DE102014002594A1 - Bulk or shaped bodies of inorganic polymers and their preparation - Google Patents

Abstract

The invention relates to a method for producing a mass or a shaped article of inorganic polymer, in which water glass is hardened with an amide in specific amounts, solid adjuvants and, if appropriate, various further substances being able to be added. In addition, compositions and moldings obtainable by this method are described and their use.

Description

Area of Expertise

The present invention relates to a process for the preparation of masses and moldings of inorganic polymers and in this process obtained masses and moldings and their use z. B. in the construction industry and for foundry molds.

background

Inorganic polymers are known. Thus, a reaction between water glass, ie sodium silicate, and metakaolin (Al ₂ Si ₂ O ₇ ) is often referred to in the literature as geopolymerization. Geopolymerisation is based on the formation of polymeric structures between oxygen, silicon and aluminum. Are reacted with water glass with metakaolin with admixture of sodium or potassium hydroxide as an activator; the optimal pH of this reaction is in the range of pH 13 to 14. After J. Davidovits in "GEOPOLYMERS Inorganic polymeric novel materials", Journal of Thermal Analysis, Vol. 37 (1991), pp. 1633-1656 this reaction is an OH-catalyzed polycondensation of SiOH and AlOH groups to a mixed silyl ether (SiOAl) with dehydration. Characteristic of this reaction is its long duration of several hours to days. For acceleration, it is usually carried out at elevated temperatures (80-160 ° C). The formed three-dimensional network consists of covalent -Si-O-Si and -O-Si-O-Al-O bonds in the form of Si and Al tetrahedra, which are linked together by four oxygen atoms. The bond lengths between silicon and oxygen (Si-O: 1.63 Å) and aluminum-oxygen (Al-O: 1.73 Å) are almost the same length. Virtually no O-Al-O-Al-O bonds are formed (Lowenstein's Rule). For example, each aluminum tetrahedron (AlO ₄ ^- M ⁺ ) is usually surrounded by four SiO ₄ tetrahedra.

From the EP 0 148 280 B1 are water-containing, curable molding compositions of inorganic components in flowable or pressable distribution with optionally contained proportions of fillers known.

From the essay "Water glass ester molding material for cast iron castings" by H. Glaß in foundry practice 1-2 / 2006, pages 22 to 26 is the use of a molding material system with quartz sand, sodium silicate as a binder liquid and glycerol esters of acetic acid, which may be present as mono-, di- or triacetate, known as a hardener component. The amount of hardener should be about 1/10 of the amount of binder.

From the essay "Mechanism of geopolymerization and factors influencing its development: a review" by D. Khale and R. Chaudary in J. Mater. Sci. (2007) 42: 729-746 Geopolymere are known, wherein reactions of Geopolykondensation, in particular the Orthosialatbildung and Alkalipolysialatbildung and the conversion of Ortho (sialate siloxo) to polysialate siloxane compounds are discussed. It is also discussed that the most important factor for the compression strength of products is the pH. The effect of phosphate salts in delaying gel solidification is discussed.

Next is out "GEOLOPOLYMERS Inorganic polymeric new materials" by J. Davidovits in Journal of Thermal Analysis, Vol. 37 (1991), pages 1633-1656 It is known that certain inorganic substances can polycondensate at temperatures below 100 ° C.

Further, please refer to: Andree Barg, Dissertation, Paderborn 2004 ; Anja Buchwald, What are Geopolymers? Concrete Plant and Precast Technology (BFT) 72 (2006), 42-49 ; Radnai, T., May, PM, Hefter, G. and Sipos, P. (1998) Structure of aqueous sodium aluminate solutions: A solution X-ray diffraction study. Journal of Physical Chemistry A, 102 (40). pp. 7841-7850 ;
James Murray, Davis King, Oil's tipping point has passed, Nature 481 (2012), 433-435 ; Ivan Sumirat, Y. Ando, S. Shimamura, Theoretical Consideration of the Effect of Porousity on Thermal Conductivity of Porous Materials, J. of Porous Materials, 13 (2006), 439-443 ; J. Davidovits, J. Mater. Educ. 16, (1994), 91-137 ; H. Rahier, B. van Mele, J. Wastiels, X. Wu: Low-temperature synthesized aluminosilicate glasses, Part I: Low-temperature reaction stoichiometry and structure of a model compound. J. Material Science, 31 (1996), 71-79 ; H. Rahier, B. van Mele, J. Wastiels, Low-Temperature Synthesized aluminosilicate glasses, Part II: Rheological transformation during low-temperature cure and high temperature properties of a model compound. J. Material Science, 31 (1996), 80-85 ; H. Rahier, W. Simns, B. van Mele, M. Briesemans, Low-Temperature Synthesized Aluminosilicate Glasses, Part III Influence of the Composition of the Silicate Solution to Production, Structure and Properties, J. Material Science, 32 (1997) , 2237-2247 ; WD Nicoll, AF Smith, Stability of Dilute Alkaline Solutions of Hydrogen Peroxides, Industrial and Engineering Chemistry, 47 (1955), 2548-2554 ; E. Rönsch, A. Porzel, Chemical modification and investigation of water glass solutions as a binder for foundry mold materials, foundry technology 27 (1988), 348-351 ; KJD MacKenzie, IWM Brown, RH Meinhold, Outstanding Problems in the Kaolinite Mullite Reaction Sequence Investigated by ²⁹Si and ²⁷Al Solid-state Nuclear Magnetic Resonance: I, Metakaolinite, J. Am.Ceram. Soc. 68, (1985), 293-297 ; Puyam S. Singh, Mark Trigg, Iko Burgar, Timothy Bastov, Geopolymer formation process at room temperature studied by ²⁹Si and ²⁷Al MAS-NMR, Materials Science and Engineering A 396 (2005), 392-402 ; Zhongqi He, C. Wayne Honeycutt, Baoshan Xing, Richard W. McDowel, Perry J. Pellechia, Tiequan Zhang, Solid State Fourier Transform and 31 P nuclear magnetic resonance spectral features of phosphate compounds, Soil Science 172 (2007), 501 -515 ; S.-P. Szua, LC Klein, M. Greenblatt, Effect of precursors on the structure of phosphosilicate gels: ²⁹Si and 31P MAS-NMR study, J. Non-Cryst. Solids 143 (1992), 21-30 ; H. Maekawa, T. Maekawa, K. Kawamura and T. Yokokawa, Structural groups of alkali silicate glasses determined from ²⁹Si MAS-NMR, J. Non-Cryst. Solids 127 (1991), 53-64 ,

EP 2 433 919 A1 describes hardener composition for controlling the setting behavior of an alkali silicate binder. Mention should also be the EP 0 495 336 B1 , the EP 0 324 968 A1 , the WO 89/02878 A1 , the JP 57063370 A , the ZA 8802627 A , the EP 0 455 582 A , the DE 32 46 602 A1 , the US 4,642,137 A , the US 4,983,218 A , the GB 1 283 301 A , the GB 1 429 803 A , the WO 95/15229 A , the DE 2 856 267 A1 , the EP 0 641 748 A1 , the DE 697 34 315 T2 , the GB 1 429 804 A and the EP 0 495 336 B1 ,

However, improvements in product properties and their manufacture are still desirable.

It is desirable that the starting materials or components used for the preparation are sufficiently stable on storage, recyclability is ensured, and only little or no safety requirements are to be observed during processing. The finished mass should be free of nail, grindable, sawn etc. Further, the material should be fungus and acid resistant; In addition, refractoriness and / or temperature and / or UV resistance would be desirable.

The object of the present invention is to provide a method for producing a mass or a shaped body which fulfills at least some of the properties described above. Another object is to provide a composition or molding having at least some of the properties described above.

The object is achieved by the method defined in the claims and the products defined in the claims.

Description of the figure

1 shows samples of various examples of the invention.

Detailed description of the invention

In the method according to the invention, a first composition (hereinafter composition a)) is brought into contact with a second composition (in the following composition b)) for a polycondensation and solid additive (preferably with OH groups) is added.

Composition a) is an aqueous composition containing sodium and / or potassium waterglass dissolved in water.

Water glasses are usually made of sand and Na or K carbonate. They consist of water-soluble silicates whose negative charge is compensated by monovalent countercations (M ⁺ ).

It is possible to use a sodium water glass (sometimes called soda water glass) or a mixture of different sodium water glasses. In addition, a potassium water glass (sometimes referred to as potassium water glass) or a mixture of different potassium water glasses can be used. The use of one or more potassium water glasses is preferred over the use of one or more sodium water glasses since higher pressure stability is achieved. According to one embodiment, a mixture of sodium and potassium water glass, such as. B. 90:10 to 10:90 mixture, e.g. As a 50:50 (based on total weight of dissolved water glass) mixture or a 90:10 mixture used.

Water glasses are characterized by their s-value, which indicates the mass ratio SiO ₂ / M ₂ O (M = alkali metal); the smaller the s value, the more alkali metals are present. Water glasses with different s-values are commercially available.

Water glasses with s values in the range of 0.7 to 8 are known. For the present invention, water glasses with an s value of 1.3-5 are preferably used.

As potassium water glasses come for the invention z. For example, those with an s value of 1.3-4.5, preferably 2-3.5 in question.

As soda water glasses come for the invention z. For example, those with an s value of 2-5 in question, preferably 3-4.5.

According to one embodiment, a mixture of water glasses is used in which the proportion of water glass having an s value of 1.3 to 5 is at least 90%, based on the total amount of water glass dissolved in composition a).

By using a mixture of potassium and soda waterglass, surprisingly, the crack resistance and the shrinkage behavior of the product could be improved. The use of potassium silicate glass has a favorable effect on the pressure stability of the product.

Aqueous solutions of water glasses are viscous. Sodium water glasses usually lead to a higher viscosity than potash water glasses with the same SiO ₂ content (s value).

For the preparation of the composition a) z. B. of commercial water glass solutions having a solids content of about 30-48 wt .-% are assumed.

Water glasses can also be characterized by their structural properties with respect to existing silicon groups:
The s value of a water glass determines the chemical constitution of the silicate. At an s value of s = 1, the silicate has on average a negative charge. Theoretically, the s value can drop to 0.25. The formula of such a potassium silicate would be K ₄ SiO ₄ , ie a four-fold negatively charged silicon / oxygen tetrahedron. This functional group is referred to below as Q ₀ . If such a Q ₀ group forms an Si-O-Si bond by condensation, a Q ₁ group is formed. There is exactly one O-Si group attached to the central silicon atom. The suffix thus refers to the number of bridging oxygen atoms that bind to this silicon atom. Accordingly, a central silicate group with two bonds to silicon atoms is called a Q ₂ -, with three bonds one O ₃ - and with four bonds a Q ₄ group. The Q ₄ group no longer carries a negative charge and is neutral.

Q₀:

Monosilikat

Q₁:

Endgruppe

Q₂:

Mittelgruppe

Q₃:

Verzweigungsgruppe

Q₄:

Vernetzungsgruppe

Thus, the different silicon groups can be characterized as follows:

Q ₀ :

mono silicate

Q ₁ :

end group

Q ₂ :

Central group

Q ₃ :

branching group

Q ₄ :

networking group

The Si-OR group stands here as a placeholder for a further branching of the Si-O-Si skeleton. The Q ₄ group, not shown, no longer has a negative charge but consists only of Si (OR) ₄ groups which can no longer react in the sense of a polycondensation reaction.

To determine the percentages of Q ₀ to Q ₄ in a given waterglass, ²⁹ Si MAS NMR spectra can be used.

In the present invention, for. For example, an Advance 500 DSX 500 WB from Bruker (Billerica, USA) is used at room temperature with a 4 mm ZrO ₂ rotor and the rotation speed of 9 or 10 kHz; the following irradiation frequency was used: ²⁹ Si: 99.36176 MHz. It was worked with single pulse program, with the following pulse time: 45-degree pulse at ²⁹ Si with a pulse duration of 2 μsec. The cooldown was ²⁹ Si: 6 sec.

In the context of the present invention and all embodiments described herein, water glasses with the following characterization are preferred:
Preferred range Q ₁ : 2-6%
Preferred range Q ₂ : 10-25%
Preferred range Q ₃ : 15-25%
Preferred range Q ₄ : 45-70%
wherein the area of those peaks associated with a particular silicon group Q (i) is related to the sum of the area of all Si NMR signals (= 100%).

For the present invention, moreover, it has been found to be essential that the pH of the composition a) at 25 ° C is at least 12 (measured with pH meter).

By using the amide hardener (I) or derivatives thereof, the pH is lowered in the polycondensation. In order that the pH in the reaction does not noticeably drop below 10, a minimum pH of 12 is required for the composition a). Usually, the pH in the reaction will drop by about 1-1.5 units.

Due to the alkaline pH, composition a) is resistant to fungal colonization and relatively stable to acid, resulting in a good storage stability.

wobei R¹ bis R⁴ unabhängig voneinander ausgewählt werden aus H und gegebenenfalls mit einer oder mehreren OH-Gruppen substituiertem C_1-6 Alkyl oder einer von R¹ und R² und einer von R³ und R⁴ mit der Gruppe

einen 5-gliedrigen Ring bilden, der gegebenenfalls ein- oder mehrfach mit Substituenten substituiert ist, die ausgewählt sind aus C₁₂ Alkyl und C₁₂ Alkyl substituiert mit einem oder mehreren OH.The composition b) contains, in addition to water, at least one water-soluble or water-miscible (preferably water-soluble) hardener, the hardener being selected from amides of the general formula (I) and derivatives selected from biurets and urethanes

wherein R ¹ to R ^{4 are} independently selected from H and optionally substituted with one or more OH groups substituted C _1-6 alkyl or one of R ¹ and R ² and one of R ³ and R ⁴ with the group

form a 5-membered ring optionally substituted one or more times with substituents selected from C ₁₂ alkyl and C ₁₂ alkyl substituted with one or more OH.

The C _1-6 (preferably C _1-4 , more preferably C _1-2 ) alkyl groups may be independently optionally substituted with one or more OH groups, which may improve the water solubility of the curing agent.

wobei ein oder mehrere H gegebenenfalls durch aliphatische (Gruppen wie z. B. Alkylgruppen ersetzt sind) und Urethan

(wobei die Ethylgruppe gegebenenfalls mit einem oder mehreren Substituenten, ausgewählt aus aliphatischen Gruppen wie z. B. Alkylgruppen, substituiert ist).Suitable examples of hardeners are urea (R ¹ = R ² = R ³ = R ⁴ = H), biuret

wherein one or more H are optionally replaced by aliphatic (groups such as alkyl groups) and urethane

(wherein the ethyl group is optionally substituted with one or more substituents selected from aliphatic groups such as alkyl groups).

The amount of added hardener determines in the product not only the number of cross-links, but also the hardness of the product.

The inventors of the present invention have found that the following condition must be met in order to obtain products having good strength:
The amount of hardener used in g (m _H ) is m _stö to x · m _stö

MG_H

= Molekulargewicht des verwendeten Härters

MG_M₂O

= Molekulargewicht von M₂O aus gelöstem Wasserglas (Zusammensetzung a)) mit M = Na oder K

m_WG

= Menge gelöstes Wasserglas in g in der Zusammensetzung a)

s

= Massenverhältnis SiO₂/M₂O des in Zusammensetzung a) verwendeten Wasserglases

Where:
m _stö = stoichiometrically required amount of hardener in g and calculated according to m _stö = (MG _H / MG _M₂O ) · (m _WG / (1 + s)) (1)

MG _H

= Molecular weight of the hardener used

MG _M₂O

= Molecular weight of M ₂ O from dissolved water glass (composition a)) with M = Na or K.

m _WG

= Amount of dissolved water glass in g in the composition a)

s

= Mass ratio SiO ₂ / M ₂ O of the water glass used in composition a)

When using a mixture of 2 or more water glasses m _stö = Σm _stö (i), where m _stö (i) the _calculated according to equation (1) for each water glass (i) with the respective s (i) value amount of hardener is.
x = 0.35 when using dissolved Na water glass in composition a) and
x = 0.45 when using dissolved K-water glass in composition a) and
x = 0.35 · y _Na + 0.45 · y _K using a mixture of dissolved Na water glass and dissolved K water glass in composition a), wherein
y _Na = weight fraction of Na water glass based on total amount of dissolved water glass calculated according to:
(Amount in g of dissolved Na water glass) / (total amount in g of dissolved water glass)
y _K = weight fraction of K water glass relative to the total amount of dissolved water glass, where y _Na + y _K = 1,
when using a mixture of hardeners: MG _H = ΣMG _H (i) * m (i)) with MG _H (i) = molecular weight of hard (i)
m (i) = weight fraction of hardener (i) relative to total amount of hardeners used, where Σm (i) = 1.

The water glass can be used according to the invention for setting a wide variety of aggregates. Preferred additives have OH groups.

Examples of suitable aggregates are flux sand, sea sand, desert sand, SiO ₂ (such as that used in porcelain manufacture), wood chips, fibers (eg having a fiber thickness of <10 μm and a length of 1-10 mm) such as glass fibers Rock wool, basalt fibers and cellulose fibers and / or glass beads (eg 1-3 mm in diameter), polystyrene beads (eg 1-3 mm in diameter) and pumice particles.

The amount of aggregate is chosen so that the mixture of water glass solution and hardener used is sufficient for complete wetting.

In addition to the above essential components, one or more optional ingredients may be included to further influence the reaction and / or properties of the products.

The solids should be mixed in as a powder (preferred average particle size ≦ 100 μm).

According to one embodiment, metakaolin is used in composition a) (preferred particle size <20 μm). In another embodiment, a mixture of metakaolin and kaolin is used.

Metakaolin is a sodium aluminum silicate and can formally be considered as a condensation product of aluminum hydroxide and silica.

If, in addition to silicon, aluminum is also present in the structure, products of considerably greater hardness result. The inventors suspect that the aluminum centers in the framework carry a net negative charge.

The conversion ratio of sodium silicate to metakaolin is preferably in a stoichiometric ratio of about 1: 1. It is believed that then forms a covalent, three-dimensional network of highest stability. In addition, all sodium atoms are used to saturate the aluminum cations. Thereafter, water glass could be reacted with metakaolin in a weight ratio of 242 g to 258 g. There are also Si: Al ratios of 2: 1 and 3: 1, and other conditions possible, even not even ratios. A weight ratio of water glass to metasilicate of 100: 1 to 100: 25 is preferred (more preferably 100: 5 to 100: 25) because such mixtures are readily pourable. However, an even higher proportion of metasilicate led to crumbly and too dry mixtures and is therefore not preferred, in particular for the production of porous shaped articles.

Since the incorporation of aluminum tetrahedra, the grid requires a charge balance, appropriate cations, such as alkali cations must be incorporated into the scaffold. This probably leads to ionic bonding of monovalent metal cations from the water glass, provided that aluminum is incorporated. The metasilicate would then act not only as a component to build a covalent network but also as a hardener at the same time. That insofar water glass cures in a mixture with metakaolin without further hardening, although this may take a long time, is understandable in this respect and in the production of multicomponent systems for producing inorganic polymers of the invention in this regard, the storage time for the starting materials of the inorganic polymer to be formed to be observed.

The use of phosphates in composition a) has a favorable effect on the compressive strength of the product and can also reduce the shrinkage in the drying process. The products obtained also show good anti-rust properties.

Mono-, di-, tri- or polyphosphates can be used, preferably di-, tri- and / or polyphosphates of sodium and / or aluminum. It is believed that in addition to silicate and aluminate and polyphosphates can be incorporated into the Si-O-Al skeleton of an inorganic polymer of the invention. This would be particularly advantageous because in the polycondensation of water glass as well as metasilicate, the molecules involved in each case have only two docking sites and thus in principle without the preferred phosphates linear polymers are formed. If, however, a phosphate such as trisodium phosphate (Na ₃ PO ₄ ), tetrasodium diphosphate (Na ₄ P ₂ O ₇ ) or pentasodium triphosphate or metaphosphates with silicates and aluminates for polycondensation brought here branching in the chains may occur.

This is due to the structure of the phosphates, cf. z. B. Trisodium phosphate (Na ₃ PO ₄ ):

The connection tetrasodium for example, has four docking points, that Na ⁺ O ^- groups:

A higher number of docking sites also results from trisodium phosphate and pentasodium triphosphate:

It can thus be formed three-dimensional space scaffoldings.

The amount of the phosphates is not particularly limited, but is preferably 0 to 3 wt .-%, more preferably 0 to 1 wt .-% based on composition a), according to another embodiment> 0 to 3 wt .-%.

Another optional component of composition a) are polyvalent metal oxides, preferably one or more selected from ZnO, TiO ₂ , MnO, PbO, PbO ₂ , Fe ₂ O ₃ , FeO, Fe ₃ O ₄ , ZrO ₂ , Cr ₂ O ₃ , CuO, BaO, SrO, BeO, CaO and MgO, preferred are oxides of divalent metals such as MgO, BeO, SrO, BaO, PbO, CuO, CaO, ZnO and MnO; particularly preferred is TiO ₂ .

If metal oxides are added to the reaction mixture, a cation exchange can take place here. It is believed that oxides of polyvalent metals, such as. B. bivalent can serve as a bridge between two negatively charged aluminum atoms and help build a three-dimensional network framework. It should be noted, of course, that the metal oxide admixtures are not problematic in the case of a later recycling required and that, if necessary, restrictions in terms of processability could occur without safety requirements.

Per se, trivalent or tetravalent ions such as Fe ³⁺ , Cr ³⁺ , Zr ⁴⁺ or Ti ^{4+ are also} usable as oxide and / or sulfate. However, a cluster-like arrangement of three or more aluminum atoms is considered unlikely, so that no advantage can be expected from such higher-valent ions.

Particularly advantageous is the addition of metal oxides whose metals are stable d. H. form sparingly soluble carbonates. In the reaction with organic carbonates as hardeners, inorganic carbonates such as potash and soda are formed. If CaO, SrO, BaO, PbO, MgO or ZnO are added, a later blooming of soda and potash can be avoided and at the same time the hardness and stability of the products can be increased.

The amounts of metal oxides are not particularly limited and are preferably 0 to 5 wt .-% based on composition a).

According to one embodiment, TiO _{2 is added} in an amount of 0 to 2 wt .-%, according to another embodiment> 0 to 2 wt .-%.

The use of alkyl siliconates (preferably C _1-18 alkyl siliconates, more preferably C _1-6 alkyl siliconates such as methyl siliconate) in composition a) is also possible and advantageous when a water-impermeable mass is desired. Thus, composite materials of water-permeable and water-impermeable mass are readily produced by appropriate stratification of reaction mixtures, optionally in carrying out the reaction of reaction mixtures with or without methyl silicate in succession. Mentioned here as methyl silicate z. For example potassium methylsiliconate, e.g. B. Rhodorsil Siliconate 51T Fa. Rhodia.

The amount of alkyl siliconates is not particularly limited, and is preferably 0 to 10% by weight, more preferably 0.1 to 5% by weight, based on the composition a).

In order to increase the strength of the products, it is also possible to add alkali metal and / or alkaline earth metal sulfates, preferably barium, calcium and / or lithium sulfate. Their amount is not particularly limited and is preferably 0 to 2% by weight based on the composition a), in another embodiment,> 0 to 2% by weight.

Of course, organic or inorganic pigments can also be added to the composition a) if dyed products are desired.

In step c) of the process according to the invention, the compositions a) and b) are brought into contact. The fact that, as can be seen from the above, toxic or harmful chemicals must not be used, thereby allowing the use of the products in the interior or interior.

For the reaction, heat is supplied from the outside, so that the reaction takes place at an ambient temperature of ≥ 80 ° C (preferably ≥ 95 ° C). At a temperature of 95 ° C, the mass or the shaped body z. B. solid after about 24 h; at higher temperatures, the time required for solidification decreases accordingly. The heating can z. B. be achieved by placing the reaction mixture in a drying oven, oven or microwave. Also, a heat cuff around the container filled with the reaction mixture is possible. It has been shown that a temperature increase from 95 ° C to 105 ° C results in an acceleration of the curing by a factor of 2.

• (1) Bereitstellen einer Wasserglaslösung
• (2) Gegebenenfalls Zugeben von Oxid eines mehrwertigen Metalls wie z. B. TiO₂ Erhalten wird eine stabile Lösung bzw. Suspension A.
• (3) Bereitstellen einer Härter-Lösung
• (4) Vermischen von Härter-Lösung und Lösung bzw. Suspension A, gegebenenfalls unter Rühren
• (5) Hinzufügen von Zuschlagsstoffen (vorzugsweise mit OH-Gruppen) und vermischen
• (6) Einfüllen in eine Form
• (7) Erwärmen auf mindestens 80°C (gemessen als Umgebungstemperatur z. B. in einem Ofen).

If other constituents are used in addition to waterglass, hardener (I) and aggregate, an exemplary sequence of the process according to the invention is as follows:

• (1) Provide a water glass solution
• (2) Optionally adding oxide of a polyvalent metal such as. B. TiO ₂ Obtained is a stable solution or suspension A.
• (3) Provide a hardener solution
• (4) Mixing of hardener solution and solution or suspension A, optionally with stirring
• (5) Add additives (preferably with OH groups) and mix
• (6) filling into a mold
• (7) Heat to at least 80 ° C (measured as ambient temperature eg in an oven).

The solidified body is then removed from the mold.

Alternatively, it is also possible to heat to at least 80 ° C. already after step (4) (for example for 2 h), then the additives are stirred in / kneaded in and then further heated.

The solidified mass can be brought into a specific shape by machining such as sawing, grinding, etc.

The products obtained by the process according to the invention are solidified compositions / moldings which are distinguished by high strength. In addition, they show a high temperature resistance up to 1600 ° C.

The density of the products obtained is preferably at least 0.3 g / cm ³ , more preferably at least 1 g / cm ³ , determined by the method described below.

Determination of density

For density determination, the volume and weight of a rectangular sample were determined and the density calculated as weight / volume.

Determination of thermal conductivity

To determine the thermal conductivity, specimens 3.5 cm thick were used together with a reference body of the same thickness and a thermal conductivity of 0.0354 W / mK (available from IRMM = Institute for Reference Materials and Measurements, Geel, Belgium) for 1 h a heating plate with constant 80 ° C and then measured with a thermal imaging camera in the dark. The measured surface temperature (as a measure of the thermal conductivity) of the sample body is used to determine the thermal conductivity of the sample body with the aid of the reference body.

Determination of compressive strength (N / mm ² )

The compressive strength of the samples was measured on a Zwick Zwick Zwick tester. For this purpose, the compressive forces (in N) were recorded graphically over the deformation section. The maximum pressure reached was related to the surface of the sample.

The product obtained by the process of the invention has a variety of applications, especially in house building and foundry molds.

The products are acid-resistant, fungus-resistant, heat-resistant up to typically 1,600 ° C; They are also sawed and / or sanded, can be milled and nailed without causing cracking.

A product can easily be dyed with color pigments.

The inorganic polymer products obtained according to the invention contain no combustible constituents (unless incombustible organic materials such as, for example, cellulose fibers or wood chips were mixed in) and are thus completely recyclable.

Due to the special heat stability up to 1600 ° C, use of the compositions according to the invention is also possible in foundry technology; Thus, the production of foundry molds is possible. The high heat resistance of the compositions / moldings obtained according to the invention (in particular with sand aggregates) allows the use also with high-melting alloys.

• 1. Verfahren zur Herstellung einer Masse oder eines Formkörpers aus anorganischem Polymer, umfassend a) Bereitstellen einer wässrigen Zusammensetzung enthaltend in Wasser gelöstes Natrium- und/oder Kaliumwasserglas, wobei die Zusammensetzung einen pH Wert von mindestens 12 aufweist, b) Bereitstellen einer Zusammensetzung enthaltend (i) Wasser, und (ii) mindestens einen wasserlöslichen oder wassermischbaren Härter, wobei der Härter ausgewählt ist aus Amiden der allgemeinen Formel (I) und Derivaten davon ausgewählt aus Biureten und Urethanen
  
  wobei R¹ bis R⁴ unabhängig voneinander ausgewählt werden aus H und gegebenenfalls mit einer oder mehreren OH-Gruppen substituiertem C_1-6 Alkyl oder einer von R¹ und R² und einer von R³ und R⁴ mit der Gruppe
  
  einen 5-gliedrigen Ring bilden, der gegebenenfalls ein- oder mehrfach mit Substituenten substituiert ist, die ausgewählt sind aus C_1-2 Alkyl und C_1-2 Alkyl substituiert mit einem oder mehreren OH; und wobei die Menge an eingesetztem Härter m_H in g von m_stö bis x·m_stö beträgt mit x = 0,35 bei Verwendung von gelöstem Na-Wasserglas in a) und x = 0,45 bei Verwendung von gelöstem K-Wasserglas in a) und x = 0,35 * y_Na + 0,45 * y_K bei Verwendung eines Gemisches von gelöstem Na-Wasserglas und gelöstem K-Wasserglas in a), wobei y_Na = Gewichtsanteil an Na-Wasserglas bezogen auf Gesamtmenge an gelöstem Wasserglas berechnet nach: (Menge in g des gelösten Na-Wasserglases)/(Gesamtmenge in g an gelöstem Wasserglas) y_K = Gewichtsanteil an K-Wasserglas bezogen auf Gesamtmenge an gelöstem Wasserglas, wobei y_Na + y_K = 1 gilt, wobei m_stö nach folgender Gleichung (1) berechnet wird: m_stö = (MG_H/MG_M₂O)·(m_WG/(1 + s)) (1) mit m_stö = stöchiometisch benötigte Menge Härter in g MG_H = Molekulargewicht des verwendeten Härters MG_M₂O = Molekulargewicht von M₂O aus gelöstem Wasserglas mit M = Na oder K m_WG = Menge gelöstes Wasserglas in g in der in a) bereitgestellten Zusammensetzung s = Massenverhältnis SiO₂/M₂O des in a) verwendeten Wasserglases und wobei bei Einsatz eines Gemisches aus 2 oder mehr Wassergläsern m_stö = Σm_stö(i) (2) gilt und m_stö(i) die nach Gleichung (1) für jedes Wasserglas (i) berechnete Menge an Härter ist; und wobei bei Verwendung von Härtergemischen für MG_H in Gleichung (1) Σ(MG_H(i)·m(i)) (3) verwendet wird mit MG_H(i) = Molekulargewicht von Härter (i) m(i) = Gewichtsanteil von Härter (i) bezogen auf Gesamtmenge an verwendeten Härtern wobei Σm(i) = 1 gilt, c) In Kontakt bringen der in Schritt a) und b) bereitgestellten wässrigen Zusammensetzungen, d) Vermischen mit einem oder mehreren festen Zuschlagsstoffen und e) Erwärmen auf mindestens 80°C zum Aushärten oder alternativ d) Erwärmen der in Schritt c) erhaltenen Mischung auf mindestens 80°C, e) Vermischen der in Schritt d) erhaltenen zähen Masse mit einem oder mehreren Zuschlagsstoffen und f) weiteres Erwärmen auf mindestens 80°C zum Aushärten.
• 2. Verfahren nach Punkt 1, wobei die in a) bereitgestellte Zusammensetzung außerdem ein oder mehrere Oxide von mehrwertigen Metallen enthält.
• 3. Verfahren nach Punkt 2, wobei es sich bei den Oxiden um eines oder mehrere, ausgewählt aus ZnO, TiO₂, MnO, PbO, PbO₂, Fe₂O₃, FeO, Fe₃O_{4 ,} ZrO₂, Cr₂O₃, CuO, BaO, SrO, BeO, MgO und CaO handelt.
• 4. Verfahren nach Punkt 2 oder 3, wobei es sich um ein Oxid von zweiwertigen Metallen oder Gemischen davon handelt.
• 5. Verfahren nach einem der Punkte 2 bis 4, wobei es sich um TiO₂ handelt.
• 6. Verfahren nach einem der Punkte 2 bis 5, wobei die Oxide in einer Menge von 0 bis 5 Gew.-% bezogen auf Zusammensetzung a) enthalten sind.
• 7. Verfahren nach einem der vorherigen Punkte, wobei die in a) bereitgestellte Zusammensetzung außerdem ein oder mehrere Sulfate, ausgewählt aus Alkalisulfaten und Erdalkalisulfaten, enthält.
• 8. Verfahren nach Punkt 7, wobei die Sulfate in einer Menge von 0 bis 5 Gew.-% bezogen auf Zusammensetzung a) vorliegen.
• 9. Verfahren nach einem der vorherigen Punkte, wobei die in a) bereitgestellte Zusammensetzung außerdem ein oder mehrere Phosphate, ausgewählt aus Mono-, Di-, Tri- und Polyphosphaten, enthält.
• 10. Verfahren nach Punkt 9, wobei das Phosphat ausgewählt ist aus Di-, Tri- oder Polyphosphaten des Natriums oder Aluminiums und Gemischen von 2 oder mehr davon.
• 11. Verfahren nach Punkt 9 oder 10, wobei die Phosphate in einer Menge von 0 bis 3 Gew.-% bezogen auf Zusammensetzung a) vorliegen.
• 12. Verfahren nach einem der vorherigen Punkte, wobei die in a) bereitgestellte Zusammensetzung außerdem ein oder mehrere Alkylsilikonate enthält.
• 13. Verfahren nach Punkt 12, wobei die Alkylsilikonate in einer Menge von 0 bis 10 Gew.-% bezogen auf Zusammensetzung a) vorliegen.
• 14. Verfahren nach einem der vorherigen Punkte, wobei es sich bei dem Harter um mindestens einen aus Harnstoff, Biuret und Urethan handelt.
• 15. Verfahren nach einem der vorherigen Punkte, wobei der Zuschlagsstoff aus Flusssand, Seesand, Wüstensand, Holzspänen, SiO₂-Pulver, Glasfasern und Perlit ausgewählt wird.
• 16. Verfahren nach einem der vorherigen Punkte, wobei es sich bei dem gelösten Wasserglas in der in a) bereit gestellten Zusammensetzung um mindestens ein Wasserglas handelt, für das gilt: Q₁: 2–6% Q₂: 10–25% Q₃: 15–25% Q₄: 45–70% wobei die Fläche derjenigen Peaks, die einer bestimmten Siliciumgruppe Q(i) zugeordnet wird, zur Summe der Fläche aller Si-NMR-Signale (= 100%) ins Verhältnis gesetzt wird.
• 17. Verfahren nach einem der vorherigen Punkte, wobei das Erwärmen in einem Trockenschrank, einem Ofen oder einem Mikrowellengerät durchgeführt wird.
• 18. Verfahren nach einem der vorherigen Punkte, wobei auf mindestens 95°C erwärmt wird.
• 19. Masse oder Formkörper erhältlich durch das Verfahren nach einem der Punkte 1 bis 18.
• 20. Masse oder Formkörper aus polykondensiertem Natrium- und/oder Kaliumwasserglas, dadurch gekennzeichnet, dass ein Zuschlagsstoff vorhanden ist.
• 21. Masse oder Formkörper nach Punkt 19 oder 20, wobei als Zuschlagsstoff Flusssand, Seesand, Wüstensand, Holzspäne, Glasfasern oder Perlit verwendet wurde.
• 22. Verwendung der Masse oder des Formkörpers nach einem der Punkte 19 bis 21 als Dachziegel, Ersatz für Betonplatten, feuerfeste Holzplatten, Gießereiformen.
• 23. Gießereiform aus einer Masse wie in einem der Punkte 19 bis 21 beschrieben.
• Die Erfindung wird im Folgenden an Hand von Beispielen und unter Bezugnahme auf die Figuren erläutert, ist aber in keinster Weise darauf beschränkt.

Some embodiments of the present invention are summarized below:

• A process for producing a mass or a molding of inorganic polymer, comprising a) providing an aqueous composition comprising sodium and / or potassium waterglass dissolved in water, the composition having a pH of at least 12, b) providing a composition comprising i) water, and (ii) at least one water-soluble or water-miscible hardener, wherein the hardener is selected from amides of general formula (I) and derivatives thereof selected from biurets and urethanes
  
  wherein R ¹ to R ^{4 are} independently selected from H and optionally substituted with one or more OH groups substituted C _1-6 alkyl or one of R ¹ and R ² and one of R ³ and R ⁴ with the group
  
  form a 5-membered ring optionally substituted one or more times with substituents selected from C _1-2 alkyl and C _1-2 alkyl substituted with one or more OH; and wherein the amount of hardener used is m _H in g from m _stö to x · m _stö with x = 0.35 when using dissolved Na water glass in a) and x = 0.45 when using dissolved K water glass in a) and x = 0.35 * y _Na + 0.45 * y _K when using a mixture of dissolved Na water glass and dissolved K water glass in a), wherein y _Na = weight fraction of Na water glass based on total amount of dissolved water glass calculated according to: (amount in g of dissolved Na waterglass) / (total amount in g of dissolved waterglass) y _K = weight fraction of K waterglass relative to total amount of dissolved waterglass where y _Na + y _K = 1, where m _{stö is calculated} according to the following equation (1): m _stö = (MG _H / MG _M₂O ) · (m _WG / (1 + s)) (1) with m _stö = _{stöchiometisch} required amount of hardener in g MG _H = molecular weight of the hardener used MG _M₂O = molecular weight of M ₂ O from dissolved water glass with M = Na or K m _WG = amount of dissolved water glass in g in the composition provided in a) s = Mass ratio SiO ₂ / M ₂ O of the water glass used in a) and wherein when using a mixture of 2 or more water glasses m _stö = Σm _stö (i) (2) and m _stö (i) is the amount of hardener calculated according to equation (1) for each water glass (i); and wherein when using hardener mixtures for MG _H in equation (1) Σ (MG _H (i) * m (i)) (3) is used with MG _H (i) = molecular weight of hardener (i) m (i) = weight fraction of hardener (i) relative to total amount of hardeners used, where Σm (i) = 1, c) bring into contact the in step a d) mixing with one or more solid additives and e) heating to at least 80 ° C for curing or alternatively d) heating the mixture obtained in step c) to at least 80 ° C, e) mixing the in step d) obtained viscous mass with one or more additives and f) further heating to at least 80 ° C for curing.
• 2. The method of item 1, wherein the composition provided in a) further comprises one or more polyvalent metal oxides.
• 3. The method of item 2, wherein the oxides are one or more selected from ZnO, TiO ₂ , MnO, PbO, PbO ₂ , Fe ₂ O ₃ , FeO, Fe ₃ O _{4 ,} ZrO ₂ , Cr ₂ O. ₃ , CuO, BaO, SrO, BeO, MgO and CaO.
• 4. Method according to item 2 or 3, wherein it is an oxide of divalent metals or mixtures thereof.
• 5. The method according to any one of items 2 to 4, wherein it is TiO ₂ .
• 6. The method according to any one of items 2 to 5, wherein the oxides are contained in an amount of 0 to 5 wt .-% based on composition a).
• 7. A method according to any preceding item, wherein the composition provided in a) further comprises one or more sulfates selected from alkali sulfates and alkaline earth sulfates.
• 8. The method of item 7, wherein the sulfates are present in an amount of 0 to 5 wt .-% based on composition a).
• 9. A method according to any preceding item, wherein the composition provided in a) further comprises one or more phosphates selected from mono-, di-, tri- and polyphosphates.
• 10. The method of item 9, wherein the phosphate is selected from di-, tri- or polyphosphates of sodium or aluminum and mixtures of 2 or more thereof.
• 11. The method according to item 9 or 10, wherein the phosphates are present in an amount of 0 to 3 wt .-% based on composition a).
• 12. A method according to any preceding item, wherein the composition provided in a) further comprises one or more alkyl silicone agents.
• 13. The method according to item 12, wherein the alkyl siliconates are present in an amount of 0 to 10 wt .-% based on composition a).
• 14. The method of any preceding item, wherein the hardener is at least one of urea, biuret, and urethane.
• 15. Method according to one of the preceding points, wherein the aggregate is selected from river sand, sea sand, desert sand, wood chips, SiO ₂ powder, glass fibers and perlite.
• 16. Method according to one of the preceding points, wherein the dissolved water glass in the composition provided in a) is at least one water glass, for which the following applies: Q ₁ : 2-6% Q ₂ : 10-25% Q ₃ : 15-25% Q ₄ : 45-70% where the area of those peaks associated with a particular silicon group Q (i) is proportioned to the sum of the area of all Si NMR signals (= 100%).
• 17. The method according to any preceding item, wherein the heating is carried out in a drying oven, an oven or a microwave oven.
• 18. Method according to one of the preceding points, wherein is heated to at least 95 ° C.
• 19. Mass or shaped article obtainable by the method according to one of the items 1 to 18.
• 20. mass or shaped body of polycondensed sodium and / or potassium water glass, characterized in that an aggregate is present.
• 21. Mass or shaped article according to item 19 or 20, wherein the aggregate used was river sand, sea sand, desert sand, wood chips, glass fibers or perlite.
• 22. Use of the mass or the molding according to any one of items 19 to 21 as a roof tile, replacement of concrete slabs, refractory wood panels, foundry molds.
• 23. Foundry mold from a mass as described in one of the points 19 to 21.
• The invention will now be described by way of example and with reference to the figures, but is in no way limited thereto.

Experimental part

Used chemicals:
Sodium water glass: s = 3.3, s _molar = 3.4, Roth Co. (Karlsruhe, D), aqueous solution with 34.5% solids content
Potassium water glass Betol 5020T: s = 1.35, S _molar = 2.2, Fa. Woellner (Ludwigshafen, D), aqueous solution with 48% solids content
Perlite: Fa. Knauf (Dortmund, D), mean grain diameter about 10 microns
sawdust
fine SiO ₂ powder for porcelain production
Titanium oxide: Merck (Darmstadt)
urea
river sand
Desert sand from Dubai

Examples

example 1

3.1 g of urea were dissolved in 5 ml of water and mixed with 41 g of Na waterglass solution (s = 3.3, solids content 34.5%); 0.5 g of TiO ₂ was added. Subsequently, 50 g of river sand were mixed with the waterglass solution. It was filled into the printing plate and heated for 2 h in a drying oven at 95 ° C, then the mixture was stirred / kneaded and then kept in an oven at 95 ° C for a further 24 h.

The solid product obtained was removed from the mold and the density and compressive strength were determined by the methods described above to give 1.38 g / cm ³ and 11.01 N / mm ² , respectively.

In an alternative implementation, the mixture of urea and water glass was first heated in a drying oven at 95 ° C for 2 h and kneaded into the then viscous mass of the river sand; then was kept at 95 ° C for a further 24 h.

Example 2

Example 1 was repeated except that 30 g of Na waterglass solution (s = 3.3, solids content 34.5%) and 10 g of K waterglass solution (s = 1.35, solids content 48%) and 100 g of river sand were used.

Properties of the product:
Density 1.61 g / cm ³
Compressive strength 1.9 N / mm ²

Example 3

Example 2 was repeated but 91 g of desert sand was used instead of river sand.

Properties of the product:
Density 1.49 g / cm ³
Compressive strength 4.9 N / mm ²

Example 4

Example 2 was repeated, but 100 g of fine SiO ₂ powder from porcelain production was used instead of 100 g of river sand.

Properties of the product:
Density 1.44 g / cm ³
Compressive strength 19.7 N / mm ²

Example 5

Example 2 was repeated, but 10 g of sawdust were used instead of 100 g of river sand.

Properties of the product:
Density 0.69 g / cm ³
Compressive strength 3.01 N / mm ²

Example 6

Example 2 was repeated, but 7 g of perlite were used instead of 100 g of river sand.

Properties of the product:
Density 0.42 g / cm ³
Compressive strength 1.4 N / mm ²
Thermal conductivity 0.135 W / mK

In 1 the following products are shown:
top left (HH) - Example 5 (sawdust)
top right (K55) - Example 3 Example 1 (river sand)
bottom left (L29) - Example 5 (fine SiO ₂ )
bottom right (L28) - Example 4 (desert sand)

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

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Claims (14)

A process for preparing an inorganic polymer composition or body comprising a) providing an aqueous composition containing sodium and / or potassium waterglass dissolved in water, the composition having a pH of at least 12, b) providing a composition comprising (i) Water, and (ii) at least one water-soluble or water-miscible hardener, wherein the hardener is selected from amides of the general formula (I) and derivatives thereof selected from biurets and urethanes

wherein R ¹ to R ^{4 are} independently selected from H and optionally substituted with one or more OH groups substituted C _1-6 alkyl or one of R ¹ and R ² and one of R ³ and R ⁴ with the group

form a 5-membered ring optionally substituted one or more times with substituents selected from C _1-2 alkyl and C _1-2 alkyl substituted with one or more OH; and wherein the amount of hardener used is m _H in g from m _stö to x · m _stö with x = 0.35 when using dissolved Na water glass in a) and x = 0.45 when using dissolved K water glass in a) and x = 0.35 * y _Na + 0.45 * y _K when using a mixture of dissolved Na water glass and dissolved K water glass in a), where y _Na = weight content of Na water glass based on total dissolved Water glass calculated according to: (amount in g of the dissolved Na water glass) / (total amount in g of dissolved water glass) y _K = weight fraction of K water glass relative to the total amount of dissolved water glass, where y _Na + y _K = 1, where m _{stö is calculated} according to the following equation (1): m _stö = (MG _H / MG _M₂O ) · (m _WG / (1 + s)) (1) with m _stö = stoichiometrically required amount of hardener in g _{MW H} = molecular weight of the hardener used MG _M₂O = molecular weight of M ₂ O from dissolved water glass with M = Na or K m _WG = amount of dissolved water glass in g in the composition provided in a) s = Mass ratio SiO ₂ / M ₂ O of the water glass used in a) and wherein when using a mixture of 2 or more water glasses m _stö = Σm _stö (i) (2) and m _stö (i) is the amount of hardener calculated according to equation (1) for each water glass (i); and wherein when using hardener mixtures for MG _H in equation (1) Σ (MG _H (i) * m (i)) (3) is used with MG _H (i) = molecular weight of Harter (i) m (i) = weight fraction of Harter (i) based on total amount of hardeners used, where Σm (i) = 1, c) contacting in step a ) and b) aqueous compositions, d) mixing with one or more solid additives and e) heating to at least 80 ° C for curing or alternatively d) heating the mixture obtained in step c) to at least 80 ° C, e) mixing the viscous mass obtained in step d) with one or more additives and f) further heating to at least 80 ° C for curing. The method of claim 1, wherein the composition provided in a) further comprises one or more polyvalent metal oxides. The method of claim 2, wherein the oxides are one or more selected from ZnO, TiO ₂ , MnO, PbO, PbO ₂ , Fe ₂ O ₃ , FeO, Fe ₃ O ₄ , ZrO ₂ , Cr ₂ O ₃ , CuO, BaO, SrO, BeO and MgO. The method of claim 2 or 3, wherein it is TiO ₂ . A process according to any one of the preceding claims wherein the composition provided in a) further comprises one or more sulphates selected from alkali sulphates and alkaline earth sulphates. A process according to any one of the preceding claims, wherein the composition provided in a) further comprises one or more phosphates selected from mono-, di-, tri- and polyphosphates. The method of claim 6, wherein the phosphate is selected from di-, tri- or polyphosphates of sodium or aluminum and mixtures of 2 or more thereof. A process according to any one of the preceding claims wherein the composition provided in a) further comprises one or more alkyl siliconates. A method according to any one of the preceding claims, wherein the hardener is at least one of urea, biuret and urethane. Method according to one of the preceding claims, wherein the aggregate of river sand, sea sand, desert sand, wood chips, SiO ₂ powder, glass fibers and perlite is selected. Method according to one of the preceding claims, wherein the heating is carried out in a drying oven, an oven or a microwave oven. A mass or shaped article obtainable by the process according to one of claims 1 to 11. Mass or molded article of polycondensed sodium and / or potassium water glass, characterized in that an aggregate is present. Use of the mass or molding of claim 12 or 13 for roof tiles, replacement for concrete slabs, refractory wood panels and foundry molds.

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