DE1694583A1 - Process for the direct one-step production of urethane-urea foams - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. BEAUTIFUL FOREST DR.-ING. TH. MEYER DR. FUES DIPL-CKEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLDPSCH COLOGNE 1, DEICHMANNHAUS

April 14, 1970 Ke / Ki

Marles-Kuhlmann-Wyandotte,

25, Boulevard de 1'Amiral Bruix, Paris (France)

Process for the direct, one-step production of urethane-urea foams

The invention relates to a straightforward one-step process for the production of urethane-urea foams.

Polyurethanes are usually considered the product of the reaction of a polyisocyanate with an active hydrogen containing organic compound, for example one containing terminal hydroxyl groups Polyester, polyesteramide or polyether. By maintaining an excess of polyisocyanate in the reaction mixture and by adding water during " the chain extension and crosslinking phases of the reaction the polyurethane product can be obtained as a foam which is suitable, for example, as insulation or for upholstery purposes.

Various processes are known for the production of polyurethane foams. The manufacture of polyurethanes is well known in many references ₄ such as "Polyurethanes" by Bernard A. Dombrow, Reinhold Publishing Corporation, New York 1957, and "Polyurethanes Chemistry and Technology" by JH Saunders and KC Frisch, Interscience Publishers, New York-London .

009849/1798

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In the prepolymer process for the production of polyurethane foams is the polyisocyanate in stoichiometric excess first with an active hydrogen containing implemented high molecular weight organic compound, whereby a "prepolymer" is formed. The "prepolymer" and water are then mixed, the "prepolymer" being polymerized and crosslinked, while excess polyisocyanate and water are formed to form gaseous Carbon dioxide react, which acts as a propellant.

In all processes in which water is used to release carbon dioxide Is used for foaming the polyurethane is due to the reaction of the water with free isocyanate or isocyanate residues in addition to carbon dioxide also form an amine, and the amine thus formed reacts with further free isocyanate or isocyanate radicals to form Urea bonds in the foam. The urea bonds result Foams used in many applications in terms of the combination of properties including mechanical Strongly superior to strength with flexibility and solvent resistance over a wide temperature range are.

It is economically advantageous to manufacture urethane-urea foams by a direct one-shot process in which all of the components required for manufacture are simply mixed together, poured into a suitable mold, and crosslinked. In a known one-step process for the production of foams, polyhydroxy compounds, water, diisocyanates and other substances are mixed with one another at the same time, and the mixture obtained is immediately injected or poured into the eleventh mold. In a variation of this process, the "Vormiscli process", the polyhydroxy compound, water and any other substances are mixed first and then mixed with the appropriate amount of polyisocyanate. The term " Einsufen- 0098Λ9 / 1795

process "includes both the process in which the reactants all mixed at the same time and foamed immediately, as well as the "premix" process mixed with polyether, diamine and other substances first the mixture is then mixed with the appropriate amount of polyisocyanate will.

When water is used in the reaction to form the carbon dioxide and urea bonds, it is difficult to the density of the foam and the amount of urea bonds in the production of a polyurethane-urea - Foam can be adjusted independently because of urea bonds and carbon dioxide are formed simultaneously in approximately equimolar amounts by the reaction. For example is often an excess in a foam with strong carbon dioxide formation and low density of urea bonds obtained above the desired level, and vice versa in the production of a foam with low carbon dioxide formation and high density, insufficient urea bonds for the desired ones Properties are obtained. It was therefore suggested that Solvent-type propellants, such as fluorine chlorine than, as a total or partial replacement for that caused by the polyisocyanate-water reaction to use formed carbon dioxide. Examples of such propellants are trichloromonofluoromethane, Ditshlordifluoromethane, Monochlorotrifluorathan, Tetrafluorocarbon, Chloromonofluoromethane, monohalodifluoromethane, Tetrachlorodifluoroethane, trichlorotrifluoroethane and dichlorotetrafluoroethane.

By adding these gaseous blowing agents, foams with a low density can be produced without the formation of excess! [-.- η * urea bonds are established. In the production of a foam with a high density, however, it is not possible to achieve the desired urea bonds from the water reaction, since a large amount of urine toi'fbii. · ¹ , at the same time generates a large amount of carbon dioxide.

009849/1795

169458

amount means that leads to a low density. Furthermore, it is often desirable to completely exclude water from the reaction and to use solvent-type blowing agents. However, no urea bonds are obtained under these conditions. Accordingly, the proposal has already been made, a chemically inactivated aromatic diamine, for example 4,4 ^f -Me.thylen - bis- (2-chloroaniline), in order to obtain the desired amount to use of urea bonds, whereby the desired characteristics are achieved can.

Polyethers are preferred as a component which contains active hydrogen for the production of polyurethanes used. However, it is known that chemically inactivated aromatic diamines are incompatible with polyethers and They tend to react faster than the hydroxyl groups to form incompatible polyurea chains. Of the The person skilled in the art thus always considered it necessary to first combine the polyether with an excess of the polyisocyanate Implement "prepolymer" before the chemically inactivated aromatic diamine was added.

The invention is based on the object of polyurethane-urea foams to manufacture by a direct one-step process, with the polyether and chemically inactivated aromatic diamines with the resulting advantages of improved properties and improved Control or adjustment of the density and the amount of urea bonds used in the end product will.

The solution to this problem is a method for direct one-step production of urethane-resin foams by reacting a polyoxyalkylene polyol or polyoxyalkylene polyol mixture with mean equivalent weights between about 150 and 50000, an oxygen / carbon ratio from about 1: 2 to 1: 4 and about 2 to 6 terminal hy-

009849/1795

hydroxyl groups has, organic diisocyanates and chemically inactivated aromatic diamines in the presence of wetting and blowing agents at temperatures up to 120 ⁰ C. This method is characterized in that

a) the aromatic diamine in such an amount that the NHg / OH ratio is 0.5: 1 to 6: 1,

b) the organic diisocyanate in such an amount that the NCO / (OH + NH ₂ ) ratio is about 0.9: 1 to 1.5: 1 and

c) also an organometallic salt as a catalyst in an amount that is about 0.025 to 1.0 wt. #, based on the total weight of polyol and diamine, corresponds to

used and the foams then at temperatures hardens in the range of 25 ° to 160 ° C.

From the German Auslegeschrift 1 112 284 and the German Patent specification 1,157,775 already discloses one-step processes for the production of polyurethane foams. Compared to these known processes, the organometallic salt is according to the invention as a catalyst especially in the Use of a chemically inactivated aromatic diamine Essential to the invention, a teaching that the skilled person through the cited publications of the prior art Technology is not suggested. While in patent specification 1,157,775 organometallic compounds at all are not mentioned, the expert can only infer from Auslegeschrift 1 112 284 that the addition of an organotin compound optionally together with triethylenediamine can be used, this organotin compound practically as an equivalent to an additionally used one tertiary or quaternary amine is proposed. According to the explanations of the above-mentioned interpretative document Such an organotin compound can easily be omitted, while organometallic salts act as catalysts in the method according to the invention an essential element of the invention Represent an addition and must be used.

009849/179 6 '

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The method according to the invention enables manufacture soft, semi-rigid and rigid polyurethane foams. The term "hard" used here in connection with Polyurethane foams include "semi-rigid" foams.

The properties of the reactants and their proportions are critically important to achieving the goals of the invention and producing high quality Polyurethane-urea foams based on polyethers according to the invention. It is possible to all respondents. mix simultaneously at one time or use the "premix" form of the one-shot process in which the polyisocyanate to the actual mixing of the glycol or polyol is kept separate.

When using water or solvents as a propellant, pour the combined reactants after they have initially been mixed into a mold for about 10 to 15 seconds, with or without external cooling or heating allows it to rise unhindered to its full height, usually for several minutes. If a solvent which boils above room temperature is used as the propellant, it can be used the temperature of the reaction mixture after mixing of the reactants is above the boiling point of the solvent rise, with the forming polyurethane rising under the pressure of the enclosed gas and after as the polyurethane foam solidifies. If necessary, it can be heated from the outside. For example If a solvent with a higher boiling point is used, the reaction mixture can be placed in a heating cabinet, for example heated to evaporate the solvent. Furthermore, solvents can be used as blowing agents, which below boiling from room temperature, used in a foaming process be, in which the foam immediately when mixing the combined reactants, for example at the outlet of a foaming nozzle. The foaming

00-9849 / 1796-

If higher-boiling propellants are used, this can be caused by external heating or, in certain cases, by the heat of reaction be achieved.

Instead of water or solvents, air or Gases inert to the reactants, such as nitrogen, can be used as propellants. The air or other gases can be injected through a suitable nozzle the mixture can be blown or incorporated by whipping to form the desired foam.

The foams are usually cured at a temperature of about 25 ° to 160 ° C. For example, the foams can be aged for one week at 75 ° C and 50 % relative humidity. After this time they have essentially reached their full strength. It is possible to use shorter curing times and higher temperatures. Even after prolonged aging, for example for 8 weeks at 70 ^° C. and 100 % relative humidity, the foams produced according to the invention retain their desired properties and good dimensional stability in a remarkable manner.

Among the polyoxyalkylenes commonly referred to as polyethers Polyols that can be used in the direct one-shot process described herein include, for example Oxyalkylene adducts of polyol bases in which the oxyalkylene content is from monomer units, such as ethylene oxide, propylene oxide, Butylene oxide and mixtures thereof. Suitable polyol bases are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, hexanetriol, glycerine, Trimethylolpropane, pentaerythritol, sorbitol and sucrose ,. Polyethers, such as polyethylene ether glycols, polypropylene ether glycols, Polytetramethylene ether glycols, and alkylene oxide adducts of polyhydric alcohols including the above mentioned, terminal hydroxyl-containing tertiary amines of the formula

009849/1795

169A 583

AH AH

^ N - R - N

wherein R is an alkylene radical having at least 2 to 6 carbon atoms and A is a polyoxyalkylene chain, amine-basic polyethers formula

AH

^> N - Y
AH

wherein A is a polyoxyalkylene chain and Y is alkyl, hydroxyalkyl or AH stands, alkylene oxide adducts of acid, des Phosphorus, such as adducts, which are produced by reaction of phosphoric acid and ethylene oxide, phosphoric acid with propylene oxide, phosphorous acid with propylene oxide, phosphonic acid with propylene oxide, phosphinic acid with butylene oxide, polyphosphoric acid with propylene oxide and phosphonic acid with styrene oxide, and polyester, like the reaction products of polyhydric alcohols including those mentioned above with dibasic carboxylic acids, such as succinic acid, maleic acid, Adipic acid, phthalic acid and terephthalic acid.

Typical suitable polyether polyols are polyoxyethylene glycol, Polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, Block copolymers, such as combinations of polyoxypropylene and polyoxyethylene glycol, poly-1,2-oxybutylene and polyoxyethylene glycol and poly-1,4-oxybutylene and polyoxyethylene glycol, and random copolymer glycols obtained from mixtures or by sequential addition can be made from two or more alkylene oxides. Adducts of the above compounds are also suitable with trimethylolpropane, glycerol and hexanetriol as well as the Polyoxypropylene adducts of higher polyols such as pentaerythritol and sorbitol. For the one-stage according to the invention Polyether polyols suitable for the process are therefore oxyalkylene polymers with an oxygen / carbon atom

009849/1706

ratio of about 1: 2 to 1: 4, preferably about 1: 2.8 up to 1: 4, and about 2 to 6, preferably about 2 to 4 terminal Hydroxyl groups. The polyether polyols have im generally a mean equivalent weight of about 150 up to 5000; preferably from about 200 to 1500. Particularly Polyoxypropylene glycols with molecular weights of about 400 to 2500 are accordingly advantageous as polyols an equivalent weight of about 200 to 125O and their Mixtures. Polyol mixtures, such as a mixture of high molecular weight polyether polyols with polyether polyols from lower ones Molecular weight or monomeric polyols can also be used to make polyurethane-urea foams can be used with good properties. For the production of 'soft foams, preference is given to polyoxyalkylene polyols with an average equivalent weight from about JOO to 2000 used, while for hard foams polyols with an average equivalent weight from about 150 to 300 are preferred.

The term "chemically inactivated aromatic diamines" as used herein refers to aromatic diamines which contain one or more negative substituents on the aromatic ring to which the amine group is attached. Examples of such negative substituents are the halogen and nitro groups. Suitable for the novel single-stage chemically inactivated aromatic diamines are, for example 4,4'-methylenebis (2-fluoroaniline), 4.4 ^{t-methylene-bis-} (2-chloroaniline), 4,4'-methylene-bis- (2-bromaniline), 4,4'-methylenebis- (2-nitroaniline) and 4,4 ^l -diaminQ-3,3 ^! -dichlorodiphenyl. The primary diamond is used in such amounts that the NH 2 / OH ratio is 0.5: 1 to 6: 1, preferably about 0.7: 1 to 1.5: 1. Since the diamines are crystalline substances, it is advisable to dissolve them in the polyoxyalkylene polyol before the reactants are reacted.

009849/17

169Λ583 - ίο -

Suitable organic diisocyanates for the production of urethane-urea foams by the direct one-step process are, for example, polymethylene diisocyanate, tetrarae ethylene diisocyanate and hexamethylene diisocyanate, and aromatic diisocyanates such as toluylene diisocyanate, 4,4'-di phenyl methane diisocyanate, and 1,5- Iaphthalene diisocyanate, the isocyanates, the melting points of which are about ÖO ° C, "are expediently dissolved in an inert liquid carrier such as dibutyl phthalate, trieresyl phosphate or trioctyl phosphate, in order to facilitate the handling of the isocyanate and the reaction of the isocyanate with the other components of the reaction mixture The isocyanates, which melt between room temperature and 80 ° C., can readily be used in the molten state, and the organic diisocyanate is used in such an amount that the NCO / (OH + NH ₂ ) ratio is about 0.9 * 1 to 1.5 : 1 * is preferably about 1: 1 to 1.1: 1.

The organometallic catalyst used in salt form for the process according to the invention is a salt of a polyvalent metal with an organic acid which contains up to about 18 carbon atoms and no active hydrogen atoms. The organic part of the salt can be linear or cyclic and saturated or unsaturated. The polyvalent metal has a valence of about 2 to 4. Typical organometallic salts are stannous acetate, stannobutyrate, stanio-2-ethylhexoate, stannolaurate, stannooleate, stannous stearate, blelcyclopentanecarboxylate, cadmium cyclohexane, cadmium cyclohexanecarboxylate, dinaphthalene naphthalene-naphthenate, dinaphthalene-naphthenate, dinaphthalene-2-naphthenate, dinaphthalene-2-naphthenate, diumnaphthalene-naphthenate, dinaphthalene-2-naphthenate, dinaphthalene-2-naphthenate, dynaphylthenate, dinaphthonaphthenate, dynaphylthenate, dinaphthenaphthenate, dynaphthenaphaltylenate, dinaphthenaphthenate, dynaphtinaphthenate, dinaphthenaphthenate, butyrate, butyrate, butyrate ethyl hexoate. The organometallic catalyst is used in an amount of from about 0.025 to 1.0 percent, preferably from about 0.05 to 0.5 percent, based on the weight of the polyether polyol plus diamine. Tertiary amines, such as triethylenediamine and 1,2,4-trimethylpiperazine, are advantageously used in conjunction with the organometallic salts as catalysts for the one-step process according to the invention.

009849/1705

Any known wetting agents or surface active agents commonly used in the manufacture of high quality polyurethane foams can be used for the purposes of the invention. Non-ionic substances are preferred surface-active substances and wetting agents. Of these, the solid or liquid organosilicones have proven to be special proved beneficial.

The amount of surfactant or wetting agent in the reactant is also important, but it will vary somewhat depending on the effectiveness of the wetting agent. Generally, about 0.05 to 2.0 # surfactant will suffice, based on the total weight of the reactants. If the amount is below the lower limit, the foams tend to have a large and uneven cell structure, while amounts above about 2.0 % do not improve the properties of the foam and appear to deteriorate its strength somewhat. The optimum appears to be around 1% by weight, especially when the preferred wetting agents are used.

As already mentioned, water, carbon dioxide being formed by the water-isocyanate reaction, solvents, air or gases which are inert to the reactants, such as nitrogen, are suitable as blowing agents. Propellants can also be used that release inert gases, such as nitrogen, for example "Ν, Ν'-Dinitrosopentamethy1entetramin. When using solvents as propellants, these must be inert to all reactants, but soluble or dispersible in at least one reactant and insoluble in the final be polyurethane foam. the greater the solubility in the reactants or in the reactants, the lower the boiling point may be the solvent, the boiling point should not preferably not lie at atmospheric pressure over about 70 ⁰ C, 49 ° E, so that by Polymerization reaction is evaporated, in general

■■ '■ • ■■: .v, v .- ^ ,. 009849/1795 _BAD ORIGINAL

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should be the halogenated alkane and any other solvent that may be used in addition to or instead of it easily liquefied and so soluble in the reactant or reactants that its vapor pressure is greatly reduced to the need of using avoid expensive high pressure equipment. If the gas is relatively insoluble, it must be so be that it is easily dispersible. The foaming takes place when the gas by reaching a temperature is released well above its boiling point. This can of course be largely controlled by fe one dissipates the exothermic heat or not dissipates it. In Cases in which the heat of reaction is insufficient to evaporate the solvent used must be from the outside be heated.

The halogenated alkanes have all the necessary properties and are particularly advantageous as blowing agents. Fluorotrichloromethane is particularly suitable as a blowing agent, which boils at about 24 ° C and, like many halogenated alkanes of the "Freon" or "Genetron" type, the advantage of solubility in the glycol or polyol or prepolymer or in the isocyanate component or the compatibility therewith. Representative blowing agents including the preferred halogenated alkanes and their boiling points at normal pressure are listed in Table I below.

009849/1795

Table I. Suitable solvents as propellants

formula

Chemical name

Mole weight Boiling point, C

CCl ₂ F ₂ CH ^ -CHF ₂

Dlchlor-difluor-methane 1,1-Di fluoroethane

(cyclic) octafluorocyclobutane CClF ₂ -CClF ₂ 1,2-dichloro-tetrafluoroethane CHCl ₂ F CC1, F

Dichloro-fluoro-methane tri-chloro-fluoro-methane

CBrF ₂ -CBrF ₂ 1,2-dibromo-te trafluoroethane CCl ₀ F-CClF ₀ 1,1,2-trichlorotrifluoroethane

CH ₂ Cl ₂

Methylene chloride

Isobutane

butane

n-pentane

Isopentane

Neopentane

η-hexane

2,2-dimethylbutane

120, 9 -29.8 66 1 -24 200 -6.17 I70, 9 +3.5 102, 9 8,915 137, 4th 23.8 259, 9 47.5 187, 4th 47.6 83 39.9 58 τΐο 58 0 72 36.1 72 27.8 72 8.9 86 69 86 49

Of course, mixtures of such gases, for example a mixture of soluble and relatively insoluble gases, can also be used Gases, can be combined as propellants. Mixtures of the halogenated alkanes with other compatible solvents or gases such as carbon dioxide, methane, ethane, propane, '' Butanes, pentanes, hexanes, heptanes, propylene or nitrogen can also be used by these solvents or gases in the reactant or in the reactants be dissolved or dispersed together with the halogenated alkane.

009849/1795

The maximum propellant amount is preferably about 30 -1b _y based on the weight of the reaction participants. '>■:;' * Pure change in the amount of solvent with a simultaneous ^ slight change in the proportions, foams with densities of 16 to 96O kg / nr can be produced. The method according to the invention is particularly suitable for the production of soft foams with densities of 16 to 800 kg / m 2 and hard foams with densities of 16 to 320 kg / m 2.

In addition to the main constituents, additives that are intended to give the foams special properties, such as fillers, extenders, pigments and dyes, im Approach can be used. .

Test methods for the evaluation of foams

The properties of the soft foams were determined according to the Test method ASTM-D 1564-59T determined. The feed rate was 51 cm / min.

The tensile strength of the hard foams was measured in accordance with ASTM-D 1623-59T and the compressive strength of the hard foams in accordance with ASTM-D-1621-59T. ■.

The percentage of closed cells was measured according to ASTM-D I940-62T.

The K-paktor (thermal conductivity) was after the "Guarded Hot Plate Method "ASTM-C-177.

example 1

A range of soft polyurethane foams from the in The composition given in Table II was prepared as follows:

0-0.9 84 9V 17 0.5

o-Dichlorobenzidine (4,4 ^f -Methylene-bis- (2-chloroaniline) was dissolved in the polyol at room temperature. The polyol-diamond mixture was freed from water and trapped gas by increasing it to Hg for 1.5 hours at 5 120 ^° C. Trimethylperazine and the surface-active substance were then added, whereupon the mixture was stirred for 0.5 hour The catalyst stannous octoate was then added and the resulting mixture was stirred for 15 minutes, after which time the icocyanate was added and stirring continued until the ingredients were thoroughly mixed. The mixture was poured into a mold It took about 0.5 to 2 minutes to climb to its full height, and foams with the properties set out in Table II below were obtained.

009849/17 95

Table II parts by weight

Components

Sample no.

Poly oil polyol polyol

(D (2) (3)

79

58.8
29.4

MOCA o-dichlorobenzidine

11.8 21

83.5

16.7

55.5

; 27, β

16.7

Tolylene diisocyanate 17th 28.5 28.5 20.5 20.5 Trimethylpiperazine 1.2 0.2 0.2 0.8 0.8 Stannous octoate 0.2 0.1 0.1 0.2 0.2 NHg / OH ratio
NCO / (OH + NH ₀ ) -
Ratio ^d Vl
i, Vi 1/1
1.04 / 1 1/1
1.04 / 1 1.5 / 1 1.5 / 1
1.1 / 1 Trichlorofluoromethane , 52 24 24 52 32 Surface active Substance '' 0.5 0.5 0.5 0.5 0.5 Curing 16 hours
at _o
100 C . 1 H.
at
70 ⁶ C 16 hours
at _o
100 ⁰ C 16 hours
at _o
100 ° C 1 H
at
70 ⁰ C properties Volume weight, kg / no 57 36 34 55 32.8 Tensile strength, kg / cm ² 1.05 2.01 2 1.2 1.5 Elongation, % 427 415 568 422 540 Tear resistance
("Split Tear"), kg / cm 0.59 1.07 1.04 0.71 _ Deformation rest at
Compressive stress
22 hours at 70 ^° C V. Deformation rest 50 % 49.9 78.1 45.7 54.8 76.1 Deformation rest 90 % 95.0 96.8 93.0 92.0 94.8 Rebound resilience
(falling ball), % 41.6 18.8 45.1

0098A9 / 1795

Table II (Ports.) Parts by weight

Components __ ₍ sample no.

6 7 8 9

(2)

Polyol J '- - - 88.8 88.2

Polyol ^{(: 5)} - -

Polyol ^v ^ ^;
/ r- V 83.3 83.3 - - MOCA ^ir>; 16.5 16.7 - 11.8 δ-dichlorobenzidine - _ 11.2 _ Tolylene diisocyanate 20.4 22.3 16.8 16.1 Trimethylpiperazine 0.15 0.10 2.0 1.0 Stannous toate 0.2 0.2 0.4 0.4 NHg / OH ratio
NCO / (OH + NH ₀ ) -
Ratio * 1.5 / 1
1.1 / 1 1.5 / 1
1.2 / 1 1/1
1.1 / 1 1/1
1.05 / 1 Trichlor fluorine than 18th 18th 31.0 11th Surface active Substance ^ ' 0.5 0.5 0.5 0.5 Curing 16 hours
at
100 ⁰ C 16 hours
at
100 ⁰ C 1 H.
at
70 ° C 16 hours
at
100 ⁰ C properties Volume weight, kg / nr ' 54 57.5 36 170 Tensile strength , kg / cra ² .1.89 1.94 0.69 3.43 Elongation, % 170 146 302 176 Tear resistance
("Split Tear"), kg / cm 0.55 0.55 0.61 1.8 Deformation rest at
Compressive stress
22 hours at 70 ^° C Pore change residual 50 % 13.7 9.5 ; - - - 8.2 Deformation rest 90 % 14.9 10.9 86.4 8.4 Rebound resilience
(falling ball), % 45.9 37.5 38

009849/1795

1.69 A 5 8 3

- i8 -

Components

Table II (cont.) Parts by weight

Sample no.

Polyol
Polyol
Polyol

(D
(2)
O)

Polyol

MOCA ^ ⁵ ^

o-dichlorobenzidine toluene diisocyanate trimethylpiperazine stannous octoate NHg / OH ratio

NCO / (OH + NH ₀ ) ratio ^d trichlorofluoromethane surface-active substance ^ ⁶ \ curing

properties

Volume weight, tensile strength, kg / cm ² elongation, % «

Tear strength ("Split Tear"), kg / cm

■ Deformation rest under pressure load 22 hours at JO ⁰ C Form change rest Deformation rest rebound resilience (falling ball), %

IO

K

11.8

12th

88.2 11.8

88.2

11.8

88.2

11.8

16.1
1.0
0.3
1/1 16.1
1.0
0.1
1/1 16.1
0.8
0.2
1/1 16.1
0.8
0.2
• i / i 1.05 / 1
11th 1.05 / 1
11th 1.05 / 1
18th 1.05 / 1
18th 0.5
16 hours
at _n
100 ° C 0.5
16 hours
bet
100 ° C 0.5 "
16 hours
at
100 ° C 0.5
16 hours
at _o
ICO ⁰ C 138
3.3
278 144
.3.27
409 69
535 72
1.98
569 1.5 2.05 0.77 1.25 16 * 5
24.8 16.9 62.7 28.3
87.7

39

28

009849/1795 ORIGINAL

Components

Table II (cont.) Parts by weight

Sample no.

14th

16

Polyol
Polyol
Polyol

(D
(2)
(3)

79

83.2

Tear resistance

("Split Tear"), kg / cm 1.4

Deformation rest under pressure
22 hours at 70 ^° C

Deformation rest 50 % 31.4 Deformation rest 90 % 85.7 Rebound resilience

(falling ball), # 29.6

4.3
5.4

20.7

10.3
77.6

21.6

Polyol ^v ' - - - - · MOCA ^ ⁵ ^ 16.7 21 21 21 o-dichlorobenzidine - - - - - - Tolylene diisocyanate 20.4 28.8 28.8 28.8 Trimethylpiperazine 0.6 0.3 0.3 . 0.3 Stannous octoate 0.2 0.15 0.15 0.15 NHg / OH ratio
NCO / (OH + NH ₀ ) -
Ratio ^d 1.5 / 1
1.10 / 1 1/1
1.05 / 1 1/1
i, 05 / i 1/1
1.05 / 1 Tr i chlorine fluorine than 18th 15th 22nd 30th Surface active 0.5 0.5 0.5 ' 0.5 Substance ^ ' Curing
properties
Volume weight, kg / m- ⁵ 16 hours
at
100 ° C 16 hours
100 ° C 16 hours
at
100 ⁰ C 16 hours
at
100 ° C Tensile strength, kg / cm ² 59 53 40.5 27.7 Elongation, % 2.42 2.45 2.3 1.25 429 143 252 328

23.2 91.0

28.6

009849/1795

'■■■■ .- 20 -'

In Table II, the numbered ingredients were the following compounds:

1. Polyoxypropylene glycol, average molecular weight 1000.

2. Polyoxypropylene glycol, average molecular weight 2000.

3. Polyoxypropylene adduct of trimethylolpropane, medium Molecular weight 3000.

4. Polyoxypropylene adduct of glycerine, medium molecular weight JOOO.

5. 4, V-methylene-bis- (2-chloroaniline).

6. Water soluble liquid surfactant based on silicone.

Example 2

A number of rigid polyurethane foams were made from the ingredients listed in Table III below the manner described in Example 1 prepared. The ingredients identified as surfactant and MOCA are the same as in Table II of Example 1. Hard Foams having the properties given in Table III were received.

009849/1795

-21.- 1 169458 3 Table III 162 Parts by weight - mm Components 88 Sample no. 0.5 CVl 3 TP 74o ^ ¹ ^ 0.25 162 1 .10 TCPPG ^ ■ 1/1
1.05 / 1 - 37.5 MOGA 50 88 60 Trimethylpiperazine 1.5 0.5 0.25 Stannous toate 1 H. '
at 70 ° G 0.25 0.25 NHp / OH ratio
NCO / COH + NH ₂ ) ratio 1/1
1.05 / 1 1, 1/1
05/1 Trichlorofluoromethane 50 50 Surface active agent 1.5 1.5 Curing 1 hour_ 1 hour
at 70 ⁰ C at 70 ° C

Isocyanate

^ 187.4

- 12Ö 88.4 properties

Volume weight kg / ra tensile strength, kg / cm compressive strength, kg / cm change in shape 5 %

Deformation 10 % 2.05 1.11 i, dö λ

Shape change 25%

Compressive strength at yield point, kg / cm ^ .5.25 1.04 1.77

Bend due to pressure load

the yield point (Compressive

deflection at yield point), % 7.0 8.3 5.6

Closed cells, # 86.2 77.7 71.3

K-factor at a medium one

Temperature of 24 ° C 0.129 0.118 0.114

46.5 52.5 4A- 6.28 6.1 4.04 2.9 0.68 1.74 2.85 1.11 1.68 3 1.27 1.78

1.' Pcilyoxypropylene adduct of trimethylolpropane, medium

Molecular weight 732.
2 * trichloropolypropylene glycol, average molecular weight 1000.

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. ^: ■ - ²² - ■ * "'■' ■ '■■■ ..'

2 crude p / p'-diphenylmethanediisoeyanate, functionality 2.5 4. Tolylene diisocyanate.

Example 3

This example describes the production of foams by foaming with air instead of incorporation; a solvent as a propellant. The foam was produced from 78 [beta] polyoxypropylene glycol with an average molecular weight of 1000, 21 g of 4,4'-methylenebis (2-chloroaniline) and 20/2 g of tolylene diisocyanate. Here the NH _r / 0H-

Ratio 1: 1, and two equivalents of excess NCO per Molecular weight 10,000 are obtained. Lead naphthenate serves as the catalyst. 1% by weight of surfactant is added to the mixture Silicone-based agent added. A mixture of the ingredients was based on that described in Example 1 Wise prepared, but no solvent was added as a blowing agent. Then air was forced into the uncured mixture that was in the mixing vessel Stir suggested. The pressure of the blown air

was 0.7 kg / cm. The foam was ^{cured at 100 °} C. for 16 hours. A foam with the following properties was obtained here:

Volume weight, kg / nr 72

Deformation rest under compressive stress, 22 hours at 70 C,

Deformation 50 % _ ■ 2 4th 14th ,1 tensile strenght , kg / cm 8th , 9 Elongation, % - -. example 178

This example describes the production of foams according to the invention, wherein water instead of a blowing agent for the formation of COp gas by the water-isocyanate reaction uses vmrde. The foam was made by mixing polyoxypropylene glycol with an average molecular weight of 2000, 4,4'-methylene-bis- (2-chloroaniline), silicone-based surfactants, water, toluene

009849/1795

diisocyanate and lead naphthenate in the following amounts:. 1 Hol glycol, 1 mole of diamine, 1 wt -% silicon, 0.129 Gew.Ji v / ater, toluene diisocyanate in an amount in excess of 2 moles UCO per 10,000 molecular weight is present, for ._ 0.05 wt.% lead naphthenate. The foam was produced in the manner described in Example 1, except that water and no solvent were added as a blowing agent. The foam was ^{cured for 10 hours at 100 °} C. and then had the following properties: density 65 kg / m-5

Deformation rest under pressure

22 hours at 70 ^° C., deformation 50 % 14.3 m

Tensile strength 70.3 kg / cm ²

Strain . 530 %

Example 5

A foam was made from 0.89 parts by weight of a triol with a molecular weight of 420 (propylene oxide adduct with a trimethylol propane base), 92.11 parts by weight of a triol with a molecular weight of 14,000 (equimolar adduct of butylene oxide and ethylene oxide with a trimethylol propane base), 7.0 parts by weight 4, 4 ^r -methylene-bis- (2-chloroaniline), 9.1 '; Part by weight of toluene diisocyanate, 0.15 part by weight of stannous octoate as a catalyst, 1 part by weight of silicone-based surfactant, 0.3 part by weight of tri- (J methylpiperazine and 15 parts by weight of trichlorofluoromethari as a propellant. A mixture of the ingredients was prepared in the manner described in Example 1. The The NHg / OH ratio obtained was 1.33: 1 and the KCC / (OH + NH ₂ ) ratio 1.15: 1. The foam obtained was ^{cured for 16 hours at 100 °} C. A good, soft foam was obtained.

Example 6

A foam was made from 86 parts by weight of a tetrahydrofuran with a molecular weight of 3,300 (adduct of propylene oxide and ethylene oxide with ethylene diamine with a terminal ethylene oxide content of 15 %), Xk parts by weight of 4,4-He-

009849/1795

-. 24 -

ethylene bis (2-chloroaniline), 16.3 parts by weight of tolylene diisocyanate, 10 parts by weight of trichlorofluoromethane, 3 parts by weight of trimethylpiperazine, 0.15 part by weight of stannous octoate and 1 part by weight of silicone surfactant. The ingredients were mixed in the manner described in Example 1. The NHg / OH ratio obtained was 1: 1 and the NCO / (OH + NH ₂ ) ratio was 1.1: 1. After curing for 16 hours at 100 ^° C., a good foam was obtained.

009849 / 17.95

Claims (3)

- 25 claims " 1.) Process for the direct one-step production of urethane-urea foams by reacting a polyoxyalkylene polyol or polyoxyalkylene polyol mixture with average equivalent weights between about 150 and 5000, an oxygen / carbon ratio of about 1: 2 to 1; 4 and about 2 to 6 terminal hydroxyl groups, organic diisocyanates and chemically inactivated aromatic diamines in the presence of wetting agents and blowing agents at temperatures up to 12O ⁰ Cj, characterized in that a) the aromatic diamine in such an amount that the NHg / OH ratio Q.5; l to 6: 1 is, b) the organic diisocyanate in such an amount that the NCO / (OH + NH ₂ ) ratio is about 0.9; l to 1.5 si and c) also an organometallic salt as a catalyst in an amount that is about 0.025 to 1.0 wt. #, based on the total weight of polyol and diamine, corresponds to is used and the foams are then cured at temperatures in the range from 25 ° to 160 ° C, 2,) Method according to claim 1, characterized _ß that one for the production of soft foams; Polyoxyalkylene polyols with an average equivalent weight of about 300 to 20% 3.) The method according to claim 1, cladurcli gekennzeichiiet that man to manufacture; harter SalmumsJoffe PolyoxyalkyXen- with iron mean equivalent weight of to JQQ