Polymer concrete and casting mortar containing slag

文档序号：1926366 发布日期：2021-12-03 浏览：12次中文

阅读说明：本技术 含炉渣的聚合物混凝土和浇注砂浆 (Polymer concrete and casting mortar containing slag ) 是由 S·科尔西 T·马米耶 T·莫泽 U·韦尔滕 F·乌尔姆利于 2020-05-28 设计创作，主要内容包括：本发明涉及可固化的粘结剂组合物,包含：a)至少一种有机粘结剂,选自a1)环氧树脂和a2)多异氰酸酯和多元醇,和b)至少50重量％的炉渣,以100重量％的粘结剂组合物计。(The present invention relates to a curable binder composition comprising: a) at least one organic binder selected from a1) epoxy resins and a2) polyisocyanates and polyols, and b) at least 50% by weight of slag, based on 100% by weight of the binder composition.)

1. A curable binder composition comprising: a) at least one organic binder selected from a1) epoxy resins and curing agents for epoxy resins and a2) polyisocyanates and polyols, and b) at least 50% by weight of slag, based on 100% by weight of the binder composition.

2. The binder composition as claimed in claim 1, characterized in that the binder composition contains from 50 to 80% by weight, in particular from 60 to 75% by weight, in particular from 65 to 70% by weight, of slag, based on 100% by weight of the binder composition.

3. Binder composition according to any one of the preceding claims, characterised in that the slag is selected from blast furnace slag, in particular blast furnace slag and slag sand, steel slag, metallurgical slag, in particular copper slag, and slag from waste incineration, of which blast furnace slag, steel slag and metallurgical slag are preferred.

4. Binder composition according to any one of the preceding claims, characterised in that the slag is an iron-containing slag and has at least 8 wt.%, in particular at least 10 wt.%, preferably at least 15 wt.%, 20 wt.% or 25 wt.% of iron, calculated as FeO.

5. Binder composition according to any one of the preceding claims, characterised in that the slag has an apparent density of at least 2.9kg/l, preferably at least 3.1kg/l, in particular at least 3.3kg/l, especially at least 3.5 kg/l.

6. Binder composition according to any one of the preceding claims, characterised in that the slag has a particle size of 0.05 to 16mm, preferably 0.06 to 8mm, more preferably 0.1 to 4mm, especially 0.12 to 3.5 mm.

7. The binder composition as claimed in any one of the preceding claims, characterized in that the slag particles have an irregular shape and/or a rough surface.

8. Binder composition according to any one of the preceding claims, characterized in that at least one further mineral filler is additionally present, chosen from limestone powder, chalk, quartz powder, silica fume, titanium dioxide, barite powder and alumina, preferably having a particle size of at most 0.1 mm.

9. Binder composition according to any one of the preceding claims, characterized in that at least one wetting and/or dispersing agent, in particular based on polycarboxylate ethers, is present.

10. The binder composition according to claim 9, characterized in that the slag and optionally at least one further filler are coated with a wetting agent and/or a dispersing agent, if present.

11. Multi-component system for preparing a curable binder composition, comprising at least one resin component comprising at least one epoxy resin and at least one curing agent component comprising a curing agent for the at least one epoxy resin, wherein slag and optionally further ingredients are present in the resin component, the curing agent component and/or optionally further components, in particular solid components.

12. Multi-component system for producing a curable binder composition, comprising at least one polyisocyanate component comprising at least one polyisocyanate and at least one polyol component comprising at least one polyol, wherein slag and optionally further ingredients are present in the polyisocyanate component, the polyol component and/or optionally further components, in particular solid components.

13. Use of the adhesive composition according to any one of claims 1 to 10 or the multi-component system according to any one of claims 11 to 12 for bonding, coating or sealing substrates, for filling edges, holes or joints, as anchoring or injection resin, as potting or casting compound, as floor covering and/or for producing molded parts.

14. Use of the binder composition according to any one of claims 1 to 10 or the multi-component system according to any one of claims 11 to 12 for the preparation of a material with improved electrical conductivity at 20 ℃, characterized in that the slag in the binder composition is an iron-containing slag with at least 8 wt.% iron and/or a slag with an apparent density of at least 3.1kg/l, the at least 8 wt.% being calculated in the form of FeO and being based on the total weight of the slag.

15. A cured binder composition obtained by curing the binder composition according to any one of claims 1 to 10 or by mixing and curing the components of the multi-component system according to any one of claims 11 to 12.

Technical Field

The invention relates to the use of slag as a filler in polymer concrete and polymer mortars.

Background

Polymer concrete is a water-impermeable material, typically comprising an organic binder and a filler. In contrast to ordinary concrete, in which cement as a binder holds the filler together after curing with water, in polymer concrete is an organic polymer that acts as a binder. Polymer concrete generally does not contain cement as a binder. The filler in polymer concrete is usually composed of natural stone materials of different particle sizes, such as granite, quartz, basalt, limestone, expanded clay, perlite or other mineral materials. Fillers are used to modify the mechanical, electrical and/or processing properties of the material while significantly reducing the content of the often more expensive matrix in the final product. Furthermore, the presence of the filler particles significantly reduces the volume shrinkage of the polymer concrete after curing of the reactive cross-linked polymer matrix and increases its compressive strength.

Curable liquid organic binders, which are generally composed of at least two components, are typically mixed with the filler after mixing of the binder components, and then shaped and cured.

In epoxy-based polymer concrete, the curable binder consists of a curable epoxy resin and a curing agent for the epoxy resin, which upon mixing react to form a cured epoxy resin. In polyurethane-based polymer concrete, the curable binder consists of a mixture of a polyisocyanate and a polyol which react to form a polyurethane after mixing. Epoxy resins and polyurethanes have the advantage over other organic binders (e.g., unsaturated polyester resins or acrylic resins) that they do not require peroxide and/or heat to cure. Peroxides are harmful substances. Epoxy resins and curing agents as well as polyisocyanates and polyols cure well even at low temperatures. Polymer concrete based on epoxy resins and polyurethanes is characterized by high strength, freeze resistance, abrasion resistance, material durability, and a closed and waterproof surface.

The growing demand for building materials and the environmental requirements have led to a shortage of natural raw materials that can be used as fillers. This is particularly the case with quartz sand and quartz gravel. Therefore, it is desirable to replace natural raw materials more and more with industrial waste. One industrial waste material produced in large quantities worldwide is slag. Slag is produced, for example, in metal refining, metal recovery or household waste incineration or sludge incineration. Slag sand is a glassy slag produced during iron making, and is used as a cement admixture and a cement substitute material due to its latent hydraulic properties in a finely ground form. Other slags (e.g., steel slag generated during steel making or steel recycling or copper slag generated during copper making) are not suitable as cement substitutes because of their poor hydraulic properties. As with blast furnace slag, they are sometimes used as road-building rubble, inexpensive backfill material, or as an abrasive like, for example, copper slag.

GB 2460707 describes the use of recycled material as aggregate for polymer concrete. Glass sand, plastic beads, crushed porcelain or recycled polymer concrete are used as a partial substitute for natural stone.

WO 2010030048 describes the use of "atomised steel slag" as a constituent of polymer concrete based on unsaturated polyester resins. Such "atomized steel slag" is produced by a special process, which causes additional costs and makes the slag more expensive. The availability of atomized steel slag is limited in both quantity and location.

There is still a need to replace natural stone particles in polymer concrete by industrial waste in an inexpensive and high quality way. While it is desirable to retain the good properties of polymer concrete.

Summary of The Invention

The object of the present invention is to provide an industrial waste to replace natural stone particles in polymer concrete based on epoxy or polyurethane, which is available worldwide in large quantities and at low cost and can be used without complex treatments.

Surprisingly, the object is achieved by the binder composition according to claim 1.

The advantage of binder compositions based on epoxy resins and curing agents or based on polyisocyanates and polyols compared with other organic binder compositions likewise used for polymer concrete, in particular compared with unsaturated polyester resins or acrylic resins, is that they can be processed and cured well even at low temperatures (for example 5 ℃ or 10 ℃) and have good pourability and good levelling. For epoxy-based adhesive compositions, the processing time can also be variably adjusted, for example up to one hour. Furthermore, compared to unsaturated polyester resins of generally high viscosity, there is no need to use initiators (e.g., peroxides) that pose a risk of explosion for curing. Furthermore, the surface of cured binder compositions based on epoxy or polyurethane is strong and non-tacky, unlike unsaturated polyester resins, the surface of which is typically poorly cured.

Slag is a waste material from metal refining, metal recovery or refuse incineration, produced in large quantities worldwide. The use of slag in epoxy-based polymer concrete helps to reduce landfills and reduce the need for high quality natural stone particles, the availability of which is gradually decreasing.

Surprisingly, slag can be used in large amounts in polymer concrete based on epoxy resins or polyurethanes without quality losses. Polymer concrete based on epoxy resin or polyurethane containing slag exhibits good properties, such as in particular high strength and good workability, even when the polymer concrete is completely free of conventional fillers, such as in particular quartz sand or quartz flour. Surprisingly, the material properties (in particular the compressive strength) are even further improved with respect to the prior art.

It is particularly surprising that the polymer concrete according to the invention, in particular when it contains steel or copper slag, has an improved electrical conductivity. The thermal conductivity can also be improved.

Other aspects of the invention are the subject of other independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims.

Drawings

Fig. 1 shows a schematic representation of an exemplary cross-section of slag particles having an irregular shape.

Examples

Examples are described below, which explain the present invention in more detail. The invention is of course not limited to the described embodiments.

"Bsp." means "example"

"Ref." means "reference example"

Materials used

The quartz sand and slag were dried before use and separated into particle fractions by sieving. The particle fractions are subsequently mixed so that the particle size distribution of the sand used corresponds to the predetermined particle size distribution (sieve curve).

EOS is electric furnace slag from Stahl gerlaffingen (switzerland). The material used had an apparent density of about 3.3kg/l and an iron content of about 19% by weight, calculated as FeO.

HOS is blast furnace clinker from Krupp Mannesmann, germany, obtained from Hermann Rauen GmbH & co. The material used had an apparent density of 2.9kg/l and an iron content of about 3% by weight, calculated as FeO.

Is a blast furnace slag of DK-Recycling und Roheisen GmbH, Germany, from Hermann Rauen GmbH&Co, under the trade mark-a mineral building material mixture. The material used had an apparent density of about 2.9kg/l and an iron content of about 1% by weight, calculated as FeO.

HS is slag sand from volestapine AG of austria. The material used had an apparent density of about 2.9kg/l and an iron content of less than 1% by weight, calculated as FeO.

CS is from Sibelco, GermanyIron silicate granules (which are glassy copper slags) having an apparent density of about 3.7kg/l and an iron content of about 51% by weight, calculated as FeO.

-42HE is an epoxy-based three-component casting mortar obtained from Sika Schweiz AG.

Polycarbonate ether (PCE) is a comb polymer with carboxylic acid groups and polyethylene glycol side chains.

Measuring method

The compressive and flexural strength of the 40x40x160mm test specimens was determined using a testing machine in accordance with DIN EN 196-1.

To determine the specific volume resistance, a conductive gel was applied to the opposing 40x40mm surface of the 40x40x160mm sample, and steel electrodes covering the entire surface were placed flush on both surfaces. The volume resistance of the sample was determined by applying a voltage of 100mV AC to the two electrodes and a frequency of 1kHz and 10 kHz.

The thermal conductivity of a test specimen having a diameter of 30mm and a height of 2mm was determined according to ASTM D5470-06 using a ZFW TIM-tester from ZFW (thermal management center) of Stuttgart, Germany.

Preparation of the samples

To prepare the test specimens, the mixed casting mortar is cast into steel molds and stored in a formwork at 20 ℃ for 24 hours. The sample was then removed from the template and stored further at 20 ℃. Specific resistance, strength and thermal conductivity were determined after 7 days of storage.

Table 1: composition of solid component

Composition (I)	By weight%
		A mixture of limestone powder and barite powder,<0.1mm	24.9
sand (slag sand or quartz sand)^*，0.12-3.2mm	74.6
		Polycarboxylate ether solution (20 wt% polycarboxylate ether dissolved in 80 wt% benzyl alcohol)	0.5

^*Sand type: see reference examples and examples.

To prepare the solid component, the solid components are dry mixed and the polycarboxylate ether solution is sprinkled during mixing.

Epoxy resin-based casting mortar strength and volume resistance

The types of sand used for the epoxy resin compositions M-1 to M-7 and their properties in a liquid state and a cured state are shown in Table 2.

TABLE 2

¹⁾No polycarbonate ether solution was added to the solid component

²⁾Liquid: self-leveling, can be poured into moulds

³⁾Viscosity: the mortar is not self-leveling and the mould must be vibrated violently to obtain a uniform sample

⁴⁾nv: no measured value

⁵⁾The specific volume resistance of the mortars M-2 to M-7 is reduced by a factor compared to the specific volume resistance of the reference mortar M1 (for example resistance M1/resistance M2)

Thermal conductivity of the casting mortar M-8 according to the invention

Example 7

Will be provided with-42HE component A (resin component based on epoxy resin; resin content 99.9% by weight) and related component B (curing agent component based on amine curing agent; curing agent content 70% by weight) were mixed thoroughly in a weight ratio of 3: 1. Then, 40g of this epoxy mixture was thoroughly mixed with a solid component consisting of:

252g of EOS sand with a particle size of 0.12-0.32mm,

86g of a mixture of limestone flour and barite flour having a particle size of less than 0.1mm, and

1.4g of a commercially available wetting agent.

Specimens 30mm in diameter and 2mm in height were prepared by casting into respective molds and allowed to cure at 20 ℃ for 7 days.

The thermal conductivity of the sample was 2.06W/(mK). This is significantly higher than the thermal conductivity of commercially available epoxy resins, which is typically 0.20W/(m.K).

Casting mortar based on epoxy resin and having different amounts of copper slag

Will be provided with-42HE component A (containing epoxy resin; resin content 99.9% by weight) and related component B (containing curing agent; curing agent content 70% by weight) were mixed thoroughly in a weight ratio of 3:1, followed by addition and thorough mixing of a self-prepared solid component having the composition shown in Table 1. The sand 0.12-3.2mm in the measurement series is CS-sand (copper slag). The weight ratio of component A to component B to solid components is shown in Table 3. The mixed casting mortar was poured into molds of 13x13x25mm (width, height, length), respectively, shaken on a shaking table for 1 minute, and stored in a form at 20 ℃ for 24 hours. After demolding, the epoxy resin layer containing almost no slag was observed on the upper side of the sample and the thickness thereof was determined by visual evaluation. Thickness of the layer andthe contents of filler and slag in the casting mortar are shown in Table 3.

TABLE 3

Compressive strength of casting mortar with different contents of epoxy resin and curing agent

Epoxy resin (prepared from 60 parts by mass of Araldit GY 250, 20 parts by mass of F-resin, 15 parts by mass of 1, 4-butane diglycidyl ether, 5 parts by mass of C12/C14-alkyl glycidyl ether) and curing agent (prepared from 55 parts by mass of triethylenetetramine, 10 parts by mass of polyaminoamide adduct (having an H activity equivalent of 115g/Eq and an amine number of about 270mg KOH/g) and 5 parts by mass of tris-2, 4, 6-dimethylaminomethylphenol) were mixed well according to the amounts shown in tables 4 and 5. The EOS and PCE were then added and mixed well according to the amounts shown in tables 4 and 5.

To prepare the test specimens, the mixed casting mortar is poured into steel molds. Flowability was evaluated on a scale from 1 to 5, where 1 indicates no flowability and 5 indicates excellent flowability. Storage in the template at 20 ℃ for 24 hours. The sample was then removed from the template and stored further at 20 ℃. The compressive strength was determined after 7 days of storage.

TABLE 4

	Bsp 13	Bsp 14	Bsp 15	Bsp 16	Bsp 17	Bsp 18
								M-14	M-15	M-16	M-17	M-18	M-19
EOS 0.12-3.2mm	29.88	29.88	29.88	29.88	29.88	29.88
							PCE solution	0.12	0.12	0.12	0.12	0.12	0.12
Epoxy resin	1.18	1.82	5.61	2.86	7.48	10.24
							Curing agent	0.27	0.42	1.31	0.66	1.74	2.38
Fluidity of the resin	1	1	4	2	5	5
							Compressive strength [ MPa ]]	7.15	19.9	87.1	31.2	87.7	85.4

20% by weight of polycarbonate ether dissolved in 80% by weight of benzyl alcohol

TABLE 5

	Bsp 19	Bsp 20	Bsp 21	Bsp 22	Bsp 23	Ref.24
								M-20	M-21	M-22	M-23	M-24	M-25
CS 0.12-3.2mm	29.88	29.88	29.88	29.88	29.88	29.88
							PCE solution	0.12	0.12	0.12	0.12	0.12	0.12
Epoxy resin	1.18	1.82	5.61	2.86	7.48	10.24
							Curing agent	0.27	0.42	1.31	0.66	1.74	2.38
Fluidity of the resin	1	1	5	2	5	5
							Compressive strength [ MPa ]]	25.2	44.2	75.4	66.6	69.8	64.6

20% by weight of polycarbonate ether dissolved in 80% by weight of benzyl alcohol

Compressive strength of casting mortar with different content of polyurethane resin

The polyurethane resin (PUR; prepared by mixing 55 parts by mass of Setathane 1150, 3.5 parts by mass of Desmophen T4011, 17.3 parts by mass of hydroxyl-terminated polybutadiene polyol, 13.8 parts by mass of ethyl-1, 3-hexanediol, 10 parts by mass of Sylosiv A3, 0.1 part by mass of Zr catalyst K-Kat A-209) and Desmodur VL were thoroughly mixed in the amounts shown in tables 6 and 7. EOS (a mixture of limestone and barite (see table 1)) and PCE were then added in the amounts shown in tables 6 and 7 and mixed thoroughly.

To prepare the test specimens, the mixed casting mortar is cast into steel molds. Flowability was evaluated on a scale from 1 to 5, where 1 indicates no flowability and 5 indicates excellent flowability. Storage in the template at 20 ℃ for 24 hours. The sample was then removed from the template and stored further at 20 ℃. The compressive strength was determined after 7 days of storage.

TABLE 6

	Bsp 25	Bsp 26	Bsp 27	Bsp 28
						M-26	M-27	M-28	M-29
EOS 0.12-3.2mm	25.4	25.05	25.05	25.72
					A mixture of limestone powder and barite powder,<0.1mm	4.48	4.83	4.83	4.16
PCE solution	0.12	0.12	0.12	0.12
					PUR	1.16	4.57	0.62	2.60
Desmodur VL	0.74	2.92	0.40	1.66
					Fluidity of the resin	1	3	2	2
Compressive strength [ MPa ]]	18.3	31.9	38.3	33.8

20% by weight of polycarbonate ether dissolved in 80% by weight of benzyl alcohol

TABLE 7

20% by weight of polycarbonate ether dissolved in 80% by weight of benzyl alcohol

Detailed Description

The subject of the invention is a curable binder composition comprising: a) at least one organic binder selected from a1) epoxy resins and curing agents for epoxy resins and a2) polyisocyanates and polyols, and b) at least 50% by weight of slag, based on 100% by weight of the binder composition.

In this context, "apparent density" is understood as the density of a solid. Apparent density is given by the quotient of the weight of the solid and its volume, including the contained pore volume.

Epoxy-based curable organic binder compositions comprise a crosslinkable epoxy resin having more than one epoxy group per molecule, which is rendered solid by forming covalent bonds upon reaction with a suitable curing agent.

The curable organic binder composition that forms a polyurethane upon curing comprises a crosslinkable polyisocyanate having more than one isocyanate group per molecule that reacts with a polyol to become solid through the formation of covalent bonds.

The binder composition according to the invention is curable in that the epoxy groups or isocyanate groups have not reacted or have only partially reacted.

Advantageously, the binder composition contains from 50 to 80% by weight, in particular from 60 to 75% by weight, especially from 65 to 70% by weight, of slag, based on 100% by weight of the binder composition.

In particular for achieving high strength and/or good electrical conductivity, it may also be advantageous if the binder composition comprises 83 to 90 wt.%, preferably 85 to 88 wt.%, of slag, based on 100 wt.% of the binder composition.

The binder composition preferably comprises at least 60 wt%, more preferably at least 65 wt% slag, based on 100 wt% of the binder composition.

Slag is typically produced in metal extraction, metal recovery or waste incineration in ore smelting. It is a mixture of substances consisting essentially of oxides and silicates of various metals. The chemical composition of the slag is generally given in the form of oxides, regardless of the compounds in which these elements are effectively present. Thus, for example, the content of Si is in SiO₂Form given, Al content is in Al₂O₃The form is given and the Fe content is given as FeO. Thus, for example, an analytical determination of 10g of iron (Fe) corresponds to an amount of 12.9g FeO. The percentages of the constituents given for the slag composition relate here to the percentages of the oxide forms of the constituents in question, calculated as the sum of all constituents in the composition (the weights of which are likewise calculated in their oxide forms). The main components of the slag are CaO and SiO₂、Al₂O₃MgO, and FeO. The content of these substances in various types of slag can vary greatly. The composition of the slag can be determined by X-ray fluorescence analysis according to DIN EN ISO 12677.

Slag, in particular slag from metal extraction or metal recovery, is usually separated from the metal melt in the liquid state and is usually stored in a slag bed for cooling. The cooling may be accelerated, for example, by water jets. The cooling process may affect the physical properties of the slag, particularly the crystallinity and particle size.

Blast furnace slag (HOS) is slag produced during the refining of pig iron in blast furnaces. During the reduction in the blast furnace, slag is formed from the iron ore accretion material and an added slag forming agent, such as limestone or dolomite. The slag is separated from the pig iron, cooled slowly in the slag bed (in which the predominantly crystalline blast furnace slag forms) or cooled rapidly with water and/or air (in which vitreous slag sand (HS) forms). Blast furnace slag generally has an iron content (calculated as FeO) of less than 3% by weight (based on the total composition of the slag) and an apparent density of from 2.1 to 2.8 kg/l.

Steel slag is produced as a by-product in the production of steel from pig iron or in the recovery of steel. Steel making uses a number of methods and steps to produce steel slag. Examples of steel slag are oxygen converter slag (BOS) which is produced as a by-product in steel making by an oxygen blowing process, LD-slag which is produced by a top-blown converter steel making process, or electric furnace slag (EOS) which is produced by an electric arc furnace in steel making or steel recovery. Other examples of steel slags are slags generated during further steel purification, such as Slag from Ladle furnaces (Ladle Slag, english). Steel slags typically have an iron content (calculated as FeO) of about 5 to 45 wt% (based on the total composition of the slag) and an apparent density of 3.0-3.7 kg/l.

Other methods of producing slag are for example metallurgical methods for refining non-ferrous metals. These slags are known as metallurgical slags and generally have a high content of iron. One such metallurgical slag is copper slag that is produced as a by-product in the copper smelting. The copper slag typically has an iron content of more than 40% by weight, calculated as FeO. The iron in the copper slag is usually present mostly in the form of ferrosilicate. The copper slag generally has an apparent density in the range of 3.7 kg/l.

Slag produced by waste incineration plants or sludge incineration plants vary widely in composition. It is generally characterized by a high iron content.

The slag is preferably selected from blast furnace slag, in particular blast furnace slag and slag sand, steel slag, metallurgical slag, in particular copper slag, and slag from waste incineration, of which blast furnace slag, steel slag and metallurgical slag are preferred.

Blast furnace slag and steel slag are readily available worldwide, and the chemical and mineral compositions and physical properties of different batches often only fluctuate slightly. Metallurgical slags, in particular copper slags, are characterized by high density and high strength.

In a preferred embodiment of the invention, the slag is an iron-containing slag and has at least 8% by weight, in particular at least 10% by weight, preferably at least 15% by weight, 20% by weight or 25% by weight, of iron, calculated as FeO. The iron-containing slag contains in particular 10 to 70% by weight of iron, calculated as FeO.

It has been surprisingly found that slag having a high iron content can improve electrical conductivity and sometimes thermal conductivity in the cured binder composition. They are therefore particularly useful for the preparation of materials with improved electrical and sometimes also thermal conductivity.

In particular, it is desirable that the slag in the binder composition having improved electrical conductivity after curing comprises 10 to 70 wt.%, preferably 15 to 60 wt.% of iron, calculated as FeO. The iron-containing slag is preferably steel slag, in particular slag from an electric arc furnace, a foundry ladle, a basic oxygen furnace steelmaking process or an oxygen blowing process, or copper slag.

In another preferred embodiment, the slag has an apparent density of at least 2.9kg/l, preferably at least 3.1kg/l, in particular at least 3.3kg/l, especially at least 3.5 kg/l. It has been found that a binder composition comprising slag having a high apparent density can, after curing, have on the upper side (upper surface) a layer of cured binder, in which layer the slag content is significantly lower than the rest of the cured binder composition. In particular, the slag content of the layer having a particle size of more than 0.1mm is less than about 10% by weight, in particular less than 5% by weight. This results in a particularly good adhesion to overlying materials, which is particularly advantageous, for example, for anchoring machines and turbines by under-pouring.

The preferred particle size of the slag depends on the application and can be as high as 32mm or more. The slag preferably has a particle size of at most 16mm, preferably at most 8mm, more preferably at most 4mm, in particular at most 3.5 mm.

Slag particles of suitable size can also be obtained by crushing and/or grinding larger slag particles.

The particle size can be determined by a sieving method according to DIN EN 933-1.

The slag can be divided into size fractions, for example by sieving, and the individual size fractions can then be mixed in different amounts to obtain the desired size distribution (sieving curve). Such methods are known to those skilled in the art.

The slag preferably has a particle size of from 0.05 to 16mm, preferably from 0.06 to 8mm, more preferably from 0.1 to 4mm, in particular from 0.12 to 3.5 mm.

The slag particles preferably have an irregular shape and/or a rough surface and are in particular non-spherical. This is particularly advantageous for the particles to intermesh and bond well to the binder.

In particular, the slag particles may have any non-spherical geometry, whether uniform or non-uniform. For example, the particles may have a pyramidal, polygonal, cubic, pentagonal, hexagonal, octagonal, prismatic, and/or polyhedral shape. The non-uniform particles may, for example, have a circular, oval, elliptical, square, rectangular, triangular, or polygonal cross-section at least partially therein. The term "non-uniform" or "irregularly" shaped particle refers to a three-dimensional particle shape in which at least two different cross-sections of the particle have different shapes. An exemplary cross-section of slag particles having an irregular shape is schematically shown in fig. 1. A summary of suitable Particle shapes is provided by S.Blott, K.Pye in "Particle shape: a review and new methods of characterization and Classification" (Sementology, (2008)55, 31-63).

Preference is given to slag, in particular steel slag, which is cooled with water, in particular in a slag bed. Also advantageous are slags, in particular copper slags, granulated by means of high-pressure water jets in the form of a slag stream.

The slag breaks into small pieces as a result of rapid cooling. This is advantageous because it saves crushing energy and also because it results in irregular, often angular shapes.

The moisture content of the slag is preferably less than 5% by weight, more preferably less than 3% by weight, particularly preferably less than 1% by weight, in particular less than 0.5% by weight.

For some applications it is advantageous that the porosity of the slag is in the range of 5 vol%. The weight of the product can thereby be reduced without seriously impairing the final properties.

It is also advantageous for some applications that the slag has a porosity of more than 5% by volume, whereby the weight of the product can be reduced. For certain applications, in particular for highly compressive materials, it may be advantageous for the porosity of the slag to be below 5% by volume, preferably below 3% by volume.

Slag may also be surface modified. For example, the surface of the slag particles may be coated or covered with a wetting agent and/or coupling aid. It is preferred within the scope of the present invention, however, that the slag surface is not modified, i.e. that the slag is not present in surface-modified form.

In addition to slag, the binder composition advantageously comprises at least one other mineral filler. Fillers are solid particulate substances that are chemically inert and are provided in a variety of shapes, sizes, and different materials. The shape of the mineral filler can vary from fine sand grains to large coarse stones. Particularly suitable fillers are sand, gravel, crushed stone, calcined gravel or light fillers, such as, in particular, clay minerals, pumice or perlite. Other suitable fillers are fine fillers such as limestone powder, chalk, quartz powder, titanium dioxide, barite or powdered alumina. Advantageously, different fillers are mixed according to type and/or particle size.

The particle size of the at least one other filler depends on the application and may be up to 32mm or more.

The particle size is preferably at most 16mm, particularly preferably at most 8 mm. The particle size is particularly preferably below 4 mm. The particle size is advantageously in the range of about 0.1 μm to 3.5 mm. The particle size can be determined by a sieving method according to DIN EN 933-1.

It is advantageous to mix fillers of different particle sizes corresponding to the desired particle size distribution curve. Particle size distribution curves suitable for various applications are known to those skilled in the art.

The at least one other mineral filler is advantageously chosen from limestone powder, chalk, quartz powder, silica dust (amorphous SiO)₂) Titanium dioxide, barite powder and alumina, preferably having a particle size of at most 0.1 mm.

In an advantageous embodiment of the invention, the binder composition is preferably substantially free of quartz sand and quartz powder. It comprises in particular less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 1% by weight, of quartz sand and/or quartz powder. Such compositions protect natural resources and enable good to excellent processability, curability and use properties.

The binder composition preferably contains slag having a particle size of greater than 0.1mm and a fine mineral filler other than slag having a particle size of at most 0.1mm without other fillers. Such compositions are easy to process and provide good strength after curing.

Preferably, the mass ratio of slag to at least one other mineral filler (in particular a mineral filler having a particle size of at most 0.1 mm) is from 100:0 to 60:40, in particular from 80:20 to 70: 30. Such a ratio achieves good filling of the mineral filler and good strength of the cured binder composition.

The slag advantageously has a particle size of more than 0.1mm in this case.

However, it may also be advantageous for the binder composition to contain no further fillers. In this case, the slag includes all mineral particles having a size of about 0.1 μm to 1mm, 2mm, 4mm, 8mm or larger. This is particularly advantageous for maximum utilization of the slag and for obtaining good strength of the cured binder composition, and in particular in the case of iron-containing slag, for obtaining improved electrical conductivity and sometimes also improved thermal conductivity.

In a preferred embodiment of the present invention, the organic binder in the curable binder composition comprises at least one epoxy resin and at least one curing agent for the epoxy resin. The epoxy resin is a low molecular weight compound or a polymeric compound having an epoxy group. Suitable epoxy resins for the preparation of plastics are known in the art and are commercially available. If the epoxy resin has a defined exact number of epoxy groups per molecule, it preferably has at least two epoxy groups per molecule, for example two, three, four or more epoxy groups per molecule. If the epoxy resin is a polymer having a different number of epoxy groups in the molecule, it has an average of more than one epoxy group per molecule. The epoxy resin then preferably contains an average of at least two epoxy groups per molecule.

According to the present invention, mixtures of various epoxy resins, for example mixtures of two, three or more different epoxy resins, may be used.

Suitable epoxy resins are obtained in a known manner, in particular by oxidation of olefins or by reaction of epichlorohydrin with polyols, polyphenols or amines.

Suitable epoxy resins are in particular aromatic epoxy resins, in particular glycidyl ethers of the following:

-bisphenol-a, bisphenol-F or bisphenol-a/F, wherein a represents acetone and F represents formaldehyde, which acts as a reactant for the preparation of said bisphenol. In the case of bisphenol-F, it is also possible to have positional isomers which are derived in particular from 2,4 '-or 2,2' -hydroxyphenylmethane. The epoxy resin has the formula (I):

wherein the substituent R¹And R²Independently of one another, H or CH₃. Further, the index n represents a value of 0 to 1. n preferably represents a value of less than 0.2.

Such epoxy resins are, for example, based onGY250、PY304、GY282(Huntsman) or d.e.r.^TM331 or d.e.r.^TM330(Dow) or Epikote 828 or Epikote 862 (Hexion).

Dihydroxybenzene derivatives such as resorcinol, hydroquinone or catechol;

other bisphenols or polyphenols such as bis (4-hydroxy-3-methylphenyl) methane, 2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol-C), bis (3, 5-dimethyl-4-hydroxyphenyl) methane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (4-hydroxyphenyl) butane (bisphenol-B), 3-bis (4-hydroxyphenyl) pentane, 3, 4-bis (4-hydroxyphenyl) hexane, 4, 4-bis (4-hydroxyphenyl) heptane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2, 4-bis (3, 5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) -cyclohexane (bisphenol-Z), 1-bis- (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (bisphenol-TMC), 1-bis- (4-hydroxyphenyl) -1-phenylethane, 1, 4-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene (bisphenol-P), 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene (bisphenol-M), 4,4 '-dihydroxybiphenyl (DOD), 4' -dihydroxybenzophenone, bis (2-hydroxynaphthalen-1-yl) methane, bis (4-hydroxynaphthalen-1-yl) methane, 1, 5-dihydroxynaphthalene, tris (4-hydroxyphenyl) methane, 1,2, 2-tetrakis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether, or bis (4-hydroxyphenyl) sulfone;

-novolakens (novolakens), in particular condensation products of phenol or cresol with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde or 2-ethylhexanal or benzaldehyde or furfural;

the epoxy resin is under the trade name EPN or ECN and556 was obtained commercially from Huntsman or as product series d.e.n.^TMCommercially available from Dow Chemical.

Aromatic amines, such as aniline, P-toluidine, 4-aminophenol, 4 '-methylenediphenyldiamine, 4' -methylenediphenylbis- (N-methyl) amine, 4'- [1, 4-phenylene-bis (1-methylethylidene) ] diphenylamine (diphenylamine-P) or 4,4' - [1, 3-phenylene-bis (1-methylethylidene) ] diphenylamine (diphenylamine-M).

Other suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular

-a di-, tri-or tetrafunctional C which is saturated or unsaturated, branched or unbranched, cyclic or open-chain₂-to C₃₀-glycidyl ethers of alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane;

-hydrogenated bisphenol-a-, -F-or-a/F-liquid resins, or glycidylation products of hydrogenated bisphenol-a-, -F-or-a/F;

n-glycidyl derivatives of amides or heterocyclic nitrogen-containing bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin and hydantoin;

epoxy resins resulting from the oxidation of olefins, such as, in particular, vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1, 5-hexadiene, butadiene, polybutadiene or divinylbenzene.

The epoxy resin is preferably a liquid resin or a mixture comprising two or more liquid epoxy resins.

"liquid epoxy resin" means a commercial polyepoxide having a glass transition temperature of less than 25 ℃.

The epoxy resin composition optionally further comprises a content of a solid epoxy resin.

The epoxy resins are in particular liquid resins based on bisphenols, in particular bisphenol-A diglycidyl ether and/or bisphenol-F diglycidyl ether, for example commercially available from Olin, Huntsman or Momentive. These liquid resins have a low viscosity for epoxy resins and enable fast curing and high modulus and high pressure resistant materials. It may contain a certain content of bisphenol a-solid resin or novolak-glycidyl ether.

The epoxy resin-based adhesive composition preferably additionally comprises at least one reactive diluent.

Suitable reactive diluents are low-viscosity, aliphatic or cycloaliphatic compounds containing epoxy groups.

The reactive diluent is preferably a monofunctional glycidyl ether, such as phenyl glycidyl ether, cresyl glycidyl ether, guaiacol glycidyl ether, 4-methoxyphenyl glycidyl ether, p-n-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-dodecylphenyl glycidyl ether, cardanol glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether or the condensation of natural alcoholsGlycerol ethers, e.g. especially C₈-to C₁₀-or C₁₂-to C₁₄-or C₁₃-to C₁₅Alkyl glycidyl ethers, difunctional glycidyl ethers such as butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether or neopentyl glycol diglycidyl ether, trifunctional glycidyl ethers such as trimethylolpropane triglycidyl ether, or aliphatic polyols having one, two, three or more functional glycidyl ether groups. Also suitable are epoxidized soybean oil or linseed oil, compounds having acetoacetate groups, in particular acetoacetylated polyols, butyrolactone, and also other isocyanates and silicones having reactive groups.

As the curing agent for the epoxy resin, a common and known compound that reacts with an epoxy group can be used. Thereby crosslinking the epoxy resin. The curing agent is preferably a basic curing agent, in particular an amine compound or an amide.

The curing agent is preferably a polyamine having at least three amine hydrogens reactive with epoxide groups.

An amine hydrogen represents a hydrogen atom which is directly bonded to an amine nitrogen atom and which is reactive with an epoxy group. The curing agent for epoxy resins preferably contains at least two primary or secondary amino groups per molecule. The amine compound having two or more amino groups per molecule is hereinafter referred to as "polyamine". Preferably, the polyamine is present in the epoxy resin composition in an amount such that the molar ratio of amine hydrogens to epoxy groups is in the range of from 0.6 to 1.5, in particular from 0.8 to 1.2.

According to the present invention, mixtures of various epoxy resin curing agents may be used, for example mixtures of two, three or more different curing agents.

Polyamines suitable as curing agents for epoxy resins are in particular:

aliphatic, cycloaliphatic or araliphatic primary diamines, in particular ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 2-methyl-1, 2-propylenediamine, 2-dimethyl-1, 3-propylenediamine, 1, 3-butylenediamine, 1, 4-butylenediamine, 1, 3-pentylenediamine (DAMP), 1, 5-pentylenediamine, 1, 5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1, 5-pentylenediamineDiamine (C11-neo-diamine), 1, 6-hexanediamine, 2, 5-dimethyl-1, 6-hexanediamine, 2, 4-and 2,4, 4-Trimethylhexamethylenediamine (TMD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, bis- (4-aminocyclohexyl) methane, bis- (4-amino-3-methylcyclohexyl) -methane, bis- (4-amino-3-ethylcyclohexyl) -methane, bis- (4-amino-3, 5-dimethylcyclohexyl) -methane, bis- (4-amino-3-ethyl-5-methylcyclohexyl) -methane (M-MECA), 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane (═ isophoronediamine or IPDA), 2- (4) -methyl-1, 3-diaminocyclohexane, 1, 3-or 1, 4-bis- (aminomethyl) cyclohexane, 1, 3-cyclohexylenediamine, 2,5(2,6) -bis- (aminomethyl) -bicyclo [2.2.1]Heptane (NBDA), 3(4),8(9) -bis- (aminomethyl) -tricyclo [5.2.1.0^2,6]Decane, 1, 4-diamino-2, 2, 6-Trimethylcyclohexane (TMCDA), 1, 8-menthanediamine, 3, 9-bis- (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5.5 ]]Undecane, 1, 3-bis- (aminomethyl) benzene (MXDA) or 1, 4-bis- (aminomethyl) benzene;

aliphatic primary diamines containing ether groups, in particular bis- (2-aminoethyl) ether, 3, 6-dioxa-1, 8-octanediamine, 4, 7-dioxa-1, 10-decanediamine, 4, 7-dioxa-2, 9-decanediamine, 4, 9-dioxa-1, 12-dodecanediamine, 5, 8-dioxa-3, 10-dodecanediamine, 4,7, 10-trioxa-1, 13-tridecanediamine and higher oligomers of said diamines, bis- (3-aminopropyl) polytetrahydrofuran and other polytetrahydrofurandiamines having a molecular weight, for example in the range from 350 to 2000, and also polyoxyalkylene diamines. The latter are generally products formed by amination of polyoxyalkylene-diols and can be obtained, for example, by name(from Huntsman), the name Polyetheramine (from BASF) or the name PC(from Nitroil). Particularly suitable polyoxyalkylene diamines areD-230、D-400、D-2000、XTJ-511、ED-600、ED-900、ED-2003、XTJ-568、XTJ-569、XTJ-523、XTJ-536、XTJ-542、XTJ-559、EDR-104、EDR-148、EDR-176、Polyetheramin D 230、Polyetheramin D 400und Polyetheramin D2000、DA 250、DA 400、DA 650 andDA 2000；

polyamines having secondary amino groups, in particular Diethylenetriamine (DETA), triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), Pentaethylenehexamine (PEHA), higher homologs of linear polyethyleneamines, Dipropylenetriamine (DPTA), N- (2-aminoethyl) -1, 3-propanediamine (N3-amine), N '-bis (3-aminopropyl) ethylenediamine (N4-amine), N' -bis (3-aminopropyl) -1, 4-diaminobutane, N5- (3-aminopropyl) -2-methyl-1, 5-pentanediamine, N3- (3-aminopentyl) -1, 3-pentanediamine, N5- (3-amino-1-ethylpropyl) -2-methyl-1, 5-Pentanediamine, N' -bis (3-amino-1-ethylpropyl) -2-methyl-1, 5-pentanediamine or bis (6-aminohexyl) amine (BHMT), 3- (dimethylamino) propylamine (DMAPA), 3- (3- (dimethylamino) propylamino) propylamine (DMAPAPA), N-alkylated polyetheramines, for exampleCompositions of type-SD-231, SD-401, SD-404 and SD-2001 (from Huntsman), N-benzyl-1, 2-ethylenediamine, N-benzyl-1, 2-propylenediamine, N-benzyl-1, 3-bis (aminomethyl) benzene, N- (2-ethylhexyl) -1, 3-bis (aminomethyl) benzene, N- (2-phenylethyl) -1, 3-bis (aminomethyl) benzene (styrenated 1, 3-bis (aminomethyl) benzene, available from Mitsubishi Gas Chemical240), N-benzyldiethylenetriamine, N-benzyltriethylenetetramine, N-benzyltetraethylenepentamine, N '-benzyl-N- (3-aminopropyl) ethylenediamine or N "-benzyl-N, N' -bis (3-aminopropyl) -ethylenediamine;

-amine/polyepoxide-adducts; in particular adducts of said polyamines with diepoxides (at a molecular weight of at least 2/1, in particular a molecular weight of 2/1 to 10/1) or with monoepoxides;

polyamidoamines which are reaction products of monovalent or polyvalent carboxylic acids or esters or anhydrides thereof, in particular dimeric fatty acids, and aliphatic, cycloaliphatic or aromatic polyamines, in particular polyalkyleneamines such as DETA or triethylenetetramine (TETA), in particular commercially available polyamidoamines, which are used in stoichiometric excess100. 125, 140 and 150 (from Cognis),125. 140, 223, 250 and 848 (from Huntsman),3607、530 (from Huntsman) in the reactor,EH 651, EH 654, EH 655, EH 661, and EH 663 (from Cytec);

-Polyethyleneimine (PEI), which is a branched polymeric amine obtained from the polymerization of ethyleneimine. Suitable polyethyleneimines generally have an average molecular weight in the range from 250 to 25000g/mol and comprise tertiary, secondary and primary amino groups. Polyethyleneimine, for example, under the trade name(from BASF) e.g.WF、FG、G20 andPR 8515.

Mannich bases, in particular phenamine, i.e. the reaction product of phenols (in particular cardanol) with aldehydes (in particular formaldehyde) and polyamines.

As curing agents for epoxy resins, it is also possible to use mercapto-group-containing compounds, in particular thiol-terminated polysulfide polymers in liquid form, thiol-terminated polyoxyalkylene ethers, thiol-terminated polyoxyalkylene derivatives, polyesters of thiocarboxylic acids, 2,4, 6-trimercapto-1, 3, 5-triazine, triethylene glycol dithiol or ethylene glycol dithiol.

As curing agents for epoxy resins, it is also possible to use acidic curing agents, in particular anhydrides. It is also possible to use curing agents having a catalytic action, such as fluorides, for example boron trifluoride.

The curing agent for epoxy resins is preferably selected from TMD, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, IPDA, 2(4) -methyl-1, 3-diaminocyclohexane, MXDA, DETA, TETA, TEPA, PEHA, N4-amine, DMAPAPA, N-benzyl-1, 2-ethylenediamine, adducts of these or other polyamines with monoepoxides or diepoxides, and Mannich bases.

In another preferred embodiment of the present invention, the organic binder in the curable binder composition comprises at least one polyisocyanate and at least one polyol. Polyisocyanates are understood to be compounds containing two or more isocyanate groups. The term polyisocyanate here also includes polymers containing isocyanate groups. Polyisocyanates produce polyurethanes by reaction with atmospheric moisture or with polyols. The expression "polyurethane" here denotes polymers formed by the so-called polyaddition of diisocyanates. The polymers may have, in addition to urethane groups, further groups, in particular urea groups.

Preferred polyisocyanates are aliphatic, cycloaliphatic or aromatic diisocyanates, in particular 1, 6-Hexamethylene Diisocyanate (HDI), 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2, 4 '-and/or-4, 4' -diphenylmethane diisocyanate (H)₁₂MDI), 4,4' -diphenylmethane diisocyanate (optionally with a content of 2,4' -and/or 2,2' -diphenylmethane diisocyanate (MDI)), 2, 4-tolylene diisocyanate or a mixture thereof with 2, 6-Tolylene Diisocyanate (TDI), a mixture of MDI and MDI homologues (polymeric MDI or PMDI) or an oligomeric isocyanate. Suitable isocyanate group-containing polymers are obtained in particular by reaction of at least one polyol with a superstoichiometric amount of at least one polyisocyanate, in particular a diisocyanate (preferably MDI, TDI, IPDI or HDI).

Suitable polyols are in particular the following commercially available polyols or mixtures thereof:

polyether polyols, in particular polyoxyalkylene diols and/or triols. Preferred polyether polyols are polyoxypropylene diols or triols, or ethylene oxide-capped (EO-capped) polyoxypropylene diols or triols.

Polyester polyols (also known as oligoester alcohols) prepared according to known methods, in particular the polycondensation of hydroxycarboxylic acids or lactones or the polycondensation of aliphatic and/or aromatic polycarboxylic acids with di-or polyhydric alcohols. Particularly suitable polyester polyols are polyester diols.

Polycarbonate polyols, such as those obtained by reaction of alcohols such as those mentioned above (used for the synthesis of polyester polyols) with dialkyl carbonates, diaryl carbonates or phosgene.

Block copolymers with at least two hydroxyl groups, having at least two different blocks with polyether, polyester and/or polycarbonate structures of the type described above, in particular polyether polyester polyols.

-polyacrylate polyols and polymethacrylate polyols,

polyhydroxy-functional fats and oils, also known as fatty acid polyols,

polyhydrocarbon polyols, also known as oligohydrocarbon alcohols,

epoxidized vegetable oils and their reaction products with monofunctional alcohols,

-a polybutadiene polyol,

reaction products of vegetable oils (in particular castor oil) with ketone resins,

-a polyester polyol based on hydrogenated tall oil,

polyester polyols based on dimerized fatty acids or dimerized fatty alcohols,

-alkoxylated polyamines.

When the binder composition comprises a polyisocyanate and a polyol as binder, it preferably comprises at least one aromatic polyisocyanate and at least one polyol selected from the group consisting of: epoxidized vegetable oils and their reaction products with monofunctional alcohols, polybutadiene polyols, reaction products of vegetable oils (in particular castor oil) with ketone resins, polyester polyols based on hydrogenated tall oil, and polyester polyols based on dimerized fatty acids or dimerized fatty alcohols.

Particularly advantageous are combinations of polyisocyanates and polyols as described in EP 3339343 and EP 3415544.

Such binder compositions are particularly hydrophobic, do not absorb moisture after curing and are hydrolytically stable, which is advantageous.

The binder composition may optionally comprise one or more additives, in particular non-reactive diluents, dispersants, defoamers, wetting agents, preservatives, accelerators, thickeners, pigments, polymer powders, fibers, plasticizers or dyes.

Suitable as non-reactive diluents, especially in adhesive compositions comprising epoxy resinsIs an organic solvent or a high-boiling point diluent, particularly xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, diphenylmethane, diisopropylnaphthalene, petroleum fractions such as xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol butyl ether, diphenylmethane, and diisopropylnaphthalene, petroleum fractions such as petroleum fractions-types (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, cardanol (from cashew nut shell oil, comprising the main component 3- (8,11, 14-pentadecatrienoyl) phenol), styrenated phenols, bisphenols, aromatic hydrocarbon resins, in particular of the phenol-containing type, alkoxylated phenols, in particular ethoxylated or propoxylated phenols, in particular 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organophosphates or sulfonates or sulfonamides.

Diluents having a boiling point of more than 200 ℃ are preferred.

The diluent is preferably selected from the group consisting of benzyl alcohol, styrenated phenols, ethoxylated phenols, aromatic hydrocarbon resins containing phenolic groups, especiallyType LS 500, LX 200, LA 300 or LA 700 (from Huntgers), diisopropyl naphthalene and cardanol.

Benzyl alcohol is particularly preferred.

The phenol group-containing diluent also exhibits an effect as an accelerator.

Suitable accelerators, in particular in the binder compositions comprising epoxy resins, are compounds which accelerate the reaction between epoxy groups and/or amino groups, in particular acids or compounds which can be hydrolyzed to acids, in particular organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic esters, other organic or inorganic acids such as in particular phosphoric acid, or mixtures of the abovementioned acids and acid esters; nitrates such as in particular calcium nitrate; tertiary amines such as, in particular, 1, 4-diazabicyclo [2.2.2] octane, benzyldimethylamine, α -methylbenzyldimethylamine, triethanolamine, dimethyl-aminopropylamine, imidazoles such as, in particular, N-methylimidazole, N-vinylimidazole or 1, 2-dimethylimidazole, salts of said tertiary amines, quaternary ammonium salts such as, in particular, benzyltrimethylammonium chloride, amidines such as, in particular, 1, 8-diazabicyclo [5.4.0] undec-7-ene, guanidines such as, in particular, 1,3, 3-tetramethylguanidine, phenols, in particular, bisphenols, phenol-resins or mannich bases such as, in particular, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol or from phenol, formaldehyde and N, N-dimethyl-1, 3-propanediamine, phosphites such as, in particular, di-or triphenyl phosphite, or compounds having mercapto groups.

Preferred accelerators are acids, nitrates, tertiary amines or mannich bases.

Particularly preferred are salicylic acid, p-toluenesulfonic acid, calcium nitrate or 2,4, 6-tris (dimethylaminomethyl) phenol or combinations thereof.

Suitable catalysts, in particular in binder compositions comprising polyisocyanates and polyols, are metal organic compounds or amines, in particular secondary and tertiary amines.

At least one wetting agent and/or dispersant, in particular based on polycarboxylate ethers, is preferably present in the binder composition. This enables better processability, in particular good flowability, and a high filler content, which is advantageous for good homogeneity and strength of the cured binder composition.

In this context, polycarboxylate ethers are understood to be comb polymers having both anionic groups and polyalkylene glycol side chains attached to the polymer backbone. Such polymers are known as plasticizers for mineral binders such as cement and gypsum.

Preferred polycarboxylate ethers comprise structural units of formula I and structural units of formula I I,

wherein

R¹Each independently of the others represents-COOM, -SO₂-OM、-O-PO(OM)₂and/or-PO (OM)₂Preferably a group of-COOM,

R²and R⁵Each independently of the other represents H, -CH₂-COOM or alkyl having 1 to 5 carbon atoms, preferably H or-CH₃，

R³And R⁶Each independently of the other, represents H or an alkyl radical having 1 to 5 carbon atoms, preferably H,

R⁴and R⁷Each independently of the others, represents H, -COOM or an alkyl group having 1 to 5 carbon atoms, preferably H,

or R¹And R⁴Forming a ring to obtain-CO-O-CO- (acid anhydride),

each M independently of the other represents H⁺Alkali metal ions, alkaline earth metal ions, divalent or trivalent metal ions, ammonium groups or organic ammonium groups, preferably H⁺Or an alkali metal ion, or a salt thereof,

p is 0, 1 or 2,

o is 0 or 1, or a combination thereof,

m is 0 or an integer of 1 to 4,

n-2 to 250, in particular 10 to 200,

x's each independently of the other represent-O-or-NH-,

R⁸each representing H, C independently of each other₁-to C₂₀-alkyl, -cyclohexyl or-alkylaryl, and

A＝C₂-to C₄Alkylene, preferably ethylene.

The molar ratio of structural units I to structural units II is preferably from 0.7 to 10:1, more preferably from 1 to 8:1, in particular from 1.5 to 5: 1.

It may also be advantageous for the polycarboxylate ether to also have structural unit III. The structural unit III is preferably derived from a monomer selected from the group consisting of: alkyl or hydroxyalkyl esters of acrylic or methacrylic acid, vinyl acetate, styrene and N-vinylpyrrolidone.

The polycarboxylate ether preferably contains carboxylic acid groups and/or salts thereof and polyethylene glycol side chains.

Preferred are polycarboxylate ethers consisting of structural units I derived from ethylenically unsaturated carboxylic acids, in particular unsaturated monocarboxylic acids, or salts thereof, and structural units II derived from ethylenically unsaturated polyalkylene glycols, in particular polyethylene glycols. In particular, the polycarboxylate ether contains no further structural units apart from structural unit I and structural unit II.

The binder composition is preferably free of organosilanes.

In particular, the binder composition does not comprise an organosilane selected from: glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethyl-aminopropyltrimethoxysilane, aminoethyl-aminopropyltriethoxysilane, aminoethyl-aminopropylmethyldimethoxysilane, aminoethyl-aminopropylmethyldiethoxysilane, phenylaminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane.

Preferably, the slag and optionally at least one other filler (if present) are coated with a wetting agent and/or a dispersing agent. The coating can be carried out here by simply spraying a liquid wetting agent and/or dispersant or a solution of a liquid or solid wetting agent and/or dispersant in a suitable solvent.

Advantageous binder compositions comprising at least one epoxy resin and at least one polyamine comprise:

5 to 30% by weight, preferably 8 to 25% by weight, more preferably 8 to 17% by weight, of an epoxy resin,

0.4 to 7% by weight, preferably 1 to 5% by weight, of a polyamine,

10 to 25% by weight of a mineral filler other than slag, in particular having a particle size of at most 0.1mm,

from 50 to 80% by weight, preferably from 60 to 75% by weight, of slag, in particular having a particle size of from 0.1 to 16mm, preferably from 0.1 to 8mm, especially from 0.1 to 4, or from 0.1 to 3.5mm, and

from 0 to 10% by weight, preferably from 0.01 to 5% by weight, of further additives,