POLYURETHANE-BASED POLYMER CONCRETES AND GROUTING MORTARS

Abstract

The present invention relates to a curable binder composition comprising: a) at least one organic binder comprising a polyisocyanate and a polyol, and b) at least 50% by weight of a filler in the form of quartz and/or slag, based on 100% by weight of binder composition.

Claims

1. A curable binder composition comprising: a) at least one organic binder comprising a polyisocyanate and a polyol, and b) at least 50% by weight of a filler in the form of quartz and/or slag, based on 100% by weight of the binder composition.

2. The binder composition as claimed in claim 1, wherein the filler has a particle size of at least 0.1 mm.

3. The binder composition as claimed in claim 1, wherein the filler is present in the form of slag or a mixture of slag and quartz, the slag being selected from the group consisting of blast furnace slags.

4. The binder composition as claimed in claim 1, wherein slag is present as the filler in the binder composition in an amount of at least 60% by weight, based on 100% by weight of the binder composition, the slag being an iron-containing slag comprising at least 8% by weight of iron, calculated as FeO, and the slag having a bulk density of at least 2.9 kg/l.

5. The binder composition as claimed in claim 1, wherein the binder composition further comprises an additional filler material different from the filler.

6. The binder composition as claimed in claim 1, wherein the composition comprises less than 10% by weight of quartz.

7. The binder composition as claimed in claim 1, wherein the polyisocyanate and the polyol together are present in the binder composition in an amount of at least 5% by weight based on 100% by weight of the binder composition.

8. The binder composition as claimed in claim 1, wherein the organic binder includes at least one mixture of polyols having different OH functionality.

9. The binder composition as claimed in claim 1, comprising: 3% to 40% by weight of polyisocyanates, 3% to 40% by weight of polyols, 50% to 94% by weight of filler in the form of slag, optionally 10% to 40% by weight of additional filler material, and 0% to 15% by weight of further additives, based on 100% by weight of the binder composition.

10. A multicomponent 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, a filler, and optionally further ingredients, wherein the filler and the optional further ingredients are present in the at least one polyisocyanate component, in the at least one polyol component, and/or in any further component optionally present.

11. (canceled)

12. A polymer concrete or grouting mortar that has improved stability towards corrosive substances and which includes the binder composition as claimed in claim 1.

13. The binder composition as claimed in claim 1, wherein the binder composition conducts electric current.

14. A material comprising the binder composition as claimed in claim 1, wherein the material has improved electrical conductivity at 20° C. as compared to a like material without the binder composition, and wherein the slag in the binder composition is an iron-containing slag comprising at least 8% by weight of iron, calculated as FeO, based on the total weight of the slag, and/or a slag having a bulk density of at least 3.1 kg/l.

15. A cured binder composition obtained (i) by curing of a binder composition comprising: a polyisocyanate and a polyol, and b) at least 50% by weight of a filler in the form of quartz and/or slag, based on 100% by weight of the binder composition; or by (ii) mixing of at least one polyisocyanate component comprising at least one polyisocyanate, at least one polyol component comprising at least one polyol, and a filler to provide a multicomponent system, and curing the multicomponent system.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0175] FIG. 1 shows: a schematic representation of exemplary cross sections of irregularly shaped slag particles;

[0176] FIG. 2 shows: the compressive strengths of inventive test specimens having a polyurethane matrix and different fillers after storage in different media (H.sub.2O, AcOH or NaOH);

[0177] FIG. 3 shows: the compressive strengths of further inventive test specimens having a polyurethane matrix and different fillers after storage in different media;

[0178] FIG. 4 shows: the compressive strengths of epoxy-based test specimens having different fillers after storage in different media.

EXAMPLES

[0179] Working examples are presented hereinbelow, the purpose of which is to further elucidate the described invention. The invention is of course not limited to these described working examples.

[0180] “Ex.” stands for “example”.

[0181] “Ref.” stands for “reference example”.

[0182] Materials Used

[0183] Setathane® 1150 is a polyol based on a reaction product of castor oil with ketone resins (Allnex Resins Germany GmbH, Germany).

[0184] Desmophen® T4011 is a polyether polyol based on 1,1,1-trimethylolpropane (Covestro AG, Germany).

[0185] Sylosiv® is a zeolite (Grace, USA).

[0186] Desmodur® VL is an aromatic polyisocyanate based on diphenylmethane 4,4diisocyanate (Covestro AG, Germany).

[0187] Desmodur® CD-L is an aromatic polyisocyanate based on diphenylmethane 4,4diisocyanate (Covestro AG, Germany).

[0188] Neukapol® 1119 is a reaction product of epoxidized vegetable oils (rapeseed oil) having a proportion of unsaturated C.sub.18 fatty acids of 91% by weight, based on the total amount of fatty acids, with monofunctional C.sub.1 to C.sub.18 alcohols; OH functionality 2.0, average molecular weight approx. 390 g/mol, OH value of 290 mg KOH/g (Altropol Kunststoff GmbH, Germany).

[0189] Neukapol® 1582 is a reaction product of epoxidized fatty acid esters of methanol with glycerol, where the epoxidized fatty acid esters, as fatty acid component, are based on fatty acid mixtures of rapeseed oil or sunflower oil, in a mixture with N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine (Altropol Kunststoff GmbH, Germany).

[0190] The quartz sand and slags were dried before use and divided into grain fractions by sieving. The grain fractions were then mixed such that the grain size distribution of the sands used corresponded to a specified grain size distribution (grading curve).

[0191] EFS is an electric furnace slag from Stahl Gerlafingen, Switzerland. The material used had a bulk density of around 3.3 kg/l and an iron content, calculated as FeO, of about 19% by weight.

[0192] BFS is a blast furnace slag from Hüttenwerke Krupp Mannesmann, Germany, available from Hermann Rauen GmbH & Co., Germany. The material used had a bulk density of 2.9 kg/l and an iron content, calculated as FeO, of about 3% by weight.

[0193] Raulit® is a blast furnace slag from DK-Recycling and Roheisen GmbH, Germany, available under the brand name Raulit®-Mineralbaustoffgemisch from Hermann Rauen GmbH & Co., Germany. The material used had a bulk density of around 2.9 kg/l and an iron content, calculated as FeO, of about 1% by weight.

[0194] FS is a foundry sand from voestalpine AG, Austria. The material used had a bulk density of around 2.9 kg/l and an iron content, calculated as FeO, of less than 1% by weight.

[0195] CS is NAstra® iron silicate granules, a glassy copper slag available from Sibelco, Germany, having a bulk density of about 3.7 kg/l and an iron content, calculated as FeO, of about 51% by weight.

[0196] Sikadur®-42 HE is a three-component epoxy-resin-based grouting mortar available from Sika Schweiz AG.

[0197] The polycarboxylate ether was a comb polymer with carboxylic acid groups and polyethylene glycol side chains.

[0198] Measurement Methods

[0199] Compressive strength and flexural strength were determined on 40×40×160 mm test specimens using testing machines in accordance with DIN EN 196-1 and EN 12190.

[0200] For determination of specific electrical volume resistance, the opposite 40×40 mm surfaces of the 40×40×160 mm test specimens were coated with electrically conductive gel and a steel electrode covering the entire surface was placed flush on both surfaces. The electrical volume resistance of the test specimens was determined by applying a voltage of 100 mV AC at a frequency of 1 kHz and 10 kHz to the two electrodes.

[0201] Thermal conductivity was determined in accordance with ASTM D5470-06 using the ZFW TIM tester from ZFW (Center for Thermal Management) Stuttgart, Germany, on test specimens 30 mm in diameter and 2 mm in height.

[0202] Polyurethane Matrix

[0203] For the examples, the polyol components (component A) and polyisocyanate components (component B) described in Tables 1 and 2 were used as the polyurethane matrix.

[0204] For each composition, the ingredients specified in Tables 1 and 2 were processed in the specified amounts (in parts by weight) of the polyol component A, by means of a vacuum dissolver with exclusion of moisture, to give a homogeneous paste and stored. The ingredients of the polyisocyanate component B specified in Tables 1 and 2 were likewise stored.

TABLE-US-00001 TABLE 1 Compositions of the polyurethane matrices (all figures except ratios in % by weight) A B C D E F Component A Setathane ® 1150 65.6 65.6 59.7 59.7 55.3 55.3 Desmophen ® T4011 4.3 4.3 3.7 3.7 3.5 3.5 Hydroxy-terminated 19.0 19.0 18.7 18.7 17.3 17.3 polybutadiene polyol Chain extender Butane-1,4-diol 4.3 4.3 — — — — Pentane-1,5-diol — — 11.2 11.2 — — Ethylhexane-1,3-diol — — — — 13.8 13.8 Sylosiv ® 6.9 6.9 6.6 6.6 10.0 10.0 Process chemicals.sup.1) 0.1 0.1 0.1 0.1 0.1 0.1 Component B Desmodur ® VL.sup.6) 100 — 100 — 100 — Desmodur ® CD-L.sup.7) — 100 — 100 — 100 Mixing ratio A:B 100:49.4 100:52.9 100:65.1 100:69.7 100:57.5 100:61.6 [wt %/wt %] NCO:OH 1.11 1.11 1.11 1.11 1.10 1.10 .sup.1)Defoamer and catalyst

TABLE-US-00002 TABLE 2 Compositions of the polyurethane matrices (all figures except ratios in % by weight) G H I J Component A Neukapol ® 1119 43.9 43.9 58.0 58.0 Neukapol ® 1582 22.0 22.0 29.0 29.0 Hydroxy-terminated 22.0 22.0 — — polybutadiene polyol Sylosiv ® 12.0 12.0 12.8 12.8 Process chemicals.sup.1) 0.1 0.1 0.1 0.1 Component B Desmodur ® VL 100 — 100 — Desmodur ® CD-L — 100 — 100 Mixing ratio A:B 100:64.6 100:69.2 100:81.9 100:87.8 [wt %/wt %] NCO:OH 1.07 1.07 1.07 1.07 .sup.1)Defoamer and catalyst

[0205] Solid Component

[0206] For production of the solid component, the solid constituents listed in Table 3 were mixed dry, during which a polycarboxylate ether solution was applied by spraying.

TABLE-US-00003 TABLE 3 Composition of the solid component Proportion Constituent [wt %] Mixture of limestone powder and 25.2 baryte powder, <0.1 mm Sand (slag sand or quartz sand)*, 74.3 0.12-3.2 mm Polycarboxylate ether solution 0.5 (20% by weight of polycar- boxylate ether dissolved in 80% by weight of benzyl alcohol) *Sand type: See examples.

[0207] Production of Curable Grouting Mortars and Test Specimens

[0208] The polyol components A and polyisocyanate components B from Tables 1 and 2 were processed into a homogeneous paste for 30 seconds using a SpeedMixer® (DAC 150 FV, Hauschild; for mixing ratios see Tables 1 and 2). A solid component as per Table 3 was then added and mixed in thoroughly. Unless otherwise stated, the solid component had a constant proportion of 89.5% by weight, while the mixed polyol components A and polyisocyanate components B together had a proportion of 10.5% by weight.

[0209] For comparison purposes, curable compositions and test specimens based on an epoxy resin matrix (hereinafter referred to as SD) were produced as follows: Sikadur®-42 HE component A (comprising the epoxy resin) was mixed thoroughly with the associated component B (comprising the curing agent) in a weight ratio of 3:1 and then a self-produced solid component as per Table 3 was added and mixed in thoroughly. Unless otherwise stated, the solid component had a constant proportion of 89.5% by weight, while the mixed epoxy resin and curable components together had a proportion of 10.5% by weight.

[0210] To produce the test specimens, the mixed curable compositions were poured into steel molds and stored in the formwork for 24 hours at 20° C. The test specimens were then removed from the formwork and stored further at 20° C. After 7 days of storage, the specific electrical resistance, strength, and thermal conductivity were determined.

[0211] Strength and Electrical Volume Resistance of Grouting Mortars

[0212] The strengths and electrical volume resistances of various grouting mortars are stated in the tables below.

[0213] The “Binder matrix” row indicates the polyurethane matrix/epoxy resin matrix used (see Tables 1 and 2), while the “Sand” row indicates the type of sand or slag used in the solid component (see Table 3).

TABLE-US-00004 TABLE 4 Results when using quartz and Desmodur ® VL as polyisocyanate component in the polyurethane matrix Ref. 1 B1 B2 B3 B4 B5 Binder matrix SD I G E C A Sand Quartz Quartz Quartz Quartz Quartz Quartz sand sand sand sand sand sand Compressive 104 99 71 74 82 64 strength [MPa] Flexural 26 26 22 24 25 24 strength [MPa] Specific electrical 243.0 21.4 23.3 24.0 24.5 24.6 volume resistance [MΩ .Math. cm] at 1 kHz Factor.sup.1) 1 kHz 0.09 0.10 0.10 0.10 0.10 Specific electrical 24.9 2.2 2.4 2.5 2.5 2.5 volume resistance [MΩ .Math. cm] at 10 kHz Factor 10 kHz 0.09 0.10 0.10 0.10 0.10 .sup.1)Factor by which the specific electrical volume resistance of a mortar as per examples B1 to B5 is reduced compared to the specific electrical volume resistance of reference mortar Ref. 1, e.g. resistance B1/resistance Ref. 1

TABLE-US-00005 TABLE 5 Results when using quartz and Desmodur ® CD-L as polyisocyanate component in the polyurethane matrix Ref. 1 B6 B7 B8 B9 B10 Binder matrix SD J H F D B Sand Quartz Quartz Quartz Quartz Quartz Quartz sand sand sand sand sand sand Compressive 104 102 75 75 82 73 strength [MPa] Flexural 26 27 23 24 26 27 strength [MPa] Specific electrical 243.0 26.0 23.3 24.5 25.9 23.6 volume resistance [MΩ .Math. cm] at 1 kHz Factor.sup.1) 1 kHz 0.11 0.10 0.10 0.11 0.11 Specific electrical 24.9 2.7 2.4 2.5 2.7 2.4 volume resistance [MΩ .Math. cm] at 10 kHz Factor 10 kHz 0.11 0.10 0.10 0.11 0.10

[0214] From the data in Tables 4 and 5, it can be seen that the electrical conductivity increases by an order of magnitude and the specific electrical resistance decreases by an order of magnitude when switching from an epoxy matrix to a polyurethane matrix with the filler unchanged. Specifically, the specific electrical volume resistance in example Ref. 1 (based on epoxy matrix SD and quartz as filler) is 243.0 MΩ.Math.cm at 1 kHz or 24.9 MΩ.Math.cm at 10 kHz, whereas the corresponding volume resistances for examples B1-1310 (all based on a polyurethane matrix and quartz as filler) are max. 26.0 MΩ.Math.cm at 1 kHz and 2.7 MΩ.Math.cm at 10 kHz.

TABLE-US-00006 TABLE 6 Results when using copper slag (CS) and Desmodur ® VL as polyisocyanate component in the polyurethane matrix Ref. 2 B11 B12 B13 B14 B15 Binder matrix SD I G E C A Sand CS CS CS CS CS CS Compressive 116 93 66 65 82 51 strength [MPa] Flexural 31 26 20 23 29 21 strength [MPa] Specific electrical 24.9 15.5 15.3 16.7 15.5 15.8 volume resistance [MΩ .Math. cm] at 1 kHz Factor.sup.1) 1 kHz 0.62 0.61 0.67 0.62 0.63 Specific electrical 3.3 1.6 1.6 1.8 1.6 1.7 volume resistance [MΩ .Math. cm] at 10 kHz Factor 10 kHz 0.48 0.48 0.55 0.48 0.52

TABLE-US-00007 TABLE 7 Results when using copper slag (CS) and Desmodur ® CD-L as polyisocyanate component in the polyurethane matrix Ref. 2 B16 B17 B18 B19 B20 Binder matrix SD J H F D B Sand CS CS CS CS CS CS Compressive 116 95 68 67 69 63 strength [MPa] Flexural 31 27 20 20 25 25 strength [MPa] Specific electrical 24.9 15.8 16.1 16.3 15.5 16.1 volume resistance [MΩ .Math. cm] at 1 kHz Factor.sup.1) 1 kHz 0.63 0.65 0.65 0.62 0.65 Specific electrical 3.3 1.7 1.7 1.7 1.7 1.7 volume resistance [MΩ .Math. cm] at 10 kHz Factor 10 kHz 0.52 0.52 0.52 0.52 0.52

[0215] Even when using iron-containing slag, the examples based on a polyurethane matrix (examples B11-620) show markedly lower specific electrical volume resistances at both 1 kHz and 10 kHz compared to an epoxy-based composition (example Ref. 2).

[0216] A comparison of Tables 4/5 with Tables 6/7 moreover shows that the use of iron-containing slag instead of quartz is able to further reduce the specific electrical volume resistances by a factor of 2-3.

[0217] Thermal Conductivity

[0218] The thermal conductivities of various grouting mortars were also measured. This was done by producing test specimens having a diameter of 30 mm and a height of 2 mm by pouring into appropriate molds and allowing them to cure at 20° C. for 7 days.

TABLE-US-00008 TABLE 8 Results for thermal conductivities Ref. 3 B21 B22 B23 B24 B25 B26 Binder matrix SD I I I I I I Sand Quartz sand BFS Raulit FS EFS CS Thermal 2.8 2.9 1.1 1.1 0.9 1.0 0.9 conductivity [W/mK]]

[0219] By using slag instead of quartz, the thermal conductivity can be markedly reduced.

[0220] Corrosion Resistance

[0221] To test the corrosion resistance of the binder compositions and of test specimens produced therefrom, various test specimens were produced as described above and allowed to cure for 7 days at 20° C. Compressive strength was then determined in accordance with ASTM D695.

[0222] Thereafter, the test specimens were each stored for 21 days (21 d) in pure water (H.sub.2O), in 10% by volume acetic acid (AcOH) or in 50% by weight sodium hydroxide solution (NaOH) and then dried to constant weight. Compressive strength was then determined again in accordance with ASTM D695.

[0223] FIG. 2 shows the compressive strengths of test specimens based on polyurethane matrix E and a solid component as described above, with quartz, FS, CS, Raulit, BFS, and EFS alternately used as sand.

[0224] It can be seen here that compressive strengths, irrespective of which medium is used (H.sub.2O, AcOH or NaOH), are not only unimpaired but increase during storage.

[0225] FIG. 3 shows the compressive strengths of test specimens based on polyurethane matrix G and a solid component as described above, with quartz, FS, CS, Raulit, BFS, and EFS alternately used as sand.

[0226] In this case too, compressive strengths increase after storage in H.sub.2O and NaOH, whereas in AcOH a slight decrease is discernible for certain solid components.

[0227] FIG. 4 shows for comparison the results for test specimens based on epoxy resin matrix SD and a solid component as described above, with quartz, FS, CS, Raulit, BFS, and EFS again alternately used as sand.

[0228] This shows clearly the sharp decrease in compressive strength on storage in H.sub.2O and AcOH. Only in NaOH is compressive strength maintained, or increases slightly during storage.

[0229] Grouting Mortars with Different Amounts of Polyurethane Matrix

[0230] Table 9 shows the compositions and compressive strengths of further grouting mortars in which the amounts of the binder matrix and the solid components were modified.

TABLE-US-00009 TABLE 9 Grouting mortars with different amounts of sand and polyurethane matrix B27 B28 B29 B30 B31 B32 Binder matrix/ E 6.0 E 6.0 E 20.0 E 20.0 E 12.5 E 12.5 Proportion [wt %] Slag/ CS 79.9 EFS 79.9 CS 66.9 EFS 66.9 CS 75.4 EFS 75.4 Proportion [wt %] Mixture of limestone 14.0 14.0 13.0 13.0 12.0 12.0 powder and baryte powder [wt %] Polycarboxylate ether 0.1 0.1 0.1 0.1 0.1 0.1 solution [wt %] Compressive 36.6 18.3 40.7 31.9 55.0 33.8 strength [MPa]

[0231] The results in Table 9 show that a proportion of binder matrix in the region of more than 6.0% by weight is advantageous in respect of compressive strength. In the case of copper slag (CS) and electric furnace slag (EFS), the test with 12.5% by weight of binder matrix shows the highest compressive strength.