An aqueous, storage-stable composition containing N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxane hydrochlorides, processes for production thereof and use thereof

Abstract

An aqueous composition contains N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxane hydrochlorides, wherein the composition after storage for 6 weeks at 60° C. has a color number of ≤1 Gardner, a content of methanol of ≤0.5% by weight, an active substance content of ≤60% by weight, and a content of water of ≥40% to ≤60% by weight, and wherein the components in the composition sum to 100% by weight.

Claims

1: An aqueous composition, comprising: an active substance comprising N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxane hydrochlorides, wherein the composition after storage for 6 weeks at 60° C. has a color number of ≤1 Gardner, a content of methanol of ≤0.5% by weight, an active substance content of ≤60% by weight, and a content of water of ≥40% to ≤60% by weight, and wherein components in the composition sum to 100% by weight.

2: The composition according to claim 1, wherein the active substance comprises N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxane hydrochlorides as a mixture of isomeric N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxanes, wherein at least one of the isomeric N-benzyl-substituted N-(2-aminoethyl)-3-aminopropylsiloxanes conforms to formula (I);
HO.sub.(1−y)(RO).sub.y[(A)SiO(OH).sub.(1−z)(OR).sub.z].sub.x—R   (I), wherein R represents methyl or ethyl, x≥1, y=0 or 1 and z=0 or 1, with the proviso that (y+z)≤1, and A represents an aminoalkyl group according to formula (II),
[—(CH.sub.2).sub.3N(H.sub.(1−a)R.sup.1.sub.a)(CH.sub.2).sub.2(NH.sub.[2−(b+c)]R.sup.2.sub.bR.sup.3.sub.c)].(HCl).sub.d   (II), where a=0 or 1, b=0 or 1 or c=0 or 1, with the proviso that (b+c)=0, 1, or 2, wherein groups R.sup.1, R.sup.2, and R.sup.3 represent benzyl, and d=0, 1, 2, or 3.

3: The composition according to claim 1, wherein the composition is storage-stable for at least 12 months at room temperature.

4: The composition according to claim 1, wherein the composition is storage-stable for at least 12 months at room temperature and has a color number of ≤1 Gardner, a viscosity of ≥50 to ≤300 mPas at 20° C., and a pH of ≥2 to ≤4.

5: A process for producing the composition according to claim 1, the process comprising: in a process variant A, in step 1 performing a controlled hydrolysis of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane with 1.15 to 1.25 mol of water per mole of Si, at a bottoms temperature of from room temperature to 60° C., in the presence of 25% to 30% by weight of methanol based on present input materials N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and water, to obtain a hydrolysate, immediately thereafter, in step 2, reacting the hydrolysate obtained in step 1 with benzyl chloride, at a bottoms temperature of 58° C. to 60° C. and subsequently adding concentrated hydrochloric acid, to obtain a product mixture, and subsequently, in step 3, distillatively removing methanol and any fractions likewise volatile under the distillation conditions, from the product mixture obtained in step 2 under reduced pressure and with addition of a defined amount of water, wherein water is simultaneously added to the distillation bottoms up to such an amount as volatile fractions are discharged overhead; or in a process variant B, initially charging an N-(N-benzyl-2-aminoethyl)-3-aminopropyltrimethoxysilane hydrochloride-comprising methanolic solution, adding concentrated hydrochloric acid in a weight ratio of N-(N-benzyl-2-aminoethyl)-3-aminopropyltrimethoxysilane hydrochloride to concentrated hydrochloric acid of 4 to 2:1, at a temperature of from room temperature to 60° C., over 20 to 40 minutes with commixing, quickly adding water in an amount of 1 to 2 mol of water per mole of N-(N-benzyl-2-aminoethyl)-3-aminopropyltrimethoxysilane hydrochloride, over 1 to 5 minutes with commixing, to obtain a product mixture, before distillatively removing volatile fractions from the product mixture at a bottoms temperature of 40° C. to 55° C. and a reduced pressure of 280 to 120 mbar wherein water is simultaneously added to the distillation bottoms up to such an amount as volatile fractions are discharged overhead; to obtain in process variants A or B in the bottom of a distillation unit, an aqueous, low-VOC composition having an active substance content of ≤60% by weight, at a content of water of ≥40% to ≤60% by weight and a content of methanol of ≤0.5% by weight, wherein components in the composition sum to 100% by weight, and wherein the composition has a viscosity of ≥50 to ≤300 mPas at 20° C., a pH of ≥2 to ≤4 and a color number of ≤1 Gardner, and is storage-stable for at least 1 year at room temperature.

6: The process according to claim 5, wherein in process variant A, the process comprises in step 2, adding/employing the concentrated hydrochloric acid in an amount of 0.9 to 1.0 mol of HCl per mole of Si.

7: The process according to claim 5, wherein in process variant A, the process comprises in step 3, distillatively removing methanol and any fractions likewise volatile under the distillation conditions from the product mixture at an absolute pressure of 303 mbar to 111 mbar and a bottoms temperature of 43° C. to 51° C., and simultaneously adding water to the distillation bottoms up to such an amount as volatile fractions are discharged overhead.

8: An aqueous composition obtainable according to the process of claim 5.

9: A method for modifying fillers, pigments, or inorganic surfaces, the method comprising: combining the composition according to claim 1 as an adhesion promoter with fillers, pigments or inorganic surfaces.

10: The process according to claim 5, wherein in process variant A, the benzyl chloride is added at a ratio of 1 mol of benzyl chloride per mole of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.)

11: The process according to claim 5, wherein in process variant A, the water added during the removing, by distillation, of methanol is in a ratio of 1.35 g of water per 1.0 g of the N-(2-aminoethyl)-3-aminopropyltrimethoxysilane used in the controlled hydrolysis.

12: A method for functionalizing polymers or for adjusting the hydrophilicity of polymers, the method comprising: combining the composition according to claim 1 as an additive with polymers, in adhesives, sealing compositions, or fibre composite materials.

13: The method according to claim 12, wherein the polymers combined with the composition are selected from the group consisting of thermoplastics, thermosets, and elastomers.

14: A method for functionalizing glass or glass fibres, the method comprising: combining the composition according to claim 1 as an additive with polymers.

15: A method for preparing glass fibre applications, the method comprising: combining the composition according to claim 1 as a constituent of an aqueous size into a glass fibre application.

Description

EXAMPLES

Input Materials

[0039]

TABLE-US-00002 Benzyl chloride chloromethyl benzene, Ineos Dynasylan ®DAMO N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, Resource Efficiency Dynasylan ®1160 N-(N-benzyl-2-aminoethyl)-3-aminopropyltrimethoxysilane (50% by weight in methanol), Resource Efficiency Dynasylan ®1161EQ N-(N-benzyl-2-aminoethyl)-3-aminopropyltrimethoxysilane hydrochloride (50% by weight active substance in methanol), Resource Efficiency Water DM water Conc. HCI concentrated hydrochloric acid (w = 34.8%), Roth Glacial acetic acid concentrated acetic acid (w > 98%), Roth Methanol ultrahigh purity methanol, w > 99%

Analytical Methods

[0040] .sup.13C-NMR- and .sup.1H-NMR-determination was carried out using a “400 MHz Bruker NMR” apparatus, the solvent employed was CDCl.sub.3.

[0041] Determination of the colour numbers [Gardner] was carried out according to ISO 6274.

[0042] Refractive indices were determined according to DIN 51423 and densities according to DIN 51757.

[0043] Determination of the content of free methanol in the composition was carried out according to SAA 1844.

[0044] Viscosity reported in mPas was determined at 20° C. according to DIN 53015.

[0045] Density determination at 20° C. and reported in [g/cm.sup.3] was carried out according to DIN 51757.

[0046] Refractive index was determined according to DIN 51423.

[0047] pH was determined according to DIN 38409-H-1.

[0048] Testing of storage stability was performed under accelerated conditions at 60° C. To this end, the liquid to be tested was stored in a glass bottle (gas space inertized with nitrogen) in a circulating air drying cabinet in the absence of light. Increasing the storage temperature by 10 K in each case simulates the doubling of the storage time. After storage, the sample was assessed and investigated for analytically detectable changes such as for example colour number.

Comparative Example 1: (as per Example 7 from EP 0 716 127 A2)

[0049] Apparatus: 1 litre four-necked flask fitted with distillation bridge, dropping funnel, KPG stirrer, bottoms thermometer, oil bath with temperature control, rotary vane vacuum pump, manometer. 446.7 g of Dynasylan® 1161 EQ were initially charged and at RT a mixture of 25.0 g of DM water and 49.5 g of glacial acetic acid were added dropwise. The bottoms temperature increased to 38.5° C. The hydrolysate was subsequently diluted with 375.0 g of DM water. At an absolute pressure of 301 mbar to 250 mbar, altogether 370.6 g of distillate were removed. DM water was added during the distillation. Yield: 758.1 g of yellow liquid having an active substance content of 28.8%.

Analytical Results

[0050]

TABLE-US-00003 Determination Result Method Free methanol [% by weight] 2.7 SAA 1844 Colour number [Gardner] 1 ISO 6274 Viscosity 20° C. [mPas] 7.1 DIN 53015 Density (20° C.) [g/cm.sup.3] 1.071 DIN 51757 Refractive index 1.3931 DIN 51423 pH 4.6 DIN 38409-H-1

[0051] After one day of storage at 50° C. the product exhibited precipitation and sediment. When the product produced according to comparative example 1 was diluted with water, for example 0.5% to 2% by weight of product in DM water, the system became milky/cloudy after only 1 hour.

Comparative Example 2: (as per Example 2 From EP 0 590 270 A2)

[0052] A composition produced according to example 2 from EP 0 590 270 A2 has a content of methanol of 59.9% by weight.

Comparative Example 3: (as per Example 4 From EP 0 590 270 A2)

[0053] A composition produced according to the teaching of example 4 from EP 0 590 270 A2 also has a content of methanol of 59.9% by weight.

Example 1

[0054] Apparatus: 15 litre double-walled laboratory reactor fitted with metering pump, distillation bridge, KPG stirrer, bottoms thermometer, rotary vane vacuum pump, manometer, oil thermostat with temperature control means.

[0055] 7724.7 g of Dynasylan® 1161 EQ (50% active substance content in methanol) were initially charged and 1160.4 g of hydrochloric acid (w=34.8%) were added to the Dynasylan® 1161 EQ over 26 minutes with stirring. The temperature increased to 51.6° C. 3892.1 g of water were then added over 2 minutes. At a bottoms temperature of 41° C. to 53° C. and an absolute pressure of 272 mbar to 141 mbar, altogether 8759.8 g of distillate were removed. DM water was added during the distillation. Yield: 6436 g of clear yellowish liquid having an active substance content of 60% by weight.

[0056] The product was storage-stable for >8 weeks at 60° C.

Analytical Results

[0057]

TABLE-US-00004 Determination Result Method Free methanol [% by weight] 0.1 SAA 1844 Colour number [Gardner] <1 ISO 6274 Viscosity 20° C. [mPas] 163 DIN 53015 Density (20° C.) [g/cm.sup.3] 1.169 DIN 51757 Refractive index 1.4620 DIN 51423 pH (10% in H.sub.2O) 2.8 DIN 38409-H-1

[0058] Colour number: <1 Gardner after production [0059] <1 Gardner after 8 weeks of storage at 60° C.

[0060] Furthermore, with regard to possible aqueous applications, for example for special primer applications, a composition obtained according to example 1 is advantageously virtually freely dilutable with water without any clouding.

Example 2

[0061] Apparatus: 4 litre four-necked flask fitted with distillation bridge, dropping funnel, KPG stirrer, bottoms thermometer, oil bath with temperature control, rotary vane vacuum pump, manometer. 889.6 g of Dynasylan® DAMO were initially charged at room temperature and 368.0 g of methanol were stirred in. The bottoms temperature increased from 21° C. to 37° C. 86.4 g of DM water were then added over 5 minutes and the mixture was stirred at 50° C. for a further 30 minutes. At a bottoms temperature of 58° C. to 60° C., 506.4 g of benzyl chloride were added dropwise over 2.7 hours and the mixture was stirred at 58° C. to 60° C. for a further 5 hours. Analysis of the bottoms sample showed a content of free benzyl chloride of <0.1% by weight. 228.7 g of conc. hydrochloric acid (w=37%) were added dropwise over 30 minutes. The reaction mixture was then diluted with 1200 g of DM water. At a bottoms temperature of 43° C. to 51° C. and an absolute pressure of 300 mbar to 111 mbar, altogether 2075 g of distillate were removed. DM water was added during the distillation. Yield: 2321 g of clear yellowish liquid having an active substance content of 60% by weight. The product was storage-stable for >14.5 weeks at 60° C.

Analytical Results

[0062]

TABLE-US-00005 Determination Result Method Free methanol [% by weight] <0.1 SAA 1844 Colour number [Gardner] 1 ISO 6274 Viscosity 20° C. [mPas] 236 DIN 53015 Density (20° C.) [g/cm.sup.3] 1.165 DIN 51757 Refractive index 1.4601 DIN 51423 pH (10% in H.sub.2O) 3.2 DIN 38409-H-1

Example 3

[0063] Apparatus: 4 litre four-necked flask fitted with distillation bridge, dropping funnel, KPG stirrer, bottoms thermometer, oil bath with temperature control, rotary vane vacuum pump, manometer. 1112 g of Dynasylan® DAMO were initially charged at room temperature and 460 g of methanol were stirred in. The bottoms temperature increased from 21° C. to 38° C. Subsequently at a bottoms temperature of 58° C. to 60° C., 633 g of benzyl chloride were added dropwise over 1.25 hours and the mixture was stirred at 58° C. to 60° C. for a further 3 hours. Analysis of the bottoms sample showed a content of free benzyl chloride of <0.1% by weight. At a bottoms temperature of 39° C., 456.3 g of conc. hydrochloric acid (w=37%) were added dropwise over 21 minutes. At a bottoms temperature of 40° C. to 57° C. and an absolute pressure of 250 mbar to 180 mbar, altogether 1570.1 g of distillate were removed. DM water was added during the distillation. Yield: 2891.4 g of clear yellowish liquid having an active substance content of 60% by weight. The product was storage-stable for >10 weeks at 60° C.

Analytical Results

[0064]

TABLE-US-00006 Determination Result Method Free methanol [%] 0.4 SAA 1844 Colour number [Gardner] <1 ISO 6274 Viscosity 20° C. [mPas] 186 DIN 53015 Density (20° C.) [g/cm.sup.3] 1.167 DIN 51757 Refractive index 1.462 DIN 51423 pH (10% in H.sub.2O) 3.3 DIN 38409-H-1

Example 4

[0065] Apparatus: 15 litre double-walled laboratory reactor fitted with metering pump, distillation bridge, KPG stirrer, bottoms thermometer, rotary vane vacuum pump, manometer, oil thermostat with temperature control means.

[0066] 5782.4 g of Dynasylan® DAMO were initially charged and 2392 g of methanol were stirred in. The bottoms temperature increased from 21° C. to 38° C. Subsequently at a bottoms temperature of 58° C. to 60° C., 3291.6 g of benzyl chloride were added dropwise over about 6 hours and the mixture was stirred at 58° C. to 60° C. for a further 3 hours. Analysis of the bottoms sample showed a content of free benzyl chloride of <0.1% by weight. At a bottoms temperature of 25° C., 2382.1 g of conc. hydrochloric acid (w=37%) were added dropwise over 3 hours. At a bottoms temperature of 30° C. to 56° C. and an absolute pressure of 250 mbar to 152 mbar, altogether 8149 g of distillate were removed. DM water was added during the distillation. Yield: 14 670 g of clear yellowish liquid having an active substance content of 60% by weight.

TABLE-US-00007 Determination Result Method Free methanol [%] 0.2 SAA 1844 Colour number [Gardner] <1 ISO 6274 Viscosity 20° C. [mPas] 249.6 DIN 53015 Density (20° C.) [g/cm.sup.3] 1.167 DIN 51757 pH (10% in H.sub.2O) 3.3 DIN 38409-H-1

[0067] Colour number: ≤1 Gardner after production [0068] ≤1 Gardner after 3 weeks of storage at 60° C. [0069] ≤1 Gardner after 6 weeks of storage at 60° C.