DE2531126A1 - Process for the preparation of unfoamed polymeric compositions - Google Patents

Description

Process for the preparation of unfoamed polymer compositions

Priority: 12/7/74 - Great Britain

The invention relates to new polymer compositions and, more particularly, to new polymer compositions based on Based on products derived from organic polyisocyanates and containing silicon dioxide fillers.

From GB-PS 1,186,771 it is known to contain silicic acid Materials by reaction of aqueous solutions of alkali metal silicates with organic polyisocyanates, if necessary in

50988 h / 1167

Essence of low molecular weight polyols to produce. However, this method results in materials with relatively poor properties, i.e. with a high degree of brittleness and low strength. This disadvantage is described in GB-PS 1,385,605, the disadvantages of the polyisocyanate / alkali metal silicate compositions can be attributed at least in part to the fact that no fine dispersion of the two components is formed. GB-PS 1,385,605 now describes the use of prepolymer ionomers for the preparation of fine emulsions with aqueous alkali metal silicate solutions, which are then used in the implementation of materials with good strength and elasticity.

It has now been found that unfoamed polymer compositions of the above type, which have polyurea units formed by the reaction of water and a polyisocyanate and a silica filler can be obtained without using special materials such as e.g. ionomers, used when considering other readily available isocyanate reactive compounds than low molecular weight polyols, namely, relatively high molecular weight polyols or tars or pitches, together with the polyisocyanate and the alkali metal silicate solution used. The polymer compositions according to the invention have good mechanical properties, which can be changed within a wide range by the selection of the isocyanate-reactive compound.

Thus, according to the invention, a process for the production of solid, unfoamed urea copolymer compositions, which contain silicon dioxide, which is carried out by making an oil-and-water emulsion manufactures, wherein the water phase from an aqueous solution consists of an alkali metal silicate and the oil phase of one Mixture of an organic polyisocyanate and an organic isocyanate-reactive polyol with a molecular weight von mi & desteaas ^ QO or one reactive with isocyanate Tar or pitch, the ratio of NCO groups to having

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Isocyanate reactive groups is greater than 1, or from the
Reaction product of an excess of an organic polyisocyanate with such a polyol or tar or pitch reactive with organic isocyanate, the reaction between the NCO groups and the water taking place at the oil / water interface and the evolution of carbon dioxide through reaction with the silicate, with the formation of silicon dioxide, is prevented.

In the previous paragraph, the oil phase of the emulsion was, according to one possibility, as a mixture of an organic polyisocyanate and an organic isocyanate-reactive compound with a molecular weight of at least 400 or
an isocyanate-reactive tar or pitch. It should be noted that the term "mixture" includes both homogeneous and heterogeneous mixtures. For example, the emulsion described can have an aqueous phase and a single oil phase. The oil phase can also consist of two mutually immiscible oil phases if the organic
Polyisocyanate and the organic isocyanate-reactive compound are not mutually soluble in one another. The nature of the emulsions is described in more detail below.

Examples of organic polyisocyanates that can be used are aliphatic diisocyanates such as hexamethylene diisocyanate, tetramethylene diisocyanate, 2,2,4- and
2,4,4-trimethyl-hexamethylene-diisocyanate, aromatic diisocyanates such as tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-4,4 ^l -diisocyanate, 3-methyl-diphenylmethane-4, 4'-diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, xylylene-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato- 3,3'-dimethyldiphenyl and diphenyl ether diisocyanate, and
cycloaliphatic diisocyanates, such as, for example, dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate and 3-isocyanatomethyl-S ^ jS-trimethylcyclohexyl isocyanate. Usable triisocyanates are, for example, aromatic triisocyanates, such as

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2,4,6-triisocyanatotoluene and triisocyanatodiphenyl ether.

Uretdione dimers and isocyanurate polymers of diisocyanate can also be used, such as tolylene-2,4-diisocyanate, Tolylene-2,6-dÜsocyanat and mixtures thereof. Furthermore, the biuret polyisocyanates can be used, which by Implementation of polyisocyanates with water can be obtained.

Mixtures of polyisocyanates can also be used, such as those mixtures obtained by phosgenation of the mixed polyamines are obtained, which in turn are obtained by reacting formaldehyde with aromatic amines, e.g. Aniline and o-toluidine, are formed under acidic conditions. An example of the latter polyisocyanate mixture is that known as crude MDI, which is obtained by phosgenating the mixed polyamines, which in turn can be prepared by reacting formaldehyde with aniline in the presence of hydrochloric acid. This mixture exists from diphenylmethane-4,4'-diisocyanate and isomers thereof and polyphenyl-polyisocyanates containing methylene bridges with more than two isocyanate groups.

It is preferred to use essentially pure diphenylmethane diisocyanate, especially the 4,4'-isomer, to be used when elastomeric Products are desired.

It is preferred to use raw MDI when hard products are desired.

Any isocyanate-reactive polyol with a molecular weight can be used of at least 400 or each isocyanate-reactive tar or each isocyanate-reactive pitch in the present invention Procedures can be used provided that it is in the form used, i.e., as such or after reaction with the polyisocyanate, forms a satisfactorily stable fine emulsion with the silicate solution. In general it means that the above-mentioned isocyanate-reactive compounds have a low solubility in water and a

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have a hydrophobic character
is often less stringent if the polyol is reacted with excess polyisocyanate prior to emulsification, but even in this case it is generally preferred that it should be hydrophobic in character.

In a preferred embodiment of the process according to the invention, organic isocyanate-reactive polyols are used with a molecular weight of at least 400 is used. So, according to a preferred embodiment of the invention a process for the preparation of solid, unfoamed urea / urethane copolymer compositions containing silica contain, proposed, which is carried out by preparing an oil-and-water emulsion, wherein the water phase consists of an aqueous solution of an alkali metal silicate and the oil phase consists of a mixture of one organic polyisocyanate and an organic isocyanate-reactive polyol having a molecular weight of at least 400, in which the ratio of NCO groups to OH groups is greater than 1, or from the reaction product of an excess an organic polyisocyanate with such an organic polyol, the reaction between the NCO groups and the water at the oil / water interface takes place and the development of carbon dioxide through conversion with the silicate, whereby silicon dioxide is formed, is prevented.

The nature of the polyol determines the character of the copolymer compositions obtained, as is the case in polyurethane technology is well known that high molecular weight linear polyols usually yield elastomeric products and that branched polyols having a low molecular weight give hard products.

Examples of polyols that can be used in the process according to the invention are polyesters and polyester amides, such as those obtained by known methods from carboxylic acids, glycols and, if necessary, minor amounts of diamines

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or amino alcohols can be obtained. Suitable dicarboxylic acids are succinic, glutaric, adipic, cork, azelaic, sebacic, Phthalic, isophthalic and terephthalic acids and mixtures thereof. Examples of dihydric alcohols are ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, diethylene glycol, Tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, Decamethylene glycol and 2,2-dimethyltrimethylene glycol. Suitable diamines or amino alcohols are hexamethylene diamine, ethylene diamine, monoethanolamine and phenylene diamines. Mixtures of polyesters and polyester amides can also be used if desired. Small amounts of polyhydric alcohols, such as glycerin or trimethylolpropane can also be used, in which case branched polyesters and polyester amides can be obtained.

Preferred polyesters for use in the process of the invention are those having a molecular weight of 1000 to 2000, in particular poly (ethylene adipate), poly (ethylene / propylene adipate), Poly (tetramethylene adipate) and poly (ethylene / tetramethylene adipate).

Examples of polyols for use in accordance with the invention are polyethers such as polymers and copolymers of cyclic Oxides, such as 1,2-alkylene oxides, e.g. ethylene oxide, Spichlorohydrin, 1,2-propylene oxide, 1,2-3utylene oxide and 2,3-butylene oxide, oxycyclobutane und.substituierte oxycyclobutane and tetrahydrofuran. Furthermore, polyethers should be mentioned, which by polymerization of an alkylene oxide in Presence of a basic catalyst and water, polyols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and triethanolamine, or amines such as aniline, tolylenediamine, Aniline / formaldehyde condensates (such as those used as precursors for pure MDI) and ethylenediamine, can be obtained. It should be noted that the polyethers linear, i.e. polyether diols, or branched, i.e. polyether triols, tetrols, etc., depending on the Functionality of the polyol or amine used to react with the alkylene oxide.

Polyethers for use in the process of the invention usually do not have a long part in their structure, which is formed by units derived from ethylene oxide, since such units generally impart an undesirable hydrophilic character to the polyether.

Preferred polyethers are derived from alkylene oxides with three or more carbon atoms per molecule. Particularly preferred are polyethers derived from 1,2-propylene oxide or from Derive tetrahydrofuran.

Polypropylene polyether glycols with molecular weights of 400-2000 represent a particularly preferred class of polyethers, with a molecular weight of 1000 being particularly preferred will.

Another preferred class of polyether diols are the poly (tetrahydrofurans) with a molecular weight of 1000 until 2000.

Another particularly preferred class of polyethers is formed by the branched polyethers of 1,2-propylene oxide. Polypropylene polyether triols with molecular weights of 400-3000 are particularly preferred. Such triplets will be by alkaline polymerization of propylene oxide in the presence of glycerol, trimethylolpropane, triethanolamine and hexanetriols obtain.

Another preferred polyol is castor oil.

Another class of preferred polyols is formed by the hydroxylated polybutadienes, d.s. the products of radical or anionic polymerization of butadiene under such conditions that a large number of hydroxyl groups is introduced into the polymer molecule. It is particularly preferred that such products have molecular weights of 400-4000, in particular from 2000-3000.

Other polyols used in the process according to the invention

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Can be det are epoxy resins, which are also made with isocyanate have reactive groups, such as the hydroxyl group-containing products produced by reaction between diphenylolpropane and epichlorohydrin are formed, hydrogenated alkyd resins modified with drying oils and non-drying oils Castor oil and the reaction products of castor oil and / or hydrogenated castor oil with a hard resin that is a rosinate Metal from group Ha of the periodic table, or a condensation product of rosin with

(I) at least one polyhydric alcohol or (II) at least one polyhydric alcohol and at least an optionally substituted phenol / formaldehyde resole resin or

(III) at least one polyhydric alcohol and at least a cc, ß-unsaturated dicarboxylic acid or an anhydride of that.

According to a further preferred embodiment of the invention, an isocyanate-reactive tar or isocyanate is used reactive pitch used. So according to this embodiment a process for the preparation of bulk, unfoamed urea copolymer compositions containing silica contain proposed, which is carried out by preparing an oil-and-water emulsion, wherein the water phase consists of an aqueous solution of an alkali metal silicate and the oil phase consists of a mixture of an organic one Polyisocyanate and an isocyanate-reactive tar or pitch, the ratio of NCO groups to isocyanate-reactive groups being greater than 1, or from the reaction product an excess of an organic polyisocyanate with such a tar or pitch, the reaction takes place between the NCO groups and the water at the oil / water interface and the evolution of carbon dioxide through Reaction with the silicate, whereby silicon dioxide is formed, is prevented.

Tars and pitches that contain isocyanate-reactive groups

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Zb3HZ6

and which are suitable for use in the process according to the invention are described in more detail in GB-PS 1,038,009. The tars obtained by degradative distillation are particularly useful for use in the process according to the invention obtained from coal, d.s. so coal tar. The pitches that are formed when these are also particularly useful Tars in turn are distilled, d.s. so coal tar pitch.

The products of the process according to the invention, which contain tars and pitches, have particularly good resistance against water, degrading organisms and pests. They are also often beneficial because of their relatively low price.

In the above preferred embodiment in which an isocyanate reactive tar or an isocyanate reactive Pitch is used, an isocyanate reactive polyol having a molecular weight of at least 400 to any may optionally Stage are incorporated in which isocyanate groups are available for the reaction with the polyol. For example the polyol can be mixed with the tar or pitch. Alternatively, both isocyanate-reactive Polyol as well as the isocyanate-reactive tar or the isocyanate-reactive pitch separately from the silicate solution and the Polyisocyanate can be added at any stage during the formation of the emulsion. It can be useful either reacting the tar or pitch or polyol with excess polyisocyanate before processing together with the silicate solution and the other tar or pitch or polyol takes place in an emulsion. It is also possible to use both To implement excess polyisocyanate before the preparation of an emulsion with the silicate solution. If here from one "Polyisocyanate excess" is spoken of, then it is to be understood as an excess over the amount required for the reaction with both the polyol and the tar or pitch is required.

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It can be any of the above-mentioned polyols having a molecular weight of at least 400 can be used in the above procedure, provided it is with the tar or pitch is compatible or becomes compatible with it during the procedure. Polyols are more likely to Systems compatible with the tar or pitch will result if the tar or pitch is first treated with excess polyisocyanate is implemented.

The compositions produced by the process of the invention other fillers such as talc, alumina, barite, asbestos, mica, zinc stearate, slate powder, Wood flour, sawdust, vermiculite, wood chips, fiberglass, fly ash, expanded clay, marble and other natural or artificial colored sands, flints or rocks, inorganic pigments such as red iron oxide, titanium dioxide and Chrome pigments, organic pigments such as azo pigments and pigments based on phthalocyanine, and synthetic ones organic polymers, namely thermoplastic or thermally curable polymers or copolymers, such as nylon polymers, Polyvinyl chloride, polyvinyl chloride / polyvinyl acetate copolymers, Urea / formaldehyde polymers, acetal polymers and copolymers, Acrylic polymers and copolymers, acrylonitrile / butadiene / styrene terpolymers, Cellulose acetate, cellulose acetate butyrate, polycarbonates, polyethylene terephthalate, polystyrenes, polyurethanes, Polyethylene and polypropylene. These polymers can be unpigmented or pigmented in the bulk and incorporated into the composition in the form of powders, lumps, chips, fibers, flakes, tapes or films.

The components used to produce the emulsion in the process of the invention can also include a catalyst which is known to catalyze the reaction between isocyanate groups and hydroxyl groups. Examples such catalysts are organometallic compounds, metal salts and tertiary amines. Specific examples are Dibutyl tin dilaurate, tetrabutyl titanate, zinc octoate, zinc

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naphthenate, tin (II) octoate, tin (IV) chloride, iron (III) chloride, lead octoate, potassium oleate, cobalt 2-ethylhexoate, N, N-dimethylcyclohexylamine, Ν, Ν-dimethylbenzylamine, N-ethylmorpholine, 1 , 4-diazobicyclo-2,2,2-octane, 4-dimethylaminopyridine, oxypropylated triethanolamines, ß-diethylaminoethanol and N, N, N ', N ¹ -etrakis (2-hydroxypropylethylenediamine.

The alkali metal silicates used are preferably potassium and especially sodium silicates. You can by the formula where Me is the alkali metal

and χ stands for the molar ratio of SiOp to MepO. In the case of potassium silicate, χ preferably varies between 1.43 and 2.48, and in the case of sodium silicate, values for χ from 1.6 to 3.3 are preferred. The solution used may be 1 to 99 wt -.% Alkali metal silicate include, in which 27-52% are preferred for sodium silicate and 35-60% of potassium silicate. If necessary, the alkali metal silicate solution used can be prepared in situ, for example by adding powdery soluble alkali metal silicate and water to a polyol with stirring, the silicate dissolving in water. Production in situ can take place before, during or after emulsification in the polyol.

The proportion of polyol or tar or pitch in the combined weights of the polyisocyanate and polyol or tar or pitch can vary widely. It will usually not be less than 25 % . It can go up to 95 % , for example when elastomeric products are to be made from polyols with a high molecular weight, such as, for example, diols with a molecular weight of 10,000.

Mixing of the components to make the emulsion can be carried out by methods known in the art. Of the The degree of mixing required to achieve a fine emulsion depends on the nature of the components. In some cases simple agitation may be sufficient, while others may require high-speed shear mixers. The addition of emulsifying agents, for example non-ionic ones

5O988 ¹ 4 ^1/1 "167

Types, such as ethylene oxide / propylene oxide block copolymers, can be useful, but seldom necessary.

A microscopic examination of the emulsions formed in the process according to the invention shows that they are often of the water, ser-in-oil types are and often also of a tertiary character i.e. that they are of the oil-in-water-in-oil type.

In those cases where the polyisocyanate and the polyol or the tar or the pitch are not reacted before emulsification it is often preferred to prepare the emulsion in two stages. For example, it is particularly preferred that the silicate solution and the polyol or the tar or the pitch are emulsified in a first stage and the polyisocyanate is then added in a second stage. The absence of mutually reactive chemicals in the emulsion the first stage allows for storage or large-batch manufacture if desired.

If you work in the reverse order, i.e. first the silicate solution and the polyisocyanate emulsify then it is necessary to ensure that the polyol or tar or pitch is added before the water / Isocyanate reaction has progressed so far that there are insufficient NCO groups for the reaction with the polyol or tar or bad luck left behind.

If the polyisocyanate is added in the second stage of the two-stage process, then it can, at least initially, be insoluble in polyol or tar or pitch. The polyisocyanate is naturally not soluble in the silicate solution, therefore a multiphase emulsion is formed. This usually takes the form of a continuous phase the polyol or tar or pitch which comprises two dispersed phases, namely silicate solution and polyisocyanate. Of the The usual procedure in such cases is that the reaction of the polyisocyanate with the polyol or tar or pitch begins takes place at the interface, the products of this reaction

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tion then the mutual solubility of the remaining polyisocyanate and improve polyol or tar or pitch, creating a homogeneous phase. The water in the silicate solution then reacts at its interface with this single phase, the polyol or tar or pitch and polyisocyanate ' and contains their reaction products.

The reaction products of polyols or tars or pitches with excess polyisocyanate, which in the invention Methods that can be used can be prepared by conventional means. Such reaction products are in commonly known in polyurethane technology under the name "prepolymers". The known techniques for preventing premature Gelation, for example the addition of acidic materials and the selection of certain amounts of branched Reactants are also applicable in accordance with the invention.

The reaction between the polyisocyanate and the water in the silicate solution results in the formation of carbon dioxide, which in turn reacts with the silicate to form silicon dioxide. To the formation of massive, unfoamed compositions To ensure that there is sufficient alkali metal silicate to react with most, and preferably all, of the amount of the released carbon dioxide be present. In practice it is usually desirable to have excess Alkali metal silicate is present.

The amount and concentration of the silicate solution should be such that there is sufficient water for the reaction with all isocyanate groups, which are not consumed in the reaction with polyol or tar or pitch is present. It is usually desirable that there is an excess of water. However, only relatively small proportions by weight of water are required, because of the low equivalent weight of water in the reaction with isocyanates. The water and the silicate should be in sufficient quantities that at least the following equation is satisfied:

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4NC0 + 3H ₂ O + Me ₂ O.XSiO ₂ -> 2 (NH) ₂ CO + 2MeHCO ₃ + xSiO ₂

The formation of the massive, unfoamed copolymer compositions, which contain silicon dioxide, the process according to the invention often takes place at room temperature according to / emulsification of the components takes place, but heating may be necessary to accelerate the reaction.

The compositions obtained by the method according to the invention may be in the form of molded articles. These are obtained, for example, by emulsifying the Components are poured into a mold in a still flowable state, v / o curing under pressure is carried out. They can be used as binders in fiber products, for example for the impregnation of woven or mats non-woven fibers with the emulsified components. Suitable fibers are e.g. cotton, jute, glass or carbon. Such Products can have a wide variety of shapes, such as panels or pipes, which are suitable for use in construction. The compositions of the invention can also be used in a wide variety of coating applications. For example, they can be used to cover floors or roofs, pipe coatings and protective and decorative Produce coatings on a wide variety of substrates such as wood, metal or concrete. The more flexible compositions are suitable as sealants, for example in expansion joints in buildings. The coatings can be known by Process are applied, for example with a brush or with a spray device.

The new procedure offers compared to the conventional incorporation of silica fillers in polymer compositions based on organic polyisocyanate condensation products have the following advantages:

(a) The silica filler becomes colloidal in situ Form formed. This eliminates mechanical mixing and pumping problems that are often associated with the addition of silica fillers.

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directly to the polymer precursor (e.g. thixotropy, Discontinuation, etc.).

(b) In the case of massive filled urethane polymers, the filler added must be carefully dried in order to avoid "gassing" due to the formation of CO ₂ . The new process completely eliminates this problem.

The invention is illustrated in more detail by the following examples, in which the parts and percentages are expressed by weight are.

example 1

100 parts of the resin made according to the instructions below has been obtained, and 100 parts of a 6596 aqueous Sodium silicate solutions are stirred together so that an emulsion is formed. This emulsion becomes 100 Portions of a "crude" diphenylmethane diisocyanate having an NCO value of 30.0 were added, whereupon the mixture was formed an emulsion is stirred. This emulsion sets into a hard, unfoamed solid within 4 hours.

The resin used in this example can be obtained as follows:

Natural rosin (colophony), glycerin and a resole resin (produced by condensation of 1 mole of diphenylolpropane and approximately 4 moles of formaldehyde under aqueous alkaline conditions) are combined in the weight ratios 8.2: 1.1: 1.0 heated to a temperature of about 275 C in an inert atmosphere until the acid value of the product is less than Is 20 mg KOH / g.

4 parts of castor oil and 1 part of this product are then heated for 45 min in common to about 24O ⁰ C.

Example 2

The procedure of Example 1 is repeated except that 50 g of a granulated automobile tire rubber having a grain size of

509884/1 ^ 67

about 3 mm before adding the polyisocyanate. A hard, slightly flexible product is obtained.

Example 3

30 parts of the product of the reaction of oxypropylated ethylene glycol with a MW of 1000 and the polyisocyanate used in Example 1 (NCO: OH ratio 10: 1), 50 parts of a 65% aqueous sodium silicate solution and 20 parts of coal tar (viscosity about 25 poise at 25 ° C) are mixed together to form an emulsion. The mixture is approximately 10 minutes processable and then sets within 4 hours into a tough, slightly flexible, non-foamed solid.

Example 4

50 parts of a polybutadiene polyol terminated with hydroxyl groups having a MW of 2,650, 50 parts of 65 # strength aqueous sodium silicate solution and 50 parts of that used in Example 1 Polyisocyanate are mixed together and put into greased polymethyl methacrylate molds with the dimensions 101.6 χ 50.8 χ 12.7 mm poured in and then left to harden. To After curing for 8 hours, a tough elastomeric product was created.

Example 5

The procedure of Example 4 is repeated except that the polybutadiene polyol is replaced by 50 parts one by hydroxyl groups terminated styrene / butadiene polymer with MW 3500 replaced will. After curing for half an hour, a tough elastomeric product is obtained.

Example 6

50 parts of a polybutadiene polyol terminated by hydroxyl groups (MW 2650) and 50 parts of a 65% sodium silicate solution are mixed together to form an emulsion. To this emulsion are added:

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400 parts of Garside-21-Sand 200 parts of Flintag grade 3 200 parts of Flintag grade 4

The whole is stirred until homogeneous.

To this mixture 50 parts of the polyisocyanate used in Example 1 are added, whereupon the whole is stirred again will until it is uniform.

The mixture produced is poured into greased mild steel molds with the dimensions 76.2 χ 76.2 χ 76.2 mm cast in and 7 Allowed to cure for days. The compressive strength of each cube is then measured.

The cubes behave elastically under pressure. They have a final compressive strength of 160.6 kg / cm.

Example 7

50 parts of the reaction product of oxypropylated ethylene glycol and polyisocyanate, which is used in Example 3, 10 parts of butyl benzyl phthalate and 1 part of "Silcolapse 430" (a polymethylsiloxane flux) are mixed together, whereupon 40 parts of a 40% solution of sodium silicate were added while the mixture is vigorously stirred. The emulsion obtained remains pourable for 25-30 minutes. From this Sheets cast in emulsion in "Perspex" molds can be demolded in 3 hours. After 7 days they own at room temperature the following properties:

Tensile strength 160.6 kg / cm

Elasticity 13 %

Flexural Strength 97.8 kg / cm

Flexural modulus 0.58 χ 10 kg / cm

Compressive strength 766.5 - 846.8 kg / cm ²

Example 8

An emulsion prepared according to Example 7 is 5 parts

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12 mm long glass fibers mixed and as in that example deformed. The composite product obtained has the following properties:

Tensile strength 255.5 kg / cm ²

Elasticity 12 %

Flexural Strength 438.0 kg / cm

Flexural modulus 0.29 x 10 " ⁵ kg / cm ²

Compressive strength 730.0 kg / cm

Maintain the fittings from this and the previous example in the absence of an external flame or other source of heat, combustion does not occur.

Example 9

100 parts of the reaction product of poly (tetrahydrofuran) with MW 2000 and pure diphenylmethane diisocyanate (NC0: OH ratio 3: 1) (NCO value = 6.21 %) are mixed with 11.3 parts of a higher% sodium silicate solution, whereby a creamy emulsion is obtained.

The emulsion is st in a compression mold under a pressure of 146.0 kg / cm at a temperature of 110 ⁰ C 3 cured in length, with 2 mm thick plates with good elastomeric Eigenschäften, ie a good tensile strength and tear resistance, and a stretchability of more than 300 % .

Example 10

100 parts of the reaction product of poly (tetrahydrofuran) with MW 1000 and pure diphenylmethane diisocyanate (NCO: OH ratio 2.5: 1) (NCO value = 7.8 %) and 14.2 parts of a 40% sodium silicate solution emulsified and cured as described in Example 9 to give a similar elastomer.

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Example 11

60 parts of oxypropylated glycerol with MW 3000 and 30 parts of sodium silicate powder (approximate composition 85 % NapSiO, 15 % water) are stirred together, during which 25 parts of water are gradually added. Stirring is then continued until the sodium silicate is dissolved.

50 parts of the crude polyisocyanate used in Example 1 are added with stirring. The emulsion obtained remains pourable for 1 minute and quickly hardens into a tough, unfoamed one Product from.

Example 12

50 parts of Epikote 828 (a commercial diphenylolpropane / epichlorohydrin condensate) and 50 parts of a 4OS6 sodium silicate solution are emulsified by rapid stirring. 50 parts of the crude polyisocyanate used in Example 1 are below Stirring is added and the resulting emulsion is poured into "Perspex" molds, where it is poured into a hard, vitreous solid hardens.

Example 13

50 parts of the reaction product of crude diphenylmethane diisocyanate with a 4: 1 mixture of polypropylene glycol with MW 1000 and oxypropylated glycerol with MW 1500 (NCO: OH ratio 2.4: 1) (NCO value 7.3 %) and 30 Portions of a 40 # strength sodium silicate solution are emulsified by stirring and poured into molds. The composition hardens at room temperature into a soft elastomer (Shore A hardness 50 °), which is suitable for use as an expansion joint sealant.

Example 14

50 parts of the reaction product of polypropylene glycol of MG 1000 and pure diphenylmethane diisocyanate (NCO: OH ratio 4: 1) (NCO value = 12.6 %) and 40 parts of a 40% sodium

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The silicate solution is emulsified by stirring and placed on a polyethylene sheet cast, where curing takes place at room temperature in a tough flexible film.

Example 15

Example 7 is repeated, the reaction product of oxypropylated ethylene glycol and crude diphenylmethane diisocyanate replaced by a similar product made from oxypropylated glycerine of MG 1000 and crude diphenylmethane diisocyanate will. A hardened product with the following properties is obtained:

Tensile strength 175.2 kg / cm ²

Elongation 7 %

Flexural Strength 292.0 kg / cm ²

Flexural modulus 0.20 10 ^ kg / cm

Compressive strength 730.0 kg / cm ²

Examples 16-18

Similar emulsions to those in Examples 9, 10 and 11 are prepared, but in all cases the amount the sodium silicate solution is increased to 40 parts. The resulting emulsions are made in a 2 mm plate printing mold cured under a pressure of 146.0 kg / cm at room temperature for 3 hours. After 7 days at room temperature, the molded panels have the following properties:

Example 16 Example 17 Example 18

Prepolymers of example 9 10 11 Tensile strength MN / nT 10.3 14.0 20.8 Elongation at break % 440 400 510 Module - 100 % 4.5 7.2 8.8 200 % 5.4 8.8 10.0 300 % 6.8 10.8 12.0 Trouser tear strength 10.0 17.0 20.0 capacity KN / m2 Hardness ⁰ BS 90 95 95

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Example 19

A similar emulsion as in Example 9 is prepared, however, 20 parts of sodium silicate solution are used in place of the 11.3 parts of that example.

The emulsion is poured into a 2 mm plate printing mold and 3 st
hardened.

sen and 3 st at 110 ⁰ C under a pressure of 146.0 kg / cm

The hardened plate has the following properties:

Tensile strength MN / m ² 21.8

Elongation at break % 640

Module - 100 % 5.4

200 % 6.8

300 % 8.6

Trouser tear strength KN / m 19.8

Hardness ⁰ BS 90

Example 20

2000 parts of polypropylene glycol of MW 2000 and 522 parts of toluene diisocyanate (80/20 mixture of the 2,4 and 2,6 isomers) reacted together to produce a prepolymer with an NCO content of 6.68%.

50 parts of this prepolymer are mixed with 20 parts of the sodium silicate solution used in Example 7 by rapid stirring mixed. The emulsion obtained has a shelf life of 40 minutes and is poured into a flat polyethylene mold and left to cure for 24 hours at room temperature.

An elastomeric solid composite product is obtained, which shows no traces of foaming.

Example 21

50 parts of a polybutadiene polyol with an OH value of 46.6 mg KOH / g (R-45HT from Atlantic Richfield) and 30 parts isophorone diisocyanate are in the presence of 0.5 parts of dibutyl

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tin dilaurate 43 st long implemented.

50 parts of the resulting prepolymer are 50 parts of the sodium silicate solution used in Example 1 under good Stirring added. The emulsion obtained is poured into a mold and cured 2 V / ochen at room temperature. It will obtained an elastomeric solid composite product showing no trace of foaming.

Example 22

Example 7 is repeated except that 40 parts of grade 120 potassium silicate from J. Grossfields Ltd. instead of the sodium silicate be used. The emulsion obtained is pourable for 10 minutes. It has a higher exothermic heat of reaction than the corresponding sodium silicate mixture of Example 7. Panels cast from the mixture can be used can be removed after 1 hour. They have similar properties to the composite products of Example 7.

Example 23

100 parts of a liquid coal tar (Orgol Tar No. 1 of British Steel Corporation) and 80 parts of that used in Example 7 Sodium silicate solutions are mixed with rapid stirring, creating a dispersion of sodium silicate solution in tar is obtained. 80 parts of the crude diisocyanate used in Example 1 are added with stirring. After 24 hours is a hard black solid product emerged.

Example 24

300 parts of Special Pitch No. 3 (from British Steel Corporation) and 100 parts of butyl benzyl phthalate are mixed together. 200 parts of castor oil (first pressing) are then slowly added with stirring, a black mixture being obtained that is thixotropic.

500 parts of the sodium silicate solution used in Example 7

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are added to the above mixture with stirring and mixed thoroughly, followed by 250 parts of that used in Example 1 crude diisocyanate are added.

After 2k st, a black flexible product is obtained which is suitable as a composition for application to roofs and floors.

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Claims (4)

PATENTA? ISPRUCHE; 1.' A process for the preparation of a solid, unfoamed ^Sy isocyanate reaction product which contains silicon dioxide, characterized in that an oil-and-water emulsion is prepared in which the water phase consists of an aqueous solution of an alkali metal silicate and the oil phase consists of a mixture of an organic polyisocyanate and one organic isocyanate-reactive polyol with a molecular weight of at least 400 or an isocyanate-reactive tar or pitch, the ratio of NCO groups to isocyanate-reactive groups being greater than 1, or from the reaction product of an excess of an organic polyisocyanate with one with organic isocyanate-reactive polyol or tar or pitch, the reaction between the NCO groups and the water taking place at the oil / water interface and the development of carbon dioxide being prevented by reaction with the silicate, whereby silicon dioxide is formed. 2. The method according to claim 1, characterized in that sodium silicate is used as the alkali metal silicate. 3. The method according to claim 1 or 2, characterized in that crude MDI is used as the polyisocyanate. 4. The method according to claim 1 or 2, characterized in that 4,4'-diphenylmethane diisocyanate is used as the polyisocyanate will. _ 24 60988A / 1167