MONO- AND BISALKYLENETRIALKOXYSILANE DISPERSANTS FOR HYDRAULIC BINDERS

Abstract

The present invention relates to mono- and bisalkylenetrialkoxysilanes of the general formula (I),

##STR00001## in which: —Y— is —O— or —N(R.sup.9).sub.2-a—; —Z— is in each case identical or different and selected from the group consisting of —O— and —CHR.sup.4b—; a is 1 if —Y—=—O—; and is 1 or 2 if —Y—=—N(R.sup.9).sub.2-a—; m is a natural number from 1 to 20; n is a natural number from 7 to 200; R.sup.1 is in each case identical or different and selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and phenyl; and R.sup.2, R.sup.3, R.sup.4a, R.sup.4b, R.sup.5, R.sup.6, R.sup.7R.sup.8, and R.sup.9 in each case independently are H, suitable linear or branched C.sub.1-C.sub.20-alkyl, or optionally C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.1-C.sub.20-alkanoyl, C.sub.3-C.sub.20-alkenoyl, ω-carboxy-(C.sub.1-C.sub.6-alkyl)carbonyl, and ω-carboxy-(C.sub.2-C.sub.6-alkenyl)carbonyl and/or C.sub.7-C.sub.20-aryloyl;
to processes for preparing them and to their use as dispersants in aqueous suspensions composed of aggregates and hydraulic binders; and to these aqueous suspensions as such.

Claims

1: A mono- or bisalkylenetrialkoxysilane of the formula (I): ##STR00027## wherein: —Y— is —O— or —N(R.sup.9).sub.2-a—; —Z— is in each case identical or different and selected from the group consisting of —O— and —CHR.sup.4b—; a is 1 if —Y—=—O—, and is 1 or 2 if —Y—=—N(R.sup.9).sub.2-a—; m is a natural number from 1 to 20; n is a natural number from 7 to 200; R.sup.1 is in each case identical or different and selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and phenyl; R.sup.2, R.sup.3, R.sup.4a and R.sup.4b are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl, or R.sup.2 together with R.sup.4a forms an alkylene chain —R.sup.2—R.sup.4a—, the alkylene chain being selected from the group consisting of —C(R.sup.5).sub.2—C(R.sup.5).sub.2— and —C(R.sup.5).sub.2—C(R.sup.5).sub.2—C(R.sup.5).sub.2—, and R.sup.3 and R.sup.4b are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl, or R.sup.2 together with R.sup.4b forms an alkylene chain —R.sup.2—R.sup.4b—, the alkylene chain being selected from the group consisting of —C(R.sup.5).sub.2— and —C(R.sup.5).sub.2—C(R.sup.5).sub.2—, and R.sup.3 and R.sup.4a are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl; R.sup.5 is in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.6-alkyl; R.sup.6 is in each case identical or different and selected from the group consisting of H, methyl, and ethyl; R.sup.7 is selected from the group consisting of linear or branched C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkanoyl, and C.sub.7-C.sub.20-aryloyl; and R.sup.8 and R.sup.9 are in each case identical or different and selected from the group consisting of H, linear or branched C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.1-C.sub.20-alkanoyl, C.sub.3-C.sub.20-alkenoyl, and also co-carboxy-(C.sub.1-C.sub.6-alkyl)carbonyl and salts thereof, ω-carboxy-(C.sub.2-C.sub.6-alkenyl)carbonyl and salts thereof, and C.sub.7-C.sub.20-aryloyl.

2: The alkylenetrialkoxysilane according to claim 1, wherein: —Z—=—O—; and R.sup.2, R.sup.3, and R.sup.4a are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl.

3: The alkylenetrialkoxysilane according to claim 1, wherein: m=3; and R.sup.5=H.

4: The alkylenetrialkoxysilane according to claim 1, wherein: —Z— is —CHR.sup.4b; and R.sup.2 together with R.sup.4b forms an alkylene chain —R.sup.2—R.sup.4b—, the alkylene chain being selected from —C(R.sup.5).sub.2— and —C(R.sup.5).sub.2—C(R.sup.5).sub.2—; and R.sup.3 and R.sup.4a are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl.

5: The alkylenetrialkoxysilane according to claim 1, wherein the alkylenetrialkoxysilane has the formula (I-d11): ##STR00028## wherein Y, a, n, R.sup.1, and R.sup.6 to R.sup.9 have the definition indicated in claim 1.

6: The alkylenetrialkoxysilane according to claim 1, wherein: —Y—=—N(R.sup.9).sub.2-a—; and a=1 or 2.

7: The alkylenetrialkoxysilane according to claim 1, wherein: —Y—=—O—; and a=1.

8: The alkylenetrialkoxysilane according to claim 1, wherein R.sup.8=H.

9: The alkylenetrialkoxysilane according to claim 1, wherein R.sup.8 is selected from the group consisting of a carboxy-(C.sub.1-C.sub.6-alkyl)carbonyl and a carboxy-(C.sub.2-C.sub.6-alkenyl)carbonyl.

10: The alkylenetrialkoxysilane according to claim 1, wherein n is a natural number from 21 to 120.

11: The alkylenetrialkoxysilane according to claim 1, wherein R.sup.6=H.

12: The alkylenetrialkoxysilane according to claim 1, wherein R.sup.7 is selected from the group consisting of methyl and acetyl.

13: A process for forming an aqueous suspension, the process comprising adding a dispersant to a mixture comprising an aggregate and a hydraulic binder, to obtain the aqueous suspension, wherein the dispersant is at least one alkylenetrialkoxysilane of claim 1.

14: The process according to claim 13, wherein the hydraulic binder is selected from the group consisting of a cement and a geopolymeric silicate binder.

15: An aqueous suspension, comprising: an aggregate; a hydraulic binder; and a dispersant comprising the alkylenetrialkoxysilane according to claim 1.

16: A process for preparing the alkylenetrialkoxysilane according to claim 1, the process comprising: (i) β-hydroxyalkylating a polyether alcohol or polyether amine of formula (II): ##STR00029## with one or more epoxy silanes of formula (III): ##STR00030## to form an alkylenetrialkoxysilane of formula (I-a), ##STR00031## and (ii) optionally acylating or alkylating the hydroxy functionality formed in step (i) and, optionally, the secondary amine function of the alkylenetrialkoxysilane of formula (I-a), with an acylating agent selected from the group consisting of a carbonyl chloride of formula R.sup.8Cl, a carboxylic anhydride of formula (R.sup.8).sub.2O, in which R.sup.8 is C.sub.1-C.sub.20-alkanoyl, C.sub.3-C.sub.20-alkenoyl, or C.sub.7-C.sub.20-aryloyl, a cyclic carboxylic anhydride of formula (IV-b 1), and a cyclic carboxylic anhydride of formula (IV-b2): ##STR00032## or with an alkylating agent selected from the group consisting of R.sup.8X, in which R.sup.8 is C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, or C.sub.2-C.sub.20-alkynyl and X is Cl, Br, I, OS(═O).sub.2CF.sub.3 (trifluoromethanesulfonate), OS(═O).sub.2CH.sub.3 (methanesulfonate), or toluenesulfonate, wherein: —Y— is —O— or —N(R.sup.9).sub.2-a—; —Z— is in each case identical or different and selected from the group consisting of —O— and —CHR.sup.4b—; a is 1 if —Y—=—O—, and is 1 or 2 if —Y—=—N(R.sup.9).sub.2-a—; m is a natural number from 1 to 20; n is a natural number from 7 to 200; R.sup.1 is in each case identical or different and selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and phenyl; R.sup.2, R.sup.3, R.sup.4a and R.sup.4b are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl, or R.sup.2 together with R.sup.4a forms an alkylene chain —R.sup.2—R.sup.4a, the alkylene chain being selected from the group consisting of —C(R.sup.5).sub.2—C(R.sup.5).sub.2— and —C(R.sup.5).sub.2—C(R.sup.5).sub.2—C(R.sup.5).sub.2—, and R.sup.3 and R.sup.4b are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl, or R.sup.2 together with R.sup.4b forms an alkylene chain —R.sup.2—R.sup.4b-, the alkylene chain being selected from the group consisting of —C(R.sup.5).sub.2— and —C(R.sup.5).sub.2—C(R.sup.5).sub.2—, and R.sup.3 and R.sup.4a are in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.10-alkyl R.sup.5 is in each case identical or different and selected from the group consisting of H and linear or branched C.sub.1-C.sub.6-alkyl; R.sup.6 is in each case identical or different and selected from the group consisting of H, methyl, and ethyl; and R.sup.7 is selected from the group consisting of linear or branched C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkanoyl, and C.sub.7-C.sub.20-aryloyl; and R.sup.9 is selected from the group consisting of H, linear or branched C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl, C.sub.1-C.sub.20-alkanoyl, C.sub.3-C.sub.20-alkenoyl, and also ω-carboxy-(C.sub.1-C.sub.6-alkyl)carbonyl and salts thereof, ω-carboxy-(C.sub.2-C.sub.6-alkenyl)carbonyl and salts thereof, and C.sub.7-C.sub.20-aryloyl.

Description

EXAMPLES

Example 1: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the Formula (I-a1)

Pluriol®A 1020 E-Amine:

[0094] ##STR00014##

[0095] 50.0 g (50 mmol, M=1000 g/mol) of Pluriol®A 1020 E-Amine (polyoxyethylenamine mixture having an average number of oxyethylene units of 22) are placed in a predried 100 mL three-neck flask and heated to 70° C. in a nitrogen atmosphere. Then 24.82 g (105 mmol, M=236.34 g/mol) of glycidyloxypropyltrimethoxysilane are added with stirring and the reaction mixture is stirred further at 100° C. At time intervals of 2 hours, the progress of the reaction is ascertained by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1; Rf (Pluriol®A 1020 E-Amine)=0.1, Rf (glycidyloxypropyltrimethoxysilane)=0.74, Rf (intermediate with a silane head group)=0.3, Rf (product)=0.5). After 4 hours, all of the Pluriol®A 1020 E-Amine has reacted, and the reaction is ended.

##STR00015##

[0096] pH (5% in water): 7

[0097] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.2 ppm, broad s, 2H, OH; 2.5-2.9 ppm, m, 6H, CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.8 ppm, m, 94H, O—CH.sub.2—CH.sub.2—O/CHOH; 3.5-3.6 ppm, m, 18H, Si—O—CH.sub.3.

Example 2: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetriethoxysilane of the Formula (I-a2)

[0098] ##STR00016##

[0099] 40.0 g (40 mmol, M=1000 g/mol) of Pluriol®A 1020 E-Amine are placed in a predried 100 mL three-neck flask and heated to 70° C. in a nitrogen atmosphere. Then 23.4 g (82 mmol, M=278.4 g/mol) of glycidyloxypropyltrimethoxysilane are added with stirring and the reaction mixture is stirred further at 100° C. At time intervals of 2 hours, the progress of the reaction is ascertained by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1; Rf (Pluriol®A 1020 E-Amine)=0.1, Rf (glycidyloxypropyltrimethoxysilane)=0.74, Rf (intermediate with a silane head group)=0.3, Rf (product)=0.5). After 8 hours, all of the Pluriol®A 1020 E-Amine has reacted.

[0100] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 1.2 ppm, t, 18H, Si—O—CH.sub.2—CH.sub.3; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.5-2.9 ppm, m, 6H, CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.6 ppm, m, 10H, CH.sub.2—O; 3.6-3.7 ppm, m, 82H, O—CH.sub.2—CH.sub.2—O; 3.8 ppm, m, 14H, Si—O—CH.sub.2—CH.sub.3/CH—OH.

Example 3: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the Formula (I-a3)

Pluriol®A 2010 E-Amine:

[0101] ##STR00017##

[0102] 100.0 g (50 mmol, M=2000 g/mol) of Pluriol®A 2010 E-Amine (polyoxyethylenamine mixture having an average number of oxyethylene units of 45) are placed in a predried 250 mL four-neck flask and heated to 70° C. in a nitrogen atmosphere. Then 24.8 g (103 mmol, M=236.3 g/mol) of glycidyloxypropyltrimethoxysilane are added with stirring and the reaction mixture is stirred at 120° C. for 8 hours and at 140° C. for a further 7 hours. At time intervals of 3 hours, the progress of the reaction is ascertained by thin-layer chromatography. After 15 hours, Pluriol®A 1020 E-Amine has completely reacted.

##STR00018##

[0103] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.2 ppm, broad s, 2H, OH; 2.5-2.9 ppm, m, 6H, CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.8 ppm, m, 188H, O—CH.sub.2—CH.sub.2—O and CHOH; 3.5-3.6 ppm, m, 18H, Si—O—CH.sub.3.

Example 4: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the Formula (I-a4)

[0104] 100.0 g (50 mmol, M=2000 g/mol) of Pluriol®A 2010 E-Amine are placed in a predried 250 mL four-neck flask and heated to 80° C. in a nitrogen atmosphere. Then first 0.05 g (2.5 mmol; M=18 g/mol) of deionized water and subsequently 24.8 g (103 mmol, M=236.3 g/mol) of glycidyloxypropyltrimethoxysilane are added with stirring. The reaction mixture is heated to 100° C. and stirred at this temperature for 1 hour. The temperature is then raised to 140° C., stirring is carried out at this temperature for 9 hours, and a further 0.05 g of deionized water is added. After a further 2 hours, the reaction is ended.

##STR00019##

[0105] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.2 ppm, broad s, 2H, OH; 2.5-2.9 ppm, m, 6H, CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.9 ppm, m, 188H, O—CH.sub.2—CH.sub.2—O and CHOH; 3.5-3.6 ppm, m, 18H, Si—O—CH.sub.3.

Example 5: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of Formula (I-a5)

[0106] 50.0 g (50 mmol, M=1000 g/mol) of Pluriol®A 1020 E-Amine are placed in a predried 100 mL three-neck flask and heated to 80° C. in a nitrogen atmosphere. Then 12.4 g (52 mmol, M=236.3 g/mol) of glycidyloxypropyltrimethoxysilane are added with stirring. The reaction mixture is heated to 140° C. and stirred at this temperature for 12 hours. Every 4 hours, the progress of the reaction is monitored by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1). A skin is formed on the mixture. After 12 hours, the reaction is ended.

##STR00020##

[0107] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.8 ppm, m, 2H, CH.sub.2—CH.sub.2—Si; 1.60-1.80 ppm, m, 2H, CH.sub.2—CH.sub.2—Si; 2.5-2.9 ppm, m, 4H, CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.9 ppm, m, 95H, O—CH.sub.2—CH.sub.2—O and CHOH; 3.5-3.6 ppm, m, 18H, Si—O—CH.sub.3.

Example 6: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the Formula (I-b1)

[0108] 15.0 g (10.2 mmol, M=1472.7 g/mol) of the crude product obtained in example 1 of (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the formula (I-a1) are placed in a predried 100 mL three-neck flask and heated to 40° C. under reduced pressure. After 30 minutes, the formation of bubbles is no longer observed. Then 2.1 g (20.9 mmol, M=98 g/mol) of maleic anhydride are added and the resulting reaction mixture is heated to 70° C. in a nitrogen atmosphere and stirred at this temperature. The progress of the reaction is monitored by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1). After 2 hours, all of the starting material has reacted, and the reaction is ended.

##STR00021##

[0109] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.2 ppm, broad s, 1H, OH; 2.5-2.9 ppm, m, 6H, CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.8 ppm, m, 94H, O—CH.sub.2—CH.sub.2—O; 3.5-3.6 ppm, m, 18H, Si—O—CH.sub.3; 4.2-4.4 ppm, m, 2H, CHOC(═O); 6.2 ppm, d, 2H, CH—C(O)OH; 6.4 ppm, d, 2H, CH—C(═O)O—C.

Example 7: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetriethoxysilane of the Formula (I-b2)

[0110] 25.0 g (16.1 mmol, M=1556.8 g/mol) of the (polyoxyethylene)amino-bis-alkylenetriethoxysilane of the formula (I-a2) obtained from example 2 are placed in a predried 100 mL three-neck flask and heated to 70° C. under reduced pressure. When the alkylenetriethoxysilane of the formula (I-a2) has liquefied, 3.37 g (33.0 mmol, M=100 g/mol) of succinic anhydride are added and the resulting reaction mixture is stirred at 70° C. in a nitrogen atmosphere. The progress of the reaction is monitored by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1). After 2 hours, all of the starting material has reacted, and the reaction is ended.

##STR00022##

[0111] pH (5% in water): 4-5

[0112] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 1.2 ppm, t, 18H, Si—O—CH.sub.2—CH.sub.3; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.55-2.65 ppm, m, 8H, CH.sub.2—CO.sub.2; 2.7-2.8 ppm, m, 6H, CH.sub.2—N; 3.35 ppm, s, 3H, O—CH.sub.3; 3.4-3.7 ppm, m, 94H, CH.sub.2—O; 3.8 ppm, q, 12H, Si—O—CH.sub.2—CH.sub.3; 5.1 ppm, m, 2H CHOC(═O); 8-9 ppm, broad s, 2H, COOH.

Example 8: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetriethoxysilane of the Formula (I-b6)

[0113] 21.1 g (13.7 mmol, M=1556.8 g/mol) of the (polyoxyethylene)amino-bis-alkylenetriethoxysilane of the formula (I-a2) obtained from example 2 are placed in a predried 100 mL three-neck flask and heated to 70° C. When the alkylenetriethoxysilane of the formula (I-a2) has liquefied, 2.8 g (28.0 mmol, M=98 g/mol) of maleic anhydride are added and the resulting reaction mixture is stirred at 70° C. in a nitrogen atmosphere. The progress of the reaction is monitored by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1). After 4 hours, all of the starting material has reacted, and the reaction is ended.

##STR00023##

[0114] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 1.2 ppm, t, 18H, Si—O—CH.sub.2—CH.sub.3; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.3-2.8 ppm, m, 6H, CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.7 ppm, m, 90H, CH.sub.2—O; 3.8 ppm, q, 12H, Si—O—CH.sub.2—CH.sub.3; 4.2-4.3, m, 2H, HCOC(═O); 6.2 d, CH—C(O)OH, 6.4, d, CH—C(═O)O—C; 10-11 ppm, broad s, 2H, COOH.

Example 9: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the Formula (I-b3)

[0115] 50.0 g (20.2 mmol, M=2472.6 g/mol) of the (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the formula (I-a3) obtained from example 3 are placed in a predried 250 mL four-neck flask and heated to 80° C. When the alkylenetrimethoxysilane of the formula (I-a3) has liquefied, 4.25 g (41.4 mmol, M=100 g/mol) of succinic anhydride are added and the resulting reaction mixture is stirred at 80° C. in a nitrogen atmosphere. The progress of the reaction is monitored by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1). After 6 hours, all of the starting material has reacted, and the reaction is ended.

##STR00024##

[0116] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H CH.sub.2—CH.sub.2—Si; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.5-2.9 ppm, m, 14H, CH.sub.2—CO.sub.2 and CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.8 ppm, m, 206H, O—CH.sub.2—CH.sub.2—O, Si—OCH.sub.3; 5.1 ppm, m, 2H CHOC(O); 11-12 ppm, broad s, 2H, COOH.

Example 10: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the Formula (I-b3)

[0117] 50.0 g (20.2 mmol, M=2472.6 g/mol) of the (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the formula (I-a4) obtained from example 4 are placed in a predried 250 mL four-neck flask and heated to 80° C. When the alkylenetrimethoxysilane of the formula (I-a4) has liquefied, 4.25 g (41.4 mmol, M=100 g/mol) of succinic anhydride are added and the resulting reaction mixture is stirred at 80° C. in a nitrogen atmosphere. The progress of the reaction is monitored by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1). After 6 hours, all of the starting material has reacted, and the reaction is ended.

[0118] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H CH.sub.2—CH.sub.2—Si; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.5-2.9 ppm, m, 10H, CH.sub.2—CO.sub.2 and CH.sub.2—N; 3.35, s, 3H, O—CH.sub.3; 3.4-3.8 ppm, m, 210H, O—CH.sub.2—CH.sub.2—O, Si—OCH.sub.3 and CH.sub.2—N; 5.1 ppm, m, 2H CHOC(O); 11-12 ppm, broad s, 2H, COOH.

Example 11: Synthesis of Inventive (polyoxyethylene)amino-bis-alkylenetrimethoxysilane of the Formula (I-b5)

[0119] 29.03 g (23.5 mmol, M=1236.3 g/mol) of the (polyoxyethylene)amino-alkylenetrimethoxysilane of the formula (I-a5) obtained from example 5 are placed in a predried 50 mL single-neck flask and heated to 100° C. When the alkylenetrimethoxysilane of the formula (I-a5) has liquefied, 4.7 g (47 mmol, M=100 g/mol) of succinic anhydride are added and the resulting reaction mixture is stirred at 140° C. for 4 hours in a nitrogen atmosphere. The progress of the reaction is monitored by thin-layer chromatography (CHCl.sub.3/MeOH/water 88:11:1). After 4 hours, all of the starting material has reacted, and the reaction is ended.

##STR00025##

[0120] .sup.1H NMR (500 MHz, CDCl.sub.3): δ=0.6-0.7 ppm, m, 4H CH.sub.2—CH.sub.2—Si; 1.65-1.75 ppm, m, 4H, CH.sub.2—CH.sub.2—Si; 2.5-2.9 ppm, m, 8H, CH.sub.2—CO.sub.2; 3.35, s, 3H, O—CH.sub.3; 3.4-3.8 ppm, m, 100H, O—CH.sub.2—CH.sub.2—O, Si—OCH.sub.3 and CH.sub.2—N; 5.1 ppm, m, 1H CHOC(O); 11-12 ppm, broad s, 2H, COOH.

Comparative Example 1: Synthesis of the Polycarboxylate Ether (PCE) (V)

[0121] Sokalan®PA 25 XS: Polyacrylic acid (M=5000 g/mol)

Pluriol®A 1020 E:

[0122] ##STR00026##

[0123] A flask is charged with Sokalan®PA 25 XS (3.0 equivalents, M=5000 g/mol), Pluriol®A 1020 E (1.0 equivalent, M=1000 g/mol), and catalytic amounts of methylsulfonic acid. Then, at a temperature of 175° C. and under a pressure of 20 mbar, the water of condensation liberated during the esterification is removed until thin-layer chromatography indicates full reaction of Pluriol®A 1020 E.

Comparative example 2: Synthesis of (polyoxyalkylene)trioxypropyleneamino-bis-methylene-phosphonic acid (VI)

[0124] The (polyoxyalkylene)trioxypropyleneamino-bis-methylenephosphonic acid (VI) is prepared in accordance with FR 2696736, example 1 b) starting from Jeffamine®M 1000.

Use Examples 12 to 28: Determination of Fresh Mortar Consistency

[0125] First of all a standardized mortar according to DIN EN196-1 is prepared from [0126] 450 g of cement (“Heidelberger Zement” CEM I, 42.5 R), [0127] 1350 g of sand, and [0128] 225 g of deionized water (taking account of the water added subsequently with the plasticizer).

[0129] The mortar components are mixed for 90 seconds, then admixed with an aqueous mixture comprising a plasticizer (0.10 to 0.20 wt %, based on the dry weight of the cement) and Degressal® SD 40 as defoamer (7 wt %, based on the dry weight of the corresponding plasticizer), followed by mixing for a further 60 seconds. The mortar thus produced is introduced in two layers into a truncated cone mold, with each layer of mortar being spread by 10 gentle taps with a pestle in such a way that the truncated cone mold is filled uniformly. Thereafter the projecting mortar is stripped off flush. After 10 to 15 seconds, the slump cone is drawn off slowly upward vertically, and the mortar is caused to slump by 15 reciprocal taps (one reciprocal tap per second). The diameter of the mortar cake is measured at two locations positioned at right angles to one another. The average from these two measurements is reported as the slump flow in table 1.

[0130] Following the measurement, the mortar is removed from the slump board. The test is repeated with the same mortar after 30, 60, 90, 120, and 150 minutes. Slump flows for mortars with different composition, determined in this way, are shown in table 1.

TABLE-US-00001 TABLE 1 wt % based Mortar slump flow [cm] Ex. Admixture.sup.[1] on cement 1 min 30 min 60 min 90 min 120 min 150 min 12 none — 17.7 15.7 15.0 13.4 (comparative) 13 Bis-silane I-a1 0.10 21.5 18.6 17.8 16.6 14 Bis-silane I-a1 0.20 26.7 20.9 19.4 18.0 17.0 15 Bis-silane I-b1 0.10 22.8 19.7 18.1 16.8 16 Bis-silane I-b1 0.20 25.5 22.4 20.0 19.1 17.8 17 Bis-silane I-a2 0.10 21.1 19.8 18.9 18.7 17.3 18 Bis-silane I-a2 0.20 22.3 21.2 21.0 20.2 20.2 19.4 19 Bis-silane I-b2 0.20 25.5 21.6 19.7 18.1 17.7 16.5 20 Bis-silane I-b6 0.20 26.3 21.7 19.7 18.1 17.0 16.0 21 PCE V 0.10 26.1 20.3 18.5 16.0 22 PCE V + 0.08 25.1 19.1 16.3 15.3 Bis-silane I-b2 0.02 23 PCE V + 0.10 26.8 19.4 16.6 15.7 Bis-silane I-b2 0.02 24 Bis-silane I-b3 0.20 26.6 22.3 20.6 19.3 18.4 17.5 25 Bis-silane I-a4 0.20 26.1 21.1 19.2 18.2 18.2 17.3 26 Bis-phosphonic 0.20 22.5 19.0 17.7 16.5 acid VI 27 Monosilane 0.20 24.6 20.8 19.6 18.3 18.1 17.4 I-a5 28 Monosilane 0.20 26.8 20.9 19.0 18.1 17.5 16.9 I-b5 .sup.[1]Admixture additionally contains 7 wt % of Degressal ®SD 40 defoamer, based on the dry weight of the respective plasticizer. .sup.[2]Water/cement value (w/c) = 0.50; ratio of sand to cement = 3.0.

[0131] From the figures in table 1 it is clear that through the addition of the inventive (polyoxyethylene)amino-bis-alkylenetrialkoxysilanes, silanes (I-la), (I-a2), (I-a4), (I-b1), (I-b2), (I-b3), (I-b6), (I-a5), (I-b5) (Ex. 13-20, 24, 25, 27, and 28), success is achieved in plasticizing the mortar to higher slump flow levels.

[0132] Example 12 in table 1 shows, for comparison, the slump flow of the same mortar without addition of plasticizer. As can be seen, the slump flow is initially around 17.7 cm, and then falls back within just 90 minutes to 13.4 cm. The addition of just 0.10 wt %, based on the dry weight of the cement, of one of the inventive bis-silanes (I-a1), (I-a2), or (I-b1) (Ex. 13, 15, 17) results in an increase in the slump flow by around 3 to 5 cm. This can be increased further by raising the amount of plasticizer (see Ex. 14, 16, 18-20, 24, 25, 27, and 28).

[0133] In comparison to the bis-phosphonic acid VI (example 26), the inventive plasticizers produce a greater increase in the slump flow for the same amount (see examples 14, 16, 18-20, 24, 25, 27, and 28).

[0134] In short testing times, the polycarboxylate ether (PCE) V of the comparative example (example 21) is approximately comparable with the inventive plasticizers in relation to the effect of plasticizing the mortar to defined slump flow levels. However, the effect subsides more quickly, and can no longer be determined over 90 minutes.

Use Examples 29 to 45: Determination of Dynamic Viscosity

[0135] For use as intended, a significant part is played not only by the plasticizing effect but also by the lowering of the fresh mortar viscosity. The viscosity is a measure of the flowability and also, in the present context, a measure of the pumpability and workability of the fresh mortar. Lower viscosity levels in this context result in better workability, and more particularly in better pumpability of the fresh mortar. Moreover, the capacity for the fresh mortar to be placed in molds is made easier.

[0136] The viscosity is measured on an Anton Paar MCR 102 rheometer. The mortar used for these measurements is prepared according to DIN EN196-1, as described above. The measuring system used is a specific cell for building materials (BMC-90). The stirrer used is the ST59-2V-44.3/120. 10 measurements are carried out, in each case at a shear rate of 10 s.sup.−1. The measurement time per measurement amounts to 5 seconds. Between the measurements, the system is allowed to stand for 595 seconds without being stirred. The values determined for the dynamic viscosity in this test are shown in table 2

TABLE-US-00002 TABLE 2 Admixture.sup.[1] (wt %, Dynamic viscosity of mortar [mPa .Math. s] Ex. based on cement.sup.[2]) 1 min 10 min 20 min 30 min 40 min 50 min 29 Bis-phosphonic acid VI 86  122 140 153 161 146 (0.20) 30 PCE V (0.10) 1583 3050 12 036   621 605    1 023 167     1 922 460     31 PCE V (0.08) + 94 2650 259 796    682 254    912 002    1 560 932     bis-silane I-b2 (0.02) 32 PCE V (0.10) + 83  87 120 142 196 230 bis-silane I-b2 (0.02) 33 bis-silane I-a1 (0.10) 433 15 022   437 448    821 556    1 012 217     1 811 457     34 bis-silane I-a1 (0.20) 72  81  92 118 115 138 35 bis-silane I-b1 (0.10) 267 14 697   357 544    591 309    1 151 576     1 479 875     36 bis-silane I-b1 (0.20) 40  50  58  65  72  79 37 bis-silane I-a2 (0.20) 471 1027 81 738   394 504    403 734    806 765    38 bis-silane I-b2 (0.20) 130  152 138 172 165 178 39 bis-silane I-b5 (0.20) 92  94 117 136 143 151 40 bis-silane I-b3 (0.20) — — —  50  51  56 41 bis-silane I-a4 (0.20) — — — 244  97  96 42 bis-silane I-a3 (0.20) — — — 102  69  75 43 bis-silane I-b4 (0.20) — — —  38  36  36 44 mono-silane I-a5 (0.20) — — — 194  88 104 45 mono-silane I-b5 (0.20) — — —  73  65  76 Dynamic viscosity of mortar [mPa .Math. s] Ex. 60 min 80 min 90 min 100 min 110 min 120 min 130 min 140 min 150 min 29 146 30 3 104 904     31 2 326 906     32 74 719   747 140    1 238 010     33 3 204 085     34 137 35 2 628 725     36  87 37 1 196 279     38 184 39 161 40  59  71  78 76 82 83 86 85  80 41  96 115 124 114 115 121 119 122 117 42  82  96 104 127 121 130 125 132 143 43  35  38  42 44 46 50 52 54  59 44 121 136 178 111 119 145 157 352 26 785   45 101 195 131 154 137 189 158 291 32 821   .sup.[1]Admixture additionally contains 7 wt % of Degressal ®SD 40 defoamer, based on the dry weight of the respective plasticizer. .sup.[2]Water/cement value (w/c) = 0.50; ratio of sand to cement = 3.0.

[0137] As can be seen from table 2, there is a sharp increase in the dynamic viscosity in a comparatively short time when PEC (V) (example 30) is used in the mortar. This leads to a reduced flowability and ultimately, in particular, to a marked curtailment of the time during which the mortar is workable.

[0138] Above a certain amount, the inventive bis-silanes (I-a1), (I-a3), (I-a4), and (I-b1) to (I-b4) (examples 34, 36, and 38 to 43) bring about a much slower increase in the dynamic viscosity by comparison with PEC (V) (example 30). The viscosity values in this case are mostly below the values reached through the use of the plasticizer bis-phosphonic acid (VI) (example 29).

[0139] Example 31 in table 2 shows that at low levels of addition of the bis-silane, no saving of PCE can be made. However, by a small addition of bis-silane to a PCE added at normal levels, it is possible to achieve a large increase in the viscosity-reducing effect (example 32). This effect, however, is of limited duration. These results suggest that a further prolongation of the desired effect may be achieved by adding the bis-silane at a higher level.

Use Examples 46 to 55: Determination of Flexural Tensile Strength and Compressive Strength

[0140] The mortar for the prism-shaped sample specimens is produced according to DIN EN 196-1, as described above. A difference, however, is that the admixtures are added to the cement directly with the water, before the sand is admixed. For each value to be determined, three mortar prisms are produced, in order to compensate for any measurement uncertainties.

[0141] The prism molds with dimensions of 40×40×160 mm are stretched out on a shaker table. The mortar is then introduced in uniform distribution into the prism molds, and compacted by vibration over a period of 120 seconds (vibration amplitude: 0.7 mm). The molds are then stretched out, and excess mortar is stripped off flush. The molds are covered and stored for 24 hours in accordance with the standard, at 20° C. and an atmospheric humidity of 90%, before demolding. The mortar specimens produced are subsequently demolded and stored further at 20° C. and 90% humidity until immediately prior to the beginning of measurement.

[0142] First of all, three each of the resulting mortar prisms are used to determine the flexural tensile strength. This is followed by measurement of the compressive strength on the six prism halves resulting from the flexural tensile strength determination.

[0143] The flexural tensile strength is determined using a Mega 10-200-10DM1 machine from Form+Test Prüfsysteme.

[0144] Table 3 shows the flexural tensile strength values (average values from three measurements in each case) determined using the mortar prisms.

TABLE-US-00003 TABLE 3 Flexural tensile % by weight based strength [N/mm.sup.2] Ex. Admixture.sup.[1] on cement.sup.[2] 24 h 168 h 336 h 720 h 46 none — 4.39 5.76 6.64 7.02 (comparative) 47 bis-silane I-a1 0.23 0.00 6.92 7.26 7.87 48 bis-silane I-b1 0.23 0.00 7.33 8.02 8.07 49 bis-silane I-a2 0.23 0.00 6.82 7.23 8.10 50 bis-silane I-b2 0.23 0.00 7.05 — — .sup.[1]Admixture additionally contains 7 wt % of Degressal ®SD 40 defoamer, based on the dry weight of the respective plasticizer. .sup.[2]Water/cement value (w/c) = 0.50; ratio of sand to cement = 3.0.

[0145] The compressive strength is determined using a Mega 10-200-10DM1 machine from Form+Test Prüfsysteme.

[0146] Table 4 shows the compressive strength values of the mortars produced (average values from six measurements in each case) determined using the prism halves.

TABLE-US-00004 TABLE 4 Compressive % by weight based strength [N/mm.sup.2] Ex. Admixture on cement 24 h 168 h 336 h 720 h 51 none — 19.90 41.91 46.39 49.98 (comparative) 52 bis-silane I-a1 0.23 0.00 44.62 43.83 48.61 53 bis-silane I-b1 0.23 0.00 45.11 48.81 54.24 54 bis-silane I-a2 0.23 0.00 43.01 48.39 54.45 55 bis-silane I-b2 0.23 0.00 42.10 — —

[0147] As can be seen from tables 3 and 4, both the flexural tensile strength and the compressive strength of the hardened mortar are influenced positively by use of the inventive bis-silanes (I-a2), (I-b1), and (I-b2) (table 3, examples 47 to 50; table 4, examples 52 to 55) after no later than 7 days (168 hours), as shown by the comparison with a mortar having the same composition but without addition of plasticizer (table 3, example 46; table 4, example 51).

Use Examples 56 to 63: Measurement of Heats of Hydration

[0148] The mortar is produced in accordance with DIN EN 196-1, as described above in connection with use examples 46 to 55. Here as well, the admixtures are added right at the start of mortar production, with the water.

[0149] The freshly prepared mortar is placed in each case into a container. A temperature sensor (K-type temperature sensor, B & B Thermo-Technik GmbH) is then mounted in the container. A second container is filled with auxiliary-free mortar and fitted likewise with a temperature probe. The containers are then sealed and are isolated appropriately by application of insulating panels (Basotect®). The temperature is then measured over several hours (Digital 4-Channel Thermometer, Voltcraft; PC Plus software, Voltcraft; K-type temperature sensor, B & B Thermo-Technik GmbH) and a record is made in each case of the time at which the temperature maximum is reached. The difference between the two times (retardation time) is shown in table 5 below.

TABLE-US-00005 TABLE 5 wt %, based on Ex. Admixture.sup.[1] cement.sup.[2] Retardation time [min] 56 bis-silane I-a2 0.20 942 57 bis-silane I-b2 0.20 795 58 bis-silane I-b6 0.20 831 59 bis-silane I-a1 0.20 1077 60 bis-silane I-b1 0.20 639 61 monosilane I-a5 0.20 453 62 monosilane I-b5 0.20 342 63 bis-phosphonic acid VI 0.20 1020 (comparative) .sup.[1]Admixture additionally contains 7 wt % of Degressal ®SD 40 defoamer, based on the dry weight of the respective plasticizer. .sup.[2]Water/cement value (w/c) = 0.50; ratio of sand to cement = 3.0.

[0150] As is clear from the retardation times listed in table 5, the inventive silanes (I-a2), (I-a5), (I-b1), (I-b2), (I-b5), and (I-b6) (examples 56 to 62) retard the development of early strength in the mortar less greatly than the prior-art plasticizer, bis-phosphonic acid (VI).

[0151] In summary, use examples 12 to 63 show that the inventive mono- and bis-silanes (I-a) and (I-b) are of similarly good suitability in the plasticizing of mortar, given a set water/cement ratio, the polycarboxylate ethers frequently employed for this purpose, such as PCE (V), for example. In contrast to the use of polycarboxylate ethers, however, the viscosity of the mortar when using the inventive mono- and bis-silanes (I-a) and (I-b) does not rise nearly as quickly, and this improves the workability of the mortar and, in particular, prolongs the time within which working (pumping, incorporating, spreading) of mortar is possible.