DE2347299C3 - Process for the production of polyurethane-polyurea gels - Google Patents

Description

The invention relates to the production of novel. stable polyurethane urine containing water or alcohol itofi gels. The (IeIe can contain up to 98% by weight Solvent contained without liaß cmc worth mentioning Evaporation of the trapped solvent animal air enters.

Ks is known in principle. Polyurethane polyurine Manufacture fabric polymers. This is done using cyanates or reaction products of polyols and polyisocyanates Excess polyisocyanates with polyfunctional amines or with water. While in the first I all depending on the chemical nature and amount of the starting components used. hard to clasii What compact masses are preserved «grounding, occurs when chains are lengthened with water and at the same time Presence of certain additives such as catalysts or foam stabilizers. Foams, which in general my usage can be referred to as polyurethane foams. The manufacture of these materials, also under technical conditions, is well known and has been published in numerous publications, e. B. in R. Viewing, A. Höchtlcn, Kunststoff-Handbuch Vol. VII, Polyurethane, Hanscr-Verlag Munich, 1966.

The production of polyurethane-polyurea-Polymcrcn usually takes place in such a way that the individual components interact with one another in the absence of solvents be mixed. With some leclmisclien pro / eat, for example the production of certain elastomer coatings or elastic fibers the reaction also carried out in solvents which are inert to the isocyanate groups, e.g. Am - dimethylformamide. According to the teaching of the U.S. PS

35 74 150 are made by reacting polyaryl-polyalkylene-polyisocyanates with certain polyol mixtures in inert organic solvents in which the resulting polymer is essentially insoluble,

κι polyurethanes obtained that have a porous structure own. During its formation, which takes about 8 to 30 minutes to complete, it becomes very unstable Go through gel state which can be recognized by the fact that the clear solution takes on an opaque appearance.

π Similar processes for the production of microporous moldings by isocyanate polyaddition reactions in bad solvents are also in DE-OS 16 94 230. the US-PS 35 82 396, the US-PS

36 81 125 and DE-OS 17 69 089 described.

.'D It has now been found that stable polyurethane-Poiyharnstoft-Geie can be obtained if one isocyanate-containing prepolymers of polyethers with more than 40% by weight of ethylene oxide units in water or alcohols with di- or polyamines as chain links

Jj implements lengthening means. The term gel is intended to mean describe the physical nature of the jelly-like or jelly-like end product rather than that exact polymer-physical structure according to today's views of colloid chemistry about it

ι »go back to the state. But this should not be ruled out It is clear that the novel gels in some cases have the same homogeneous structure as today it is generally ascribed to gels, d. Iu that swollen by water or alcohols, more or

r> less branched polymer networks from the Polyurethane polyureas are present.

The isolation of the individual components below Formation of the new type of water and / or alcohol containing dele takes place spur. ·: 'Without the

■ ι »dispersants via their hydroxyl groups with the Isocyanate groups come into reaction. Due to the high formation speed, the production of the gels can easily be designed continuously, which is very beneficial for many purposes. is

■ Γι (if you have a patent application is therefore a Process for the production of stable, water and / or alcohol-containing poly urethane urea gels by I imsetziing of

anatgruppen to 20dew% of an LSI, "\ a) 2 containing the prepolymer, which is / ung a hydroxyl-containing polyether having more than 40 wt.% of ethylene oxide units with a Polvisocyanal in NC O / OH ratio ym by I Imset was obtained ßerals 1, nut

b) a diamine or polyamine in the presence of

c) water and an alcohol

which is characterized by. dali one either

the components a. b and c in one shot so combines or a solution of component a in Component c with component b, optionally dissolved in component c, ti, older intensive mixture united.

From FR-PS 15 60 629 the Icrstcllung is aqueous til solutions of polyurethane urea opened: the objective is therefore completely different from that of the

present invention different.
According to IR PS, the same output

compounds are used as in the method according to the invention, the difference, however, is that one (as the embodiments of the cited patent show) the isocyanate component in the form a dilute solution in acetone and slowly an aqueous solution of the chain extender zuiropft, whereby the formation of a gel is just avoided.

The gels can be produced in various ways. So it is possible to use all components, i. H. the Prepolymers, the dispersant, i.e. water and / or alcohol, and the chain extender in to put together in one shot. But you can also first a solution of the prepolymer in water or Prepare alcohol and then either use the pure chain extender or a solution Mix the same in additional water and / or alcohol. In any case, the Gel formation.

Through an intensive mixing of the starting components gel formation is facilitated and the quality of the gels is improved. Mixing can be done in simplest case in a zone of increased turbulence caused by a mechanical stirring device will take place. Better results are obtained when using fast-running mixing units, for example of centrifugal homogenizing machines or of agitator mixing chambers known from literature or commercial polyurethane foaming machines. Intensive mixing can also be achieved by using the mixing devices of polyurethane foaming machines .Treat. in which the mixing takes place by countercurrent injection.

The prepolymer of ethylene oxide-rich polyethers and polyisocyanates of higher functionality, which still contains free isocyanate groups at the end, is converted into an excess amount of polyisocyanate by reaction of the corresponding polyethers. Thus, in a NC'O / OH Vcrhältnis greater than 1. preferably 1.5 20, particularly preferably 2 - 10 prepared.

The optimal ratio for carrying out the process depends in each case on the molecular weight, the functionality and structure of the polyether. In general, the isocyanate content of the prepolymers between 2 and 20% by weight, preferably between 5 and 10% by weight.

For the formation of the gels essentially equal amounts of prepolymers and \ m \ n are required. In the technical implementation of the process, however, in order to achieve a suitable residence time in the mixing units, it has proven to be advantageous to work with a l'lberschull of the Amiri component, ie with an NH> / N ('() ratio greater as!. preferably 1 to 1.2.

When the gels are formed, the amount of water and / or alcohol present is within wide limits variable and not critical. In relation to the overall dimensions of the gel, the weight of alcohol and / or water can be up to 98%. By the Amount ratio between polymer and dispersant abc- the properties of the gels obtained are strongly influenced. In general, the Gels are more stable and harder with increasing polymer content and with decreasing polymer content up to Border of about 2% by weight softer and less stiff.

Suitable dispersants are water as well as water optionally branched (eyolo) aliphatic alcohol

47 299

Ie with I to 8 carbon atoms, for example methanol, ethanol, hopropanol, Ethyienglykol and Butanol.

It is particularly surprising that the gels according to the invention are extremely stable. Even after prolonged storage no visible phase separation occurs. B. by a clouding of the material would make noticeable. The dispersant is very firmly bound in the gel, so that no noticeable Evaporation or diffusion of the water and / or alcohol occurs.

The starting material for the process according to the invention are at least 2 active hydrogen atoms containing polyethers with a molecular weight of 500-10,000, preferably 2000-8C00, the at least Contain 40% by weight of ethylene oxide groups. Such polyethers are made by reacting Compounds with reactive hydrogen atoms, such as. B. polyalkchols. with ethylene oxide and given optionally alkylene oxides, such as propyl oxide. Butylene oxide, styrene oxide. Epichiorhydrin or C.-mix these Alkylene oxides. Suitable polyalcohols and phenols are, for. B.

Ethylene glycol, diethylene glycol.

Polyethylene glycol. Propanediol- (1,2), propanediol- ( 1J). Butanediol- (1.4).

Hexanediol-f 1.6), decanediol- (1.2).

Butyne-2-di- (1.4). Glycerin. ButanedioI- (2.4).

Hexanetriol- (1.3, b). rrimethylolproprn.

Resorcinol. Hydroquinone.

4,6-Di tert-butylbrenzka: echin.

3-hydroxy-2-naphtho !.

6.7 Dihydroxy-1 naphthol.

2.5 dihydroxy-1-naphthol.

2.2 bis (p-hydroxyphenyl) -pr> > pan.

Bis (p-hydroxy phenyl) methane and \. \. (r) Tris (hydroxyphenyl) alkanes, such as ζ. Β.

1.1.2 Tris (hydroxyphenyl) ethane or

1.1.3-Tris (hydroxyphenyl) propane. Other suitable polyethers are the 1,2-alkylene oxide Der'vate of aliphatic or aromatic mono- or polyamines, such as. B. ammonia. Methylamine, ethylenediamine. NN-Dimelhy! Ethylenediamine. Telra- or hexamethylene diamine. Diethylene; riamine. Ethanolamine. Diethanolamine. Oleyl diethanolamine. Methyl diethanolamine. Triethanolamine. Aminoethylpipcra / in. o-, miind p-phenylenediamine. 2.4 and 2.6 diamino toluene. 2.6-Diaminop xylene and polynuclear and kondensiei th aromatic polyamines, such as 1.4-Naphthylcridiamine. 1.5-nephihvlindiamine. Benzulin. Toluidine. 2.1 Di chloro 4.4 -DiaminodiphenylmethiiM. I l'hiorciianiiii. 1,4-anthradiamine. 9.10 Diaminophenanren or 4.4 Diami'iuazobcnzol Ms Siarimolcktile of the polyethers also hard materials of the phenol and Rcsol type come into question.

All of these polyethers are built using ethylene oxide. where more than 40 wt. "/ < > of the alkylene oxide groups should be ethylene oxide.

As starting components to be used according to the invention, kc.-mmen continue to be aliphalic. Cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates into consideration, as they are described by f .. B. von W. Sicfgen in Lustus Liebigs Annalcn der Chemie, 562, pages 75 to 136, for example ethylene diisoryanate, l / t-tramernylene diisocyanal, 1,6-hexamethylene diisocyanate. I. ^ - Dodecane diisocyanate, cyclobutane-IJ-diisocyanate. Cyclohexane-1,3- and -1,4'diisocyanate, sou ie any mixtures of these isomers, l-iso-

cyanato ^ .S-trimethyl-S-isocyanalomethylcyclohexane (DE-AS 12 02 785), 2,4- and 2,6-hexahydrotolylene diisocyanate as well as any Gemiselic of these isomers, l-lexahydro-l, 3- and / or 1,4-phenylcn-diisocyanate, per hydro-2,4'- ühd / odef -4,4'-dipheriylmc (hah-diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate and any mixtures of these isomers, Diphcnylmethah-2,4'- and / or ^ / T-diisocyanate. Naphthi ylene-l ^ -diisocyanate, triphenylmethane-4,4 ', 4 "-triisoijyanat, Polyphenylene-polymethylcn-polyisocyanals, such as those produced by aniline-formaldehyde condensation and subsequent Get phosgenation and z. B. in GB-PS 8 74 430 and 8 48 671 are described, perchlorinated aryl polyisocyanates, such as those used, for. B. in the DE-AS 11 57 601 are described, Carbodiimidgruppcn containing polyisocyanates, as described in DE-PS 10 92 007, diisocyanates, such as they are described in US-PS 34 92 330, Aiiuphanaigruppen containing polyisocyanates according to GB-PS 9 94 890. BE-PS 7 61626 and published Dutch patent application 71 02 524, polyisocyanates containing isocyanurate groups, like siez. B. are? N DE-PS 10 22 789.12 22 067 and 10 27 394, as well as in DE-OS 19 29 034 and 20 04 048 to be discribed. Urcthangruppcn containing polyisocyanates, such as are z. B. in BE-PS 7 52 261 or in US-PS 33 94 164 are described, acylicrtc Polyisocyanates containing urea groups according to DE-PS 12 30 778. Biuret groups containing Polyisocyanates such as those used, for. B. in DE-PS 11 01 394. in GB-PS 8 89 050 are described, polyisocyanates produced by telomization reactions, how they z. B. in BE-PS 7 23 640 are described. Polyisocyanates containing ester groups, such as sic z. B. in GB-PS 9 56 474 and 10 72 956. in US-PS 35 67 763 and in DE-PS 12 31 688 are mentioned or reaction products of the above-mentioned isocyanates with acetals according to DE-PS 10 72 385.

As a low molecular weight reducing agent become aliphatic. cycloaliphatic or aromatic di- or polyamines are used. Examples "for solrlip connections are ·

Ethylenediamine. Hexamethylenediamine.

Diethylenetriamine. Hydrazine.

Guanidine carbonate.

N.N'-diisopropyl-hexamethylenediamine.

1.3-ßis-aminomethyl-ben / ol.

N.N'-bis- (3-aminopropyl) -

ethylenediamine.

N.N'bis- (2-aminopropyl) -ethylenediamine.

N.N'-bis- (2 a ~ iinr> ethyl) -ethylcndiamine.

4.4'-Dimethylamino-diphenylinethane.

4.4'-dimethylamino-3,3'-dimethyl-

diphynyl methane,

4,4'-diamino-diphenyl-methane. as

2.4- or 2.6-DiaminotoIuoI.

The manufacture of prepolymers from polyethers and the polyisocyanates according to known processes, with NCO / OH ratios greater than 1 can be set.

During the production of the gels, the A wide variety of fillers are added, such as silicates, flic various types of silicic acid. Aluminum oxides, the tin oxides. Antimony oxide. Titanium dioxide, graphite and graphitized carbon. Soot. Reliability. Flying sand, powdery types of cement, the most varied inorganic and organic Farhstciffpigmente./. B.

Iron oxide pigments, bleaching roinate, lead oxide and red lead. Short or long fibers made of natural or synthetic materials, such as cellular materials, can also be used as fillers. use. It is also possible to use soaps, surfactants, vegetable ingredients, To add salts, fertilizers or aqueous solutions of other natural or synthetic polymers,

As mentioned at the beginning, a particular advantage of the method according to the invention is that it is very

can easily be designed continuously.

The hydrophilic prepolymer containing NCO groups and, separately therefrom, the Keltenverlängcrungs · agent and the dispersant are for this purpose at a temperature above the melting point

r, and below the decomposition point of NCO prepolymer and chain lengthening agents are continuously introduced into a mixing zone in such a mass flow, that the isocyanate polyaddition in the mixed zone is not yet fully completed. That me flowable or deformable. Polyurethane gel with high water or alcohol content then becomes continuous removed from the mixing zone and, if necessary, then passed through a short retention tube, which is provided with a profile mouthpiece. so that the resulting polyurethane gel as a molded endless Rope, tape or sheet goods accumulate.

You can also use the mixing space in addition to the prepolymer, the chain extender and add a gaseous component to the dispersion medium which, in its volume flow, has the Multiples (1 to 10 timesc) the volume of the liquid Phase can be.

In this way, air-containing gels are created whose spatial density (kg / m ¹ ) depends on the built-in air pressure

Μ more or less compared to the compact material is greatly reduced.

The volume flows that are continuously flowing into the mixing chamber are fed, are expediently chosen in this process variant so that the

• Not yet complete in polyaddition in the mixing zone is completed. The still flowable or deformable Sinrk solvent-like polyurethane-Gcl foam is then continuously removed from the mixing zone and, if necessary, then through a short Vcrweilzcitrohr with a profile mouthpiece is provided. so that the resulting polyurethane foam gel as a molded endless Strand-. Tape or plate goods are incurred.

The reaction between the prepolymer and the

-, O Keltern derUingcrer runs very quickly and strongly exothermic. By varying the following parameters, the reaction temperature and thus the reaction rate adjusted so that the components within the reaction vessel to about 60-90%.

ν; preferably about 75-80%. implemented together will:

1) Throughput: The higher the throughput for the given dimensions of the mixing vessel and residence zone

mi is chosen per unit of time, the lower it becomes

of course the degree of implementation. The throughput can optionally also by a Narrowing at the outlet nozzle of the mixing zone can be regulated:

h <i 2) Temperature of the input components:

3) Amount of chain lengthening agent: the larger the excess of the chain extension used

fers is opposite the NCO Präpolymereri, the faster the reaction is generally carried out at extends Kfcnnzahlen NH ₂ / NCÖ of about 1.0 to 1.2.

4) Mixing intensity: It goes without saying that the intensity fed into the system as a result of the mixing process is also included Energy of influence on the speed of reaction.

In general, it is necessary to increase the reaction temperature by varying the parameters mentioned To be throttled below 60 ° C so that a gel that has not yet fully reacted can be removed from the mixing zone can. The degree of conversion of the reaction mixture can advantageously be used in the process according to the invention however, they can easily be followed by measuring the pH. At a relationship NI-WNCO of 1.0, the pH of the fully reacting mixture is 7, with an index of 1.2 driven, at about 8. In any case, the pH of the system is immediately when the Output components between 11 and 14, then in the course of about 10 to 120 seconds on his End value decrease.

Does the reaction between prepolymers and chain extenders take place in comparison to the mixing speed? too fast, then inhomogeneous gels arise as a result of phase separation. By suitable variation of the However, a horrogenic gel formation can easily be ensured.

What has just been said applies mutatis mutandis even if the production of a foam gel is continuous shall be.

From the foregoing it can be seen that the gels of the invention can be used on a large scale are sensibly produced continuously, since in in any case, the mixing zone must be very small compared to the volume to be mixed. The auxiliary equipment like storage kettle. Pumps and tanks are therefore large compared to the actual production zone. That is also the reason why such systems can easily be mounted on trucks in order to uai Fiuuuki uiickt Place of the consumer (e.g. agriculture or construction industry). A schematic arrangement for the continuous implementation of the process according to the invention is indicated in FIG. 1. the Liquid phase (water and / or alcohol) is taken from tank 1, via pump 2 the heat exchanger 3 and blended with the solution of the Ketlenverlängeren from tank 4 via pump 5 and fed to the mixer 6 in such a way that it reaches the mixing zone 6a separately from the prepolymer. That Prepolymers are obtained from tank 7, which is provided with a temperature control jacket, via pump 8 and Heat exchanger 9 is fed to the mixing zone 6a of the mixing device 6. If necessary, a gas is supplied via the Gas knife 10 introduced into the interior of the mixing zone.

The product leaves the system as a continuous product via the outlet nozzle 11, which is then transferred to the next Consumption can be fed.

It is of course also possible in continuous operation to add various types of gel to the mixing device 6 Mix in fillers. For example, you can the reaction mixture seeds or fertilizer and / or Add pesticides and lay the rope directly in the seed grooves.

The gels obtained can be used for the most varied of purposes. So let them get on Due to their high elasticity, use them as upholstery or shock-absorbing parts, water gels are suitable due to their flame retardancy for the production of fire-resistant cladding and plant nutrients containing water gels as substrates for hydroponics. They are also excellent binders for solid and fibrous fillers. Air-containing water gels are z. B. excellent flame retardant insulation materials.

example 1
a) Preparation of the prepolymer

43.3 kg of a polyether based on glycerol with 40 wt .-% propylene oxide and 60% ethylene oxide, one A hydroxyl number of 28 and a molecular weight of 6000 are placed in a kettle, 6.8 kg Hexamethylene diisocyanate was added and the mixture was heated to 110-120 ° C. for 6 hours with stirring. The received Prepolymers has an isocyanate content of 5.13% (calculated 5.0%) and a viscosity of 7990 Centipoise at 25 ° C.

b) Preparation of the gel

500 parts by weight of the prepolymer described under la) are in 4000 parts by weight of water Emulsified to form a component A: on the other hand, 16 parts by weight of ethylenediamine are used in 5000 parts by weight Water dissolved to form a component B. Both components are removed by means of high pressure injection pumps conveyed separately into a mixing chamber in which they are mixed with one another by countercurrent injection will. A milky emulsion emerges from the chamber, which is converted into a form in which in the course of the process solidification occurs after 2 seconds. A gel forms in the process. around 95 percent by weight of water and 5 percent by weight polyurethane-polyurea polymer contains. The gel is highly elastic and, at 20% load, has a compressive stress of 4.5 KPa (Kilopascal) after the 1st and a compressive stress of 3.0 KPa after the 4th load. It can repeat through Cool to - 10 ° C and can be frozen by warming, without affecting its properties loses.

Example 2
a) Preparation of the prepolymer

38.6 kg of a trifunctional started on glycerine Polyether, the 40 weight percent propylene oxide and Contains 60 percent by weight ethylene oxide units, a hydroxyl number of 28 and a molecular weight of 6000 possesses are presented in a cauldron, 11.4 kg Hexamethylene diisocyanate was added and the mixture was heated to 110-12 ° C. for 6 hours with stirring. The received Prepolymers has an isocyanate content of 10.3% (calculated 10.0%) and a viscosity of 1269 Centipoise at 25 ° C

b) Preparation of the gel

30 parts by weight of the prepolymer described under 2a) are added in 60 parts by weight of water a Α component emulsified; parallel to this, 1.56 parts by weight of ethylenediamine in 10 parts by weight Water dissolved to form a B component. 90 parts by weight of component A and !!, 56 Parts by weight of component B conveyed separately to the mixing chamber of a polyurethane foaming machine, in which the mixing by means of a stirrer

he follows. The exiting mixture forms in a mold after one second a very hard, pressure-resistant water gel with a polymer content of 30%.

Example 3
a) Preparation of the prepolymer

687 g of a trifunctional polyether started on glycerine, the 40 weight percent propylene oxide and Contains 60% ethylene oxide units, has a hydroxyl number of 28 and a molecular weight of 6000, are placed in a flask, 113 g of toluene diisocyanate (80% 2,4- and 20% 2,6-isomer mixture) are added and with stirring at 120 ° C for 2.5 hours heated. The prepolymer obtained has an isocyanate content of 5.6% (calculated 5.0%) and a viscosity of 5680 centipoise at 25 ° C.

b) Making the Geis

A mixture of 100 parts by weight of water and 20 parts by weight of the prepolymer prepared according to 3a) is placed in a beaker and a solution is obtained while stirring well with a mechanical stirrer added from 0.8 parts by weight of ethylenediamine in 100 parts by weight of water. It imagines itself immediately Water gel with a polymer content of 10% and a compressive stress of 1.2 KPa (kilopascals) after the 1st Load at 20% total load. The gel can be repeatedly frozen and permeated by cooling Thaw warming without losing its properties.

Example 4

a) Preparation of the prepolymer

615 g of a trifunctional polyether started on glycerine, the 30 weight percent propylene oxide and Contains 70 weight percent ethylene oxide units, a hydroxyl number of 26.5 and a molecular weight of 6460 are presented in a flask. 185 g of hexamethylene diisocyanate added and stirring 6 Heated at 1JU "C for hours. The resulting prepolymer has an isocyanate content of 9.6% (calculated 10.0%) and a viscosity of 2900 centipoise 25 ° C.

b) Production of a water bottle

A mixture of 100 parts by weight of water and 20 Parts by weight of the prepolymer prepared according to 4a) are placed in a beaker and placed under good Stirring with a mechanical stirrer, a solution of 1.37 parts by weight of ethylenediamine in 100 parts by weight of water is added. It forms after 4 Hours a water gel with a polymer content of 10%, which at 20% load a compressive stress of 4.1 KPa (Kilopascal) after the 1st load and is highly elastic.

c) Preparation of a methanol gel

A mixture of 100 parts by weight of methanol and 20 parts by weight of the prepolymer prepared according to 4a) is placed in a beaker and with good stirring with a mechanical stirrer one Solution from 13? Parts by weight of ethylene diamine and! 00 Parts by weight of methanol are added. After 25 seconds, a methanol gel with a Polymer content of 10% is formed, which is very stable

Example 5

a) Preparation of the prepolymer

590 g of a trifunctional started on glycerin

■ 3 polyethers, the 55 percent by weight propylene oxide and

Contains 45 weight percent ethylene oxide units, a hydroxyl number of 56 and a molecular weight of 30ÖÖ are placed in a flask, 210 g of hexamethylene diisocyanate are added and the mixture is stirred

ίο Heated for 4.5 hours at 120 ° C .. The resulting Prepolymers has an isocyanate content of 10.2 (calculated 10.0%) and a viscosity of 1670 Centipoise at 25 ° C.

_{| 5} b) Manufacture of a water gel

A mixture of 100 parts by weight of water and 20 parts by weight of the prepolymer described under 5a) are placed in a beaker and, while stirring well with a mechanical stirrer, a

A solution of 1.39 parts by weight of ethylenediamine in 100 parts by weight of water was added. After 5 seconds has become a water gel with a polyrricity of 10% is formed, which is highly elastic and a compressive stress of 6.1 KPa (kilopascal) at 20% load after the 1st load.

c) Manufacture of an ethanol gel

The procedure is as described in Example 5b), except that ethyl alcohol is used instead of water. After 29 seconds, an ethanol gel with a polymer content of 10% has formed, which is highly elastic and is stable.

Examples 6-8
Manufacture of water gels

A mixture of 100 parts by weight of water and 15 Parts by weight of the prepolymer prepared according to la) are placed in a beaker and under ■ 40 good mechanical mixing with a solution the amines given below in 100 Gewir.htsteile Water brought together. According to the reaction time given below, it always has a stable water content formed with a polymer content of around 7.5%.

Tabel I. Parts by weight Reaction at Aniin Time game Type 1.28 (lake.) 2 6th 1,3-diaminomethyl 0.71 benzene 1 7th Tetraethylene 1.13 pentamine 100 8th Guanidine carbonate

Example 9
Manufacture of a fiber-reinforced gel

The preparation of the water gel described in Example Ib) is repeated, but with as much Cellulose powder was mixed into component B that 2.5 percent by weight in the finished gel Cellulose powder are present. After mixing the two components, the solidification takes place

11th

Gels takes about a second. It then has to be thawed as a gel without affecting its properties

formed, which is highly elastic and loses at 20% load.

a compressive stress of 6.8 KPa (kilopascals) according to The examples in Table 2 below were with

"■■ Has stress. The gel can be repeated by a continuously operating machine according to

Cooling down to -10 ⁰ C frozen and carried out by heating 5 Fig.).

Table 2

example

Prepolymer chain extension code NCO middle number

NlIj / NCO

kg / h

kg / h

Liquid phase

(distilled

IhO)

kg / h

Temperature pH of the

at the outlet gel

the salary

Machine run-out

C%

Remarks

8-9 6th soft gel
(stable) S-Q ς ς ci »hr wfMrhpc 8-9
8-9
Il 3.3
4.7
10.5 not really anymore
lig homogeneous
gel
solid rope 1Γ 8.9 solid rope 9-10 5.8 soft strands 9
8th 5.6
6.5 homogeneous gel
cut-resistant gel 8th
8th 6.5
6th cut-resistant gel
Foam gel

IO

iib

lic

tie

12b
12c

a
13b

5.13 30

il J ₁ Ui J \ J

20th
20th
24

24

12a 2,3 15

20th
3Ü

30th
5.13 30

Ethylenediamine 64
(2% in H ₂ O
solved)

1.2

42.5 1.2

42.5 1.2

Ethylenediamine 87.5 1.0

87.5 1.0

Ethylenediamine 2?, 5 1.2

42.5
58

58

Ethylenediamine
(2% in H ₃ O
solved)

1.2 1.1

1.1 1.2

406

563 385 128

156

(Water with 0.1%

Nutrient salt)

186

300

372

(Water with 0.1%

Nutrient salt)

372

406

+ 1600 l / h air

For this purpose i sheet of drawings

Claims (5)

Patent claims: 1. Process for the production of stable, water- and / or alcohol-containing polyurethane urea gels, where one a) one containing 2 to 20% by weight of NCO groups Prepolymer, which by reaction of a hydroxyl-containing polyether with more than 40% by weight of ethylene oxide units with a polyisocyanate in an NCO / OH ratio greater than 1 was obtained with b) a diamine or polyamine in the presence of c) water and / or an alcohol reacts, characterized in that that either the components a, b and c are combined in one shot or a solution of component a in component c with component b. optionally dissolved in component c, combined under intensive mixing. 2. The method according to claim 1, characterized by the use of a centrifugal homogenizing machine / to mix the components. 3. The method according to claim 1, characterized by the use of eir./r device Countercurrent injection chamber for mixing the components. 4. Method according to claim 1 to 3 thereby characterized in that a Prapoly as component a meres based on a polyether with a molecular weight zvv'sehen '' 00O and 8000 included scl / t becomes. 5. Method according to An \ ppii: '· I to 4. thereby characterized in that as a component .ι a Prapoly more on Uasis of one au? Glycerin-launched Infunctional Polyathcrs is used