Construction chemical compositions comprising a bisulfite adduct of glyoxylic acid

Abstract

The present invention relates to construction chemical compositions comprising a bisulfite adduct of glyoxylic acid or a salt or mixed salt thereof and an inorganic binder. The composition is useful as a hydration control agent of the inorganic binder.

Claims

1. A construction chemical composition, comprising a bisulfite adduct of glyoxylic acid or a salt or mixed salt thereof and an inorganic binder.

2. The construction chemical composition of claim 1, wherein the bisulfite adduct is of formula (I): ##STR00018## wherein: R1 is COOX; and X is, independently of one another, H or a cation equivalent K.sub.a wherein K is selected from the group consisting of an alkali metal, alkaline earth metal, zinc, iron, ammonium, or phosphonium cation, as mixtures thereof, and a is 1/n wherein n is the valence of the cation.

3. The construction chemical composition of claim 1, wherein X is H, Na, K, Li or mixtures thereof.

4. The construction chemical composition of claim 1, wherein the inorganic binder is selected from the group consisting of a hydraulic binder, a calcium sulfate-based binder, and a mixture thereof.

5. The construction chemical composition of claim 4, wherein the hydraulic binder is an aluminate-containing cement.

6. The construction chemical composition of claim 5, wherein the aluminate-containing cement is selected from the group consisting of a CEM cement, an aluminate cement, a sulfoaluminate cement, and mixtures thereof.

7. The construction chemical composition of claim 6, wherein the aluminate-containing cement is CEM cement.

8. The construction chemical composition of claim 5, wherein the aluminate-containing cement is a mixture of CEM cement and aluminate cement, or a mixture of CEM cement and sulfoaluminate cement, or a mixture of CEM cement, high alumina cement and sulfoaluminate cement.

9. The construction chemical composition of claim 4, wherein the inorganic binder is calcium sulfate dihydrate, calcium, sulfate hemihydrate or anhydrite and mixtures thereof.

10. The construction chemical composition of claim 5, wherein the inorganic binder is a mixture of an aluminate-containing cement and a calcium sulfate-based binder.

11. The construction chemical composition of claim 1, further comprising at least one additive.

12. The construction chemical composition of claim 11, wherein at least one additive is selected from the group consisting of inorganic carbonates, alkali metal sulfates, latent hydraulic binders, dispersants, hardening accelerators, hardening retarders, fillers, essentially aluminate-free cement, and aggregates or a mixture of two or more thereof.

13. The construction chemical composition of claim 12, wherein the additive is at least one polymeric dispersant, phosphorylated polycondensation product or a sulfonic acid and/or sulfonate group containing dispersant.

14. The construction chemical composition of claim 13, wherein the dispersant is a sulfonic acid and/or sulfonate group containing a dispersant selected from the group consisting of lignosulfonates, melamine formaldehyde sulfonate condensates, -naphthalene sulfonic acid condensates, sulfonated ketone-formaldehyde-condensates, and copolymers comprising sulfo group containing units and/or sulfonate group-containing units.

15. The construction chemical composition of claim 12, wherein the additive is selected from the group consisting of essentially aluminate-free cement, fillers, and aggregates or a mixture of two or more thereof.

16. The construction chemical composition of claim 12, wherein the inorganic carbonate is an alkali metal carbonate or alkaline earth metal carbonate.

17. The construction chemical composition of claim 12, wherein the additive is a hardening retarder.

18. The construction chemical composition of claim 1, wherein the weight ratio of the inorganic binder to the bisulfite adduct is in the range from 10:1 to 10000:1.

19. The construction chemical composition of claim 1, wherein the weight ratio of the inorganic binder to the bisulfite adduct is in the range from 1:10 to 1:10000.

20. A building product, comprising the construction chemical composition of claim 1.

21. The building product of claim 20, wherein a weight ratio of the inorganic binder to the bisulfite adduct is in the range from 10:1 to 1000:1.

Description

EXAMPLE 1: MORTAR COMPOSITION WITH IMPROVED FLOW PROPERTIES AND SUFFICIENT 24 H STRENGTH

(1) The cement mortar investigated was composed by 25 wt.-% inorganic binder and 75 wt.-% norm sand (according EN 196-1).

(2) Cement 1 was mixed with 10 wt.-% sodium carbonate. The resulting mixture was used as inorganic binder in experiments V1, V2, and V3.

(3) For experiments V4, V5, and V6 cement 2 was used as inorganic binder.

(4) The water/inorganic binder ratio was 0.5. The retarder (inventive or comparative) was added in powdered form in an amount of 0.5 wt.-% by weight of inorganic binder (summarized in Table 1).

(5) The production of the cement mortar was done according to EN. 196-1:2005 in a mortar mixer with a batch volume of 5 L. The inorganic binder, the additive (if used), and water were placed into the mixing vessel and the mixing was started at 140 rpm of the mixer: After 30 s of mixing the norm sand was added slowly during 30 s. After complete addition of the norm sand the mixer speed was set to 285 rpm and mixing was continued for another 30 s. After that step the mixing was stopped for 90 s. Within the first 30 s of this break of mixing the mortar attached to the wall of the vessel was removed and given to the mortar again. After the break of 90 s the mixing was continued at a mixer speed of 285 rpm. The total mixing time was 4 minutes.

(6) The spread of the mortar was determined according to EN 1015-3 directly after the end of mixing (value at 4 min) and 15 minutes after the beginning of mixing (value at 15 min). The results are given in table 1.

(7) TABLE-US-00002 TABLE 1 Additive Spread (cm) Strength after 24 h.sup.1) Mortar Type no. 4 min 15 min BS (MPa) CS (MPa) V1 Ref 10.0 10.0 n.d. n.d. V2 Inv 1 21.8 21.0 4.4 15.8 V3 Ref 2 20.9 21.0 1.1 3.5 V4 Ref 19.5 17.0 4.5 19.4 V5 Inv 1 21.3 21.2 2.8 11.6 V6 Ref 2 10.0 10.0 0.9 2.8 BS-bending strength, CS-compressive strength, n.d.-not determinable .sup.1)determined as described in EN 196-1:2005

(8) The results demonstrate the advantage of the additive 1 (according to the invention) in comparison to tartaric acid (prior art): In experiments V1 to V3 using cement 1 both additives provide a strong increase of the spread whereas the strength is much higher after 24 h when using additive 1 (according to the invention).

(9) When using cement 2 (experiments V4 to V6) additive 1 strongly increases the spread whereas the use of tartaric acid results in a stiffening of the mortar. Furthermore, the use of additive 1 significantly improves the 24 h strength compared to the use of tartaric acid.

EXAMPLE 2

(10) The following experiments were carried out:

(11) For experiments 1-21 cement 2 was used as inorganic binder and as filler norm sand was used. The cement mortar investigated was composed with a sand/cement ratio of s/c=2.2. The water/inorganic binder ratio was 0.42. The additive (inventive or comparative) was added in powdered form in an amount by weight of inorganic binder summarized in Table 2. Mixing procedure was according to example 1. Components, dosages and water/cement ratios (W/C) are given in table 2. The results of the mortar test are given in table 3.

(12) TABLE-US-00003 TABLE 2 Disper- Addi- Additional sant Dos tive Dos Additional Dos dispersant Dos Exp. no. [%] no. [%] additive [%] no. [%] W/C 1 2 0.04 1 0.25 Propylene carbonate 0.25 1 0.125 0.42 2 2 0.04 1 0.25 Ethylenecarbonate 0.25 1 0.125 0.42 3 2 0.04 1 0.25 Glycerol carbonate 0.25 1 0.125 0.42 4 2 0.07 1 0.25 Sodium carbonate 0.50 1 0.125 0.42 5 2 0.04 1 0.25 Boric acid 0.25 1 0.125 0.42 6 3 0.04 1 0.25 Propylene carbonate 0.25 1 0.125 0.42 7 4 0.04 1 0.25 Propylene carbonate 0.25 1 0.125 0.42 8 5 0.04 1 0.25 Propylene carbonate 0.25 1 0.125 0.42 9 5 0.40 0 0 0 0 0 0 0.42 10 2 0.23 0 0.00 0 0.00 0 0. 0.42 11 2 0.04 1 0.25 Tartaric acid 0.25 1 0.125 0.42 12 2 0.04 1 0.25 HEDP 0.25 1 0.125 0.42 13 2 0.04 1 0.25 Citric acid 0.25 1 0.125 0.42 14 2 0.04 1 0.25 Sodium Gluconate 0.25 1 0.125 0.42

(13) TABLE-US-00004 TABLE 3 Results of mortar tests: Spread cm 24 h Strength Experi- 4 10 30 60 [MPa] ment min min min min bending compressive 1 28.3 27.3 25 20.2 3.17 15.08 2 27.8 26.3 22.5 17.1 3.20 16.43 3 28.3 27.8 27.6 18.2 3.58 19.41 4 23.1 24.6 25.3 solid 3.90 19.63 5 24.7 24.8 25.5 22.4 0.80 11.57 6 27.4 27.1 21.7 18.7 2.80 14.46 7 27.6 27.8 25.4 18.8 3.19 16.18 8 27.5 27.1 21.7 19.1 2.97 16.91 9 25.3 26.4 26.5 25.5 2.10 11.95 10 23.9 20.8 17.8 17.3 4.94 18.82 11 22.7 23.3 24.6 23.9 1.03 3.00 12 20.1 19.1 18.6 17.4 n.d. n.d. 13 25.9 25.9 23.7 solid 2.16 11.38 14 28.2 27.6 27.4 27.1 n.d. n.d.

EXAMPLE 3

(14) The strength development within the first day was determined in the composition of experiments 1 and 10 of example 2 (EXP 1 and 10) using cement 3 instead of cement 2. The results are given in table 4.

(15) TABLE-US-00005 TABLE 4 Spread Compressive [cm] after strength [MPa] 40 min 50 min 4 h 6 h 1 d 7 d EXP 1 0 2.5 5.4 5.7 33.4 62.5 EXP 10 0 0 0 0.975 42.5 61.5

(16) The inventive additive (EXP 1) results in an improved early strength formation especially in a time period below 24 hours whereas the mixture without the inventive additive shows a very slow strength formation in the comparable time period.

EXAMPLE 4

(17) For experiments 15-18 cement 2 was used as inorganic binder. The cement mortar investigated was composed with a sand (norm sand)/cement ratio of s/c=2.2. The water/inorganic binder ratio was 0.42. The additive (inventive or comparative) was added in powdered form in an amount by weight of inorganic binder summarized in Table 5. Mixing procedure was according to example 1. Components and dosages are given in table 5. The results of the mortar test are given in table 6.

(18) TABLE-US-00006 TABLE 5 Experiment Dispersant Additive 15 PNS 1% 16 PNS 0.3% 0.3% 17 Ligninsulfonate 1.1% 18 Ligninsulfonate 0.5% 0.3% PNS: Polynaphthalene sulfonate (Melcret 500, available from BASF Construction Solution GmbH);

(19) The used additive was additive 1, ethylene carbonate and dispersant 1 in the weight ratio of 1:1:0.5.

(20) TABLE-US-00007 TABLE 6 Compressive Spread [cm] after Initial strength Experi- 10 20 30 60 Set [MPa] ment min min min min [min] 1 d 15 25.5 24.9 24.6 22.4 465 23 16 25.7 24.9 23.3 68 28 17 17.8 18.5 18.6 16.7 787 12 18 20.4 20.8 22.3 71 19

(21) From the results can be seen that the addition of the additive of the invention provides sufficient open time, an early setting and high 1d strength.

EXAMPLE 5

(22) The experiments in this example illustrate the use of the additive of the invention in different cementitious systems containing limestone powder or slag.

(23) The cement mortar investigated was composed of 25 wt.-% inorganic binder and 75 wt.-% norm sand (according EN 196-1). For experiments 19, 20 and 23, a binder mixture of 35% of Portland Cement (CEM I 42,5R) and 65% of ground slag (Blaine 4000) was used. For experiments 21, 22 and 24, a mixture of 70% Portland Cement (CEM I 42,5R) and 30% limestone powder was used. Components, dosages and water/cement ratios (WIC) are given in table 7. The results of the mortar tests are given in table 8.

(24) TABLE-US-00008 TABLE 7 Additional Dispersant Dos Additive Dos Additional Dos dispersant Dos Exp. no. [%] no. [%] additive [%] no. [%] W/C 19 2 0.04 1 0.11 Ethylene 0.11 1 0.075 0.42 carbonate 20 2 0.142 . 0.00 0.000 0.42 21 2 0.04 2 0.11 Ethylene 0.11 1 0.075 0.42 carbonate 22 2 0.15 . . 0.000 0.42 23 2 0.04 1 0.11 Sodium 0.25 1 0.075 0.42 carbonate 24 2 0.04 1 0.11 Sodium 0.25 1 0.075 0.42 carbonate

(25) TABLE-US-00009 TABLE 8 Spread in cm after Compressive strength MPa 10 20 30 60 Initial 1 d 2 d 7 d 28 d min min min min Set [min] strength strength strength strength 19 25.5 24.9 24.9 51 2 13 32 62 20 25.7 18.0 17.1 598 13 31 61 21 23.4 23.3 49 13 39 50 22 23.7 18.7 301 13 39 50 23 25.5 25.8 23 1 14 31 51 24 25.4 25.3 27.3 88 13 39 50

EXAMPLE 6 (COMPARATIVE EXPERIMENTS)

(26) The experiments were designed to provide a comparison with the use of the bisulfite adduct of glyoxal as described in JP S546013 A1 and FR 2 471 955 A1. The composition of the tested mortar mixtures is given in table 9. The dosage of the additive 1 was adapted to achieve in mixture CR4 an initial stiffening time (100 g cone) of 60 min15 min. This identified dosage of additive 1 was then used for all other mixtures to identify the effect of the different additives at constant dosage.

(27) For characterization of the mortars the parameters were determined as follows: 1. The setting time was determined according to the standard DIN EN 196-3. Begin of setting and final setting was determined with a 100 g cone (0.5 mm.sup.2) at 23 C./50% relative humidity. The setting time is difference between finale setting and initial setting. 2. Compressive strength: Fresh mortar is filled into a polystyrene form to produce 4416 cm mortar prisms: The form is covered and stored at 23 C./50% relative humidity for the desired time after which the compressive strength is to be determined: The compressive strength is then measured on the prisms, for example after 24 h.

(28) TABLE-US-00010 TABLE 9 Mortar Composition (values in wt.-% by weight of the sum of mortar components) Experiment CR1 CR2 CR3 CR4 CR5 CR6 CR7 Type Ref. Inv. Comp Inv. Comp Inv. Comp Composition Cement 4 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Quartz sand 0.3-1.0 mm 69.92 69.90 69.90 69.89 69.89 69.86 69.86 Limestone Powder.sup.1) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Cellulose Ether.sup.2) 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Foaming agent.sup.3) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ethylene Carbonate 0.17 0.17 Sodium Carbonate 0.4 0.4 Additive 1 0.17 0.17 0.17 Additive 3 0.17 0.17 0.17 Sum mortar component 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Water 15.5 15.5 15.5 15.5 15.5 15.5 15.5 .sup.1)Omyacarb 15 AL (Omya) .sup.2)Methylcellulose Culminal C 4053 (Ashland) .sup.3)Loxanol K12P (BASF)

(29) TABLE-US-00011 TABLE 10 Results of mortar test Experiment CR1 CR2 CR3 CR4 CR5 CR6 CR7 Type Ref. Inv Comp Inv Comp Inv Comp Initial Setting (min) 234 29 572 74 32 52 109 Final Setting (min) 474 682 n.m. 154 735 113 4023 Setting time (min) 240 653 >3500 80 703 61 3914 Compressive strength (in MPa) After 24 h 1.7 1.1 n.m. 2.1 n.m. 2.4 n.m. n.m.-not measureable (prism was too soft for measurement or was broken before measurement).

(30) CR2 (inventive) shows an early initial setting whereas CR3 (comparative, prior art) shows strong retardation of initial setting which is not the target of the invention. CR3 shows no final setting within 8 hours in opposite to CR2 where the final setting is only-slightly retarded compared to the reference. The examples of the invention show that the addition of the additive of the invention (CR2, CR4, CR6) provides a sufficient open time and a short setting time whereas comparative samples show a significant longer setting time. Additionally all mortars containing inventive additive 1 show a compressive strength after 24 h whereas the compressive strength of all comparative examples with additive 2 could not be determined (prism where to soft and could not be measured).

EXAMPLE 7: SELF LEVELLING UNDERLAYMENT (SLU)

(31) TABLE-US-00012 TABLE 11 Components used in SLU mortar Type Component Supplier Binder Fondu (High Alumina Cement, HAC) Kerneos Binder -hemihydrate Knauf Binder Cement A (Ordinary Portland Cement), HeidelbergCement CEM I 52.5N, Blaine value: 4100 cm.sup.2/g AG Filler Quartz sand H33 Quarzwerke Frechen Filler Limestone powder (Omyacarb 15 AL) Omya Additive Sodium Carbonate (Soda light) BASF Additive Diutan Gum (Vicosity modifying agent) CP Kelko Additive Defoamer (Vinapor DF 9010) BASF Construction Solutions GmbH Additive redispersible polymer powder (ethylene- Wacker vinylacetate polymer) (Vinnapas 5028 E)

(32) The constructions chemical composition according to the invention was used for a composition of a self levelling underlayment (SLU). The compositions of the different mortars are summarized in table 12:

(33) The water content relates to the total sum of mortar components given in table 12.

(34) The dry compositions given in table 12 were mixed with the amount of water (given in table 12) according to EN 1937 (mixing procedure with waiting time).

(35) TABLE-US-00013 Mixing procedure: (Mortar mixer according EN196-1) Time after start Duration Description 0 00 0 00-0 20 20 s Addition of powder and dispersants to the water 0 20-1 20 60 s Stirring (140 U/min) 1 20-1 40 20 s Clean mixer and bowl 1 40-2 40 60 s Stirring (285 U/min) 2 40-7 40 300 s Ripening time 7 40-7 55 15 s Stirring (285 U/min)

(36) Production Additive CP1 (According to the Invention):

(37) Cement A, Dispersant 1, Dispersant 4, Additive 1 and sodium carbonate were mixed together in amounts according to table 12 in a knife mill GrindoMix GM 200 (Retsch) for 1 min at 3000 rpm.

(38) TABLE-US-00014 Component Weight (g) Cement A 25.94 Dispersant 1 7.78 Dispersant 4 14.41 Additive 1 28.82 Sodium Carbonate 23.05

(39) The constituents of the tested compositions are given in table 12 and the test results are given in table 13.

(40) TABLE-US-00015 TABLE 12 Mortar composition for a SLU composition (values are given in wt.-% by weight of the sum of mortar components). Composition SLU1 SLU2 SLU3 Type Comp Inv Ref Component (%) (%) (%) Cement A 31.59 31.50 31.59 Fondu (HAC) 3.51 3.51 3.51 -hemihydrate 1.4 1.4 1.4 Limestone powder 19.23 19.23 19.23 Quartz sand H33 41.90 41.98 41.98 Latex Powder 2 2 2 Dispersant 1 0.050 0.050 Dispersant 2 0.027 0.027 Sodium Carbonate 0.1 0.1 Additive CP1 0.347 Additive 2 (tartaric 0.1 acid) Diutan Gum 0.04 0.04 0.04 Defoamer (Vinapor 0.064 0.064 0.064 DF9010) Sum mortar 100 100 100 components Water 20 20 20

(41) TABLE-US-00016 TABLE 13 Results of mortar testing of compositions from table 11 Composition SLU1 SLU2 SLU3 Test method Unit Inv Ref Ref Flow after (according to DIN EN 12706) 8 min cm 15.9 15.8 8 15 min cm 15.3 15.2 5.2 30 min cm 13.7 13 45 min cm 7.0 10.5 60 min cm 3.0 6.4 Setting (according to DIN EN 196-3) Initial Setting min 114 113 91 Final Setting min 152 141 176 Shore D (according to DIN 53505) 3 h 8 13 0 4 h 16 17 10 5 h 20 23 13 6 h 23 25 16 7 h 26 27 21 Compressive strength after (according to DIN EN 196-1) 1 d MPa 10.9 10.3 13.1

(42) The additive CP1 used in SLU2 contains the bisulfite adduct according to the invention. Compared to the reference SLU1 in mortar SLU2 shows a longer constant flow over time which is the main benefit. SLU2 shows an improved early strength development (Shore D value) compared to SLU1. SLU3 is a comparative formulation without use of any additive influencing the hydration of the cementitious material. SLU3 shows a bad flow behavior over time and Shore D development compared to SLU2.