6th 21 4, ö 5 1.4 6th 8th 0 24 5.2 45 1.5 6th 4th 4th 30th 5.4 50 1.6 6th 0 8th 27 4.8 35 1.7 6th 4th 6th 31 5.1. 20th 1.8 Ö 34 6.2 5 "1.9 8th 5/5 55 1.10 8th 6.0 . 36 1.11 10 6.5 5 1.12

According to a special embodiment of the method according to the invention the polyurethane resin can be the prepolymer made by Reaction of polyhydroxypolyether with a stoichiometric excess of polyfunctional isocyanate under such conditions has been established that the ratio of NXC groups to OH groups greater than 1.5: 1 (isocyanate-terminated reactive prepolymers resulting) is. It is even more useful if the isocyanate Is toluene diisocyanate and the ratio of NCO: OH between 1.5: 1 and 2.5: 1 and the reaction in the presence of 0.1 wt. Water (calculated on the polyether) is carried out; The reaction is expediently carried out by heating the reaction components to a temperature of 80-120 ° C. for 30-240 minutes

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_{f |} 157Ό & 85

by. These reactive intermediates can advantageously be converted into other urethane derivatives.

The structure of these reactive prepolymers can vary considerably depending on the ratio of isocyanate groups to hydroxyl groups and the type of polyhydroxy polyether or mixture of these which are employed. If diols are reacted solely with toluene diisocyanate, essential linear intermediates are obtained which, in their final form, give soft products. With triols one obtains reactive intermediate products which have at least three branched chains, each of which bears an isocyanate group at the end, and which can be very strongly branched, and with these products hard resins can be obtained during the final reaction Suitable combination of diols and triols In general, any given reactive intermediate can be cured by incorporation of small amounts of polyhydric low molecular weight alcohols such as ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol, sorbitol, and the products can be plasticized or plasticized by incorporation of a lesser than molar amount of a monohydric alcohol, for example by the general formula R ^f (0 CpHj.) (0 CpHg). OH can be illustrated where a and b are zero or a positive integer and R ^{f is} a hydrocarbon radical. Examples of such alcohols are butanol, Ocfcmol, cetyloleyl alcohol or nonylphenyl. When adding these additives, care must be taken to ensure that the overall ratio of MCX: OH is used in order to achieve good results

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does not hold less than 1.5 * 1 '. You can also use the reactive Prepolymers in undiluted form or mixed with other quantities of di- or polyfunctional isocyanates or isocyanates of the same or different type. The intermediate product can, either on its own or in a mixture with further isoyanate, can be used in the form obtained, or one can

don't put it in a solvent that is essentially related to the isocyanate groups reacts, use diluted. Examples of such solvents are toluene, the xylenes mixed with hydrocarbon fractions, carbon tetrachloride, ethyl acetate or acetate of ethylene glycol monoethyl ether.

If you have the reactive intermediate over a considerable amount Want to cancel time span, the production should expediently in the presence of small amounts (e.g. up to 0.01 #) one Acid chloride, for example acetyl chloride, benzoyl chloride or Chlorobenzoyl chloride. You can also instead prepare the prepolymer in a solvent.

The inventive method can be used if you Wants to apply prepolymers, using the solution of the reactive prepolymer as a means of producing a surface coating on wood, metal or leather if you use one a smooth surface finish or painting. The hardening The reactive intermediates can be used with or without a catalyst make. The solvent is preferably allowed to evaporate from the film applied to the surface to be coated, and the reactive intermediate is by reaction of the terminal Isocyanate groups with the humidity or with reactive Cross-linked groups in the substrate. According to the invention

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1 * 15708 * 5.

produced new polyhydroxypolyethers are in this invention Particularly effective application as they are somewhat hydrophilic; the humidity in the air can thereby be absorbed more easily, and nevertheless cured films are obtained which have good hydrophilic properties Have stability. As will be apparent to a person skilled in the art, numerous variants of this system can be practiced.

Another advantageous type of application of the method according to the invention consists in partially impregnating leather in order to improve its wear properties, as described is in the applicant's parallel application no. L45 IVd / 39c. In this case, the intermediate products are partially allowed to react with groups of the leather fibers and partially crosslinked them by reacting with water.

The reactive intermediate products can be hardened to form rubber-like substances, which are molded into the desired shape. Blessed curing agents are those compounds which have two or more groups with which the terminal isocyanate groups of the reactive intermediate are able to react. Examples of such compounds are substances with two or more of the following groups: hydroxyl groups, primary amine groups, secondary amine groups or carboxyl groups. Such compounds include ethylene glycol, 1,4-butanediol, ethyl; enediamine, hexamethylenediamine, diethylenetriamine, m-phenylenediamine, 2-amino-inapthol, 2-aminoethyl alcohol, aminobenzoic acid, aminoacetic acid, hydroxide acid, 4.4 ^l -dichanordiphenyl-3-diaminodiphenyl.

The novel polyhydroxy ethers made in accordance with the present invention can be made into prepolymers for flexible urethane foam by any one

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the usual working methods. For example, 1.1 equivalents of isocyanate groups, which are usually present in the form of 80 % 2 ° toluene diisocyanate and 20 % 2x6 toluene isocyanate, with one equivalent each of hydroxyl groups in the polyol at a temperature of 10 ° C for about 2-3 hours, until the viscosity has reached the desired value (often 3Q0 cP at 105 ° C). An excess of isocyanate is added to this mixture at 105 ° C. in order to bring the free isocyanate content to 8-10%. The free isocyanate content can be determined by titration with dibutylamine and is expressed as the percentage by weight of NGO groups based on the total weight. The prepolymer is cooled as desired to 20 ° C and has a viscosity of 1000-25000 cSt, depending on the composition. It can be prepared by reacting about 100 parts of the prepolymer with 2.5 parts of water in the presence of a tertiary amine catalyst - * Sator converted into a flexible urethane foam ^ where the catalyst is advantageously present in an amount of 1 part of N-methylmorpholine and 0.5 part of triethylamine. Here ilikonöls low viscosity should be incorporated as Schaumstabilisierungsiiüfc tel in the reaction mixture up to a part of a water-insoluble ^ü. A polydimethylsiloxane with a viscosity in the range of 10-100 oSt at 25 ° C. can be used as the water-insoluble silicone oil; the particularly suitable silicone oil has a. Viscosity of 50 cSt at 25 ° C. You have to cure these ^ foams for several hours at 120 ° C before they have reached their maximum strength. The presence of ethylene oxide fragments facilitates the difficult addition of quantities of water and catalyst to the mass,

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One can manufacture the foam in such a way that it absorbs good energy Has properties and low rebound properties, so that it is particularly suitable for fragile parts in cars. The production of prepolymers and their further processing has therefore a particular advantage because you have the option of using two different isocyanates with largely different reactivities use, since the time and the temperature can be varied during the preparation of the prepolymers. However, it is desirable that the iso.oyanate used for dilution is 2: 4 toluene diisocyanate (Ratio 80/20) is. In a similar way, one can also use polyols with largely different reactivities according to this Build up work style.

The products manufactured according to the invention have the greatest importance and the greatest value for the one-step formation of flexible urethane foam, in particular for one-shot molding. In the known one-step processes, the foaming of the polymer mass takes place during the additional chain lengthening by means of carbon dioxide, which arises from the reaction of the isocyanate groups with the water (which is preferably present in an amount of 1 - J% ) as follows:

R.NCO + H ₂ O - ~ * k NH.CO.flM.R

The crosslinking reactions then take place by means of this Reaction substituted with an excess of isoeyanate groups Urethanes as follows:

. * go -

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- R NH. CO. HN. R- + - R.NCO -> - R.N.CO.HN.R -

CO.NH.R

Additional propellants can have a reinforcing effect, using volatile halogenated hydrocarbons with boiling points below 50 ° C at 76O mm pressure, such as methylene dichloride or trichlorofluoromethane, or mixtures of such substances are used »

The catalysts generally used for the production of the commercially available single-stage foams are chosen with advantage, including tertiary amines, such as 1,4-Dlazay bicyclooctane, N, N ^f -tetramethyl-li> -butanediarnine, N-methylmorpholine, organotin catalysts, such as Dibutyltin dilaurate, and salts of divalent tin such as stannous ooate. The catalysts which are particularly advantageous for these purposes are a binary or tertiary mixture or a mixture consisting of even more components. If you choose a composition of tin octoate-1,4-diaza, bicyclicpoctane, you can reduce the total concentration of catalyst to 20 "■> 30 % if, instead of a conventional polyoxypropylene, a polyhydroxy polyether prepared according to the invention, based on Trol with a similar molecular weight.

Particularly valuable results in deformation can be obtained with a catalyst combination as in the parallel ongoing registration of the applicant with the file number ' L 50 169 IVo / 39b is described * Preferred catalyst combinations, as described in the aforementioned application DeschrieDen Herd,

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are Ν, Ν-dimethylethanolamine, Ν, Ν-diethylethanolamine, N ,, N-dimethylisopropanolamine, which are used together with a salt of divalent tin, preferably tin octoate.

Foam stabilizers which can advantageously be used are polysiloxane polyoxyalkylene block copolymers, such as SiIikonöl L-520, a commercial product from Union Carbide Corporation, which is believed to have the following average composition:

0 (Me ₂ SiO ^ (C ₂ H ₄ O) ₁₇ (C ₅ H ₆ O) ₁₅ 0 C ₄ H ₉ 0 (Me ₂ SiO) ₆ (C ₂ H ₄ O) ₁₇ (C ₅ H ₆ O) ₁₅ 0 C ₄ H ₉ 0 (Me ₂ SiO) ₆ (C ₂ H ₄ O) ₁₇ (C ₅ H ₆ O) ₁₅ 0 C ₄ H ₉

Other polysiloxane-polyoxyalkylene copolymers which can be used with advantage are described in the applicant's parallel application no. L 48 350 Ivc / 39b.

Since the new polyhydroxypolyethers produced according to the invention have a hydrophilic part, they can be mixed very quickly with the isocyanate and the organotin compound or the tin salt on the one hand, and also mixed well with the aminocatalyst, the silicone oil and the water, which are usually in the form of an aqueous solution, on the other hand can be added. It has been found that, assuming normal mixing times, the speed of the agitators can be reduced to $ 0% compared to the speed required to mix polyoxypropylene-based polyols of similar molecular weight. The foaming reaction is remarkably simple, and im

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In contrast to polyoxypropylene triols with molecular weights of 3500 and more, even foam structures can be achieved in a simple -Wedse.

It has now become easy to produce foams, as a result a denser structure harder or by reducing the Density, especially due to the incorporation of trichlorofluoromethane as a propellant, softer can be adjusted. The foam has extraordinarily good rebound properties and is quite substantial better tensile strength and elongation values than commercially available foam with the same density, which is made from polyoxypropylene triols will.

The examples given below serve to describe the process according to the invention and its application in greater detail Unless otherwise stated, quantities are given in terms of quantity. percentages or parts by weight.

The foam made in these examples below were tested according to the following standard methods:

Compression - British Standard Specification No. 337951961 * wherein a test specimen is compressed to 25% of its original height and held at 70 ° G for 22 seconds. After recovery, the loss in amount is given as a percentage of the original amount.

Elongation to break and tensile strength: British Standard Specification No. 3379: 1961, the tests were carried out on a standard foam after heat aging for 16 hours at 140 ° 0 U _n ^

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Moisture aging in a steam autoclave for 3 hours 105 ° C.

Hardness; According to British Standard Specification No. 2379:

I96I checked, with the difference that a flat disc with

ο an area of 322.6 cm was used. The sample was 2 inches thick.

Springback properties: Ball fall technology results as impact height as a percentage of the fall height.

Tensile strength: Samples with the dimensions 15 * 24 χ 2.54 x 2.54 cm were cut 3.81 cm deep. The two sections were pulled apart at a clamping speed of 508 cm per minute.

Cloud point; The temperature at which a 50/50 volume sample and a 50/50 weight percent mixture of isopropanol and water became cloudy.

Reference is made for the manufacture of single-stage urethane foam on the T.D.I. Index. This contains the excess of toluene diisocyanate defines that in the compositions on the stoichiometric requirements of hydroxyl-containing substances

■ ΐ

in addition, their acidity, their water content and the additional amount of water that is used to generate carbon dioxide to expand the foam «The amount of toluene diisocyanate T in percent by weight, necessary for the implementation with 100 Gew.Jt

• c Pll

00981 1 / U07 ^ßAD ORiGiN

of a polyether is required to have the following characteristics Has;

Hydroxy value = H mg KOH / g Acid number = A mg KOH / g

Water content = w wt.%.

and which contains additional water (in % by weight per 100 of polyether) = W is given by

T = TDI index ^ ₁₅₅ χ ( _{H +} A) ₊ 9.67 (W + w) _ / "...

Numerous kinetic methods have been used in the past few years with which the content of primary hydroxyl groups in Polyalkylene polyols should be determined in which mixtures of primary and secondary alcohol groups are present. These analytical methods are based on the different rate of reaction of the hydroxyl groups and are well known to the person skilled in the art.

A suitable method to use in the investigation of the invention Polyhydroxypolyäther produced can apply, based on the different Veresteruhgsfrequenz of primary and secondary hydroxyl groups with phthalic anhydride, This method is carried out as follows:

A precisely weighed amount of polyether is poured into a 200 ml Large bottle filled with 25 ml of dry fyridine are; the weight of the polyether used rubbed depends on the hydroxyl number and is about 60 g for a hydroxyl number between 40 and 50 and 50 g for a hydroxyl number

between 50 and 60. The flask with the sample is in a

00 9811/140 7 BAD ORJGiNAL -25 «

bath kept at constant temperature is used. The temperature depends on the content of primary hydroxyl groups to be achieved; that is, if one expects a primary hydroxyl group content of less than 20 % , then a constant temperature bath of 25 ° C is used, and if one expects a primary hydroxyl group content of more than 20% , then the bath is used at a Temperature of 35 ° C. It then becomes a

second flask with 400 ml of an approximately one molar solution of Phthalic

acid anhydride in pyridine is used in the bath kept at constant temperature. After 50 minutes, 100 ml of the phthalic anhydride solution are pipetted into the flask containing the sample, and the solution is made up to 200 ml with dry pyridine. The time at which the mixing occurs is set as time zero.

10 ml samples are taken every half hour for the first two hours taken and analyzed, and during the further 4 hours Samples taken every hour. The samples are placed in a conical, 250 ml flask, 5 ml of water are added added to bring the reaction to a standstill, and the solutions are made against standard 0.1 normal potassium hydroxide solution with phenolphthalein titrated as an indicator. A sample of the pure pyridine-phthalic anhydride solution is titrated in the same way. the end the difference between the blank titration of the phthalic acid anhydride reagent and the titration of the test sample is the concentration of hydroxyl groups "x" (in moles per liter) that corresponds to the corresponding Time "t" were implemented, determined. From the titration value the initial concentration of phthalic anhydride "b" (in moles per liter) is calculated on the blank sample. From the hy-

00981 1 / U07

ORIGINAL BATHROOM - 26 -

hydroxyl number of the PolyätUerpolyol and the weight of the used Sample WjLrd the initial concentration "a" in moles per liter Hydroxyl groups calculated. If you then get the values for

log ( b - x) versus time t, then initially (a - x)

the points on a smooth curve. Later the points lie on a straight line, which is characteristic of the reaction of the secondary hydroxyl groups. If you extrapolate this line to time zero, you can use the intersection "z" * to calculate the content of alcohol groups that are present as primary alcohol groups. - '
It applies!

z = log

if χ is the concentration as primary hydroxyl groups in moles per liter, and therefore the percentage of alcohol groups is di "e are present as primary alcohols, = 100 χ.

Example I.

A low molecular weight condensate from {Jlyeerin / liÖ Propylene oxide * molecular weight 57O and hydroxyl number 295 mg < KOH / gj, was obtained by reacting glycerine with 1: 2 propylene oxide produced in the presence of potassium methoxide as a catalyst.

13.6 kg of this unneutralized material were put into a autoclaves equipped with a stirrer and heating and cooling devices filled. The air was displaced by means of nitrogen,

00981 1 /14.0 7 - 27 -

uiid then 0.48 kg of a 50% strength aqueous potassium hydroxide solution were added. The mixture was stirred and heated under vacuum and kept at 115 ° C. for about 2 hours. 3.4 kz ethylene oxide were then pumped in at such a rate that the temperature rose to about 115 ° C. and the pressure 1.41 kg / cm After the addition was complete, stirring was continued in the container until the reaction pressure had dropped to zero. The product was further reacted with about 68.4 kg of propylene oxide, which was fed in at such a rate that that the temperature was kept at about 115 C and the pressure at about 4.92 ktj / cm. After the pressure was increased to about 0.14 kg /

2
cm had fallen, the container was evacuated and the product was further reacted with ~ $, h kg of ethylene oxide under the conditions described above as in the case of the first addition of ethylene oxide. After the pressure had dropped again to about zero, the container was evacuated, purged with nitrogen, and the product was neutralized and filtered. The amount output, calculated on the material introduced, was 98 #. The hydroxyl number of the product was 47 * 5 * which corresponds to a molecular weight of 3540. It was calculated that the main block of 1: 2 propylene oxide residues in the polymer with the low molecular weight accounted for 13.1% of the alkylene oxide residues, the following block of ethylene oxide residues was 3 * 9 % , the penultimate block of 1: 2 propylene oxide residues was 79 * 1 % and the terminal Äthylenoxydrest block 3 * 9 # made up. The physical properties are given in Table 2. Those physical properties * which the products produced according to the invention differ from the usual triol-based polyoxypropylene compounds

differentiate
'gen and the products * to which ethylene oxide is attached are

009811 / U07 >. 2B 4 ''

BATH

higher specific density ^ the ability to dissolve more water. and the higher cloud. "" Point *

'■■ "' ■ Bgi ^ gpial" 2 .. "'"'
The products conjured up in this example all have molecular weights of around 3500 and are almost the same. Wet be like. in "Example 1 besc.hF & ebsß, manufactured _a The conditions are so changed _# .that. the position and. size of the. blocks are different" ». From the physical properties given in Table 2 it can be seen that. the Cloud- foint-unü 'die. ^: Measures "absorption" increase when the ethylene oxide residue rises and - when the block of ethylene oxide residues at the / end is closer - to the terminal hydroxyl groups . "-. ■ ■ -, -.-.; - ■ :. .-.: ■ · ■.

As a control and 2U ". 'Vergl @ iöhSÄW @ ok © n some.-Polyple
synthesized in which all S.-fehylesoscydreate as endsfeSndiger. "■ block were present, ■ and-anasi ³ ©,. in which © lie
s te as not final. Blocks-were-present .- ■

- 29 Sf ί 1/140 7 .. BAD OBlGiHAL

% Oxyc Ä.O. P.O. K. O. OH- Tabel 2 Viscosity (RSt) 27.7 C a Refractive Example no. 2.9 79.2 2, 9 number Molecular 100 C 25 ⁰ C index 4.0 O O weight 222 nD ²⁵ I admitted to 4.0 82 O 47.5 27.2 288 522 1.4525 1 Glycerin 6.1 O O 47.1 2540 27.7 207 548 1.4520 2 ■ · (control) P.O. 6.0 oil O 45.0 2575 40.2 ayi 591 1.4522 2.2 (control) 12.0 8.0 O O 47.5 2740 27.1 271 522 1.4522 ■ 2.2 (control) 96.0 2.05 81.0 4, O 4y, 2 2540 27.4 2yy 52b 1.4520 2.4 (control) 12.0 2.8 81 2, 10 47.2 2420 2b, 5 209 555 1.4525 ' 2. 5 (control) 94 5.7 77 2, 9 46.5 2550 2t, 1 271 501 1.4522 2.6 12th 4b, O 2620 27, b 279 525- 1.4522 2.7 92.0 46.5 2500 2o, 4 566 1.4525 2.8 12th 2620 I.
O
- ». f
UT O
O 12th 0 ■ · - ·
GO. j (O
OO 12th ; ■ - ■ ■ - "'" ... * · * ■■■■ '■■ O

Clear
Point
⁰ C cioua-
Point % primary
OH groups 1570885 β Polyol Specific
density
85 ° c -27 27 + Solubility
of water 1.011 -30 19th 40 • 5 * 5 ■ ' 1.011 ^ -30 16 5 • 4, ü ',, ■, ι, οιο -30 2 B 49 'ί ■■ ' * ' 1.012 -29 24 5 5.2 1.012 -30 30th 56 ,, 5,2 ■ (, ' 1.014 -31 23 35 o, 2 1.013 -30 21 20th 5.0 1.012 -30 ^ , b 37 4, G 1.016 + g on »Jasser / 100 ml I. 8 6 00

It / "> S

, Umstellung ^c ines κ « shaped Urel'-jan pillow

The polyether of Example 1 was used to make a flexible molded Ur-ethaa pillow as follows used;

GewAoMsttlle

Polyether (hydroxyl value = 47.5 mg KOH / g) 100

Tin octoate 0.2

Tri chi or * '] ·.,? or me tnan. 2

Water J », 4

Dimethylethanolamine 0.8

Silicone oil (L.520, as previously described) 1.5

80/20 toluene diisocyanate (T.D.I. index -104) 41.9

The components from this combination are served in four portions shared

Portion no. Qewloht parts Polyether I. ■ :. 96 Polyether [ 4th Tin octoate < II 0.2 Trichiorfluoromethane , 2 Water ] 3.4 Dimethylethanolamine < III 0.8 Silicone oil L-520 \ 1.5

80/20 toluene diisocyanate IV 41.9

The four servings were poured into individual containers of a foam spreading machine equipped with heat exchangers, and the main servings I and IV were regulated to 24 ° C. The pump was set so that insgiesaiat 9 kg

0 0 9 8 1 1 / U 0 7 _fiÄn . '■■

SAD OHiGiNAL -? Ί -

Minute -dessladen '% w & a®n _a iiööei- öi® SMpepisiaB © » im calibrated ' im & am® vt% ® es" tier

Sine ^: Qi $ .® & tarm- ans AMraiiiiiaa mlfe-etem 23 1, Pias a g © eöiiö. @ Rfc © B DselceXt-sÄi £? Af.5ü _it keä fsü. feesfe @ h @ M © n MnW © F ^ MSfpaitfe ©! h®hozi & ® &% ~ v * m & -eil® la QiMssm E @ tMlMit, ®g (sn on 40- S eiar © g? iil @ rfe _o bis desi

ii in "eiaei" - g ^ .in Keafeatefe-gebra.Äfej- -ö # f © 1p. ©

digJceit voa 1500 Örriäf ^ liwigeÄ / Miniit © eiliofo '-tos .ä was, © in © ".so ausE'eiohend © ll © Bg © d © ^ ¹ g @ raig © iifc @ r &

^: dt® form. "- in 5 ρ 5 S © kunö © n

- miä in ö © r "St © S.Ximg festge & XeranW and € ®ü Gans © .tiis? de In at 1S5 ° ö - getel-feeacsB Heiilisftofaa © ing © s © fcz-t _e - MasEs 20 ■:"

ivy © ssi los ⁵ liig®Äss.fe aüfwieso lieim maa ssus Ieich

fegt.cf ₅ - scs fesimife © ^ - -i-ii © gsfimdsn -iäb ⁵ ©! ® ^ --Foffiiiliog © in--

- ia

tjn? öo © fetm S

ORIGlMAL BATHROOM

average density kg / nr ⁵ = 36.

Pillow thickness about 9.8 oai

Identity hardness index (1)
• (kO ) ύ compression - about 30.5 cm

Diameter of the Identor) ■ 34.3 kg

Static identification check (2)

Identification hardness change in % ** 14

- 1.4

- kg / om ² «■ 1.24

Elongation at Br'ach (3) % »■ 300

Tensile strength (4) s - kg / cm - 5.7

permanent compression (5) * - % - 6.5

en

The tests described above for determining the physical properties, tests (i), (.2) and (3) and (5) are described in British Standard Regulation 3379 * 1961, Annex A, B, C and D. Test (5) was carried out according to the specification of the American Society for Tests and Materials, - ASTM Bestirnffiungi D 15ü * f-5 ^ r, Appendix 0.

The moldings, 41e from Example 1 produced new ones. Polyethers have been developed, have excellent physical properties, oeisplelawelse very high tensile strength, elongation. Bi'ucn - ^ a Zerrelüi'eutl ^ i & lt and let siöin nonetheless be easily misrepresented, so that one obtains form bodies that are free of internal and dated defects.

Example 4

The polyols listed in Example 2 and in Table 2 as 2.6, 2.7 and 2.8 are: r ^; i? b: in are, as described in Example 3, ix ν 3-f foam ⁵ ; ■ ** ';.,. r.usi ^ i'onat "The resulting living ** foam bodies had g <.; ie pfc

Patent a 0038 · ί / UO?

SAD ORlGiMAL

Claims (1)

a'fchsrs αϊ !!; a molecular weight from 1000 to -60-0O ₀ die.dr * 5l "or melir hydroxyl groups, contain per molecule, which are suitable for the production of Folyyretlianvef'bindUii ^ eii ^ in which an inehr & ^T e3? ^r : i a Älkalimefeallkat.alysators be .gebracht the reaction iiiuo Tithyienoxfu in the presence, characterized gek _'s n'niseicnnet- that la · Ejner first Verfaiirensstufe - ■ ·> ger-.Alkohol with three or Bielir HyciroKylgrwppeii medium-IIZ propylene oxide. the strong alcohol either one after the other or (each of them converted propylene oxide and ethylene »■ then added propylene oxide to the product resulting from the first process stage in a second process stage, and finally ethylene oxide to the product resulting from the second reaction stage in a final process stage i ^ an amount of 0.2 to 1 * 46 mol per hydroxyl group in the polyhydric alcohol per molecule of this polyhydric alcohol is added, with the total amount of ith reacted ylene oxide is zv / isehen k and 20 % of the total amount of reacted alkylene oxide, 2. The method according to claim 1, characterized in that a triol is used as the polyhydric alcohol. "3" »method according to claim 1 or 2, characterized in that that the propylene oxide in the second process stage in an amount of at least 1% by weight, based on the total amount of reacted alkylene oxide, used. , - 34 00 98 1 1 / U07 BAD ORIG'NAL 4. The method according to Anapruuii 1 - jj, characterized in that the ethylene oxide in the last process stage in a Mcii ^ e of C, j biü O ₁ Jl ^ mol each in your r..ehrv; erti ^ en Alrtonol contained ⁰ hydroxyl group used. ^{00981 l / 1} ^ 07 BADOR _IG , _NAL - 35 -