Quaternary amino alcohol functional organosilicon compounds, composition containing the latter and their production and use

Abstract

The invention relates to novel quaternary amino alcohol functional organosilicon compounds, aqueous compositions containing the latter, and a method for their production, in particular in the form of oligomers and polymers which can be present in the partially or fully hydrolyzed form and are in particular water-soluble. The compositions comprise only an extremely small portion of VOCs. The invention further relates to their use, preferably in the production of inkjet photographic papers.

Claims

1. A quaternary-amino alcohol-functional, organosilicon compound, comprising a quaternary-amino alcohol-functional silanol and a quaternary-amino alcohol-functional siloxanol oligomer with Si—O-crosslinked structural elements, which form catenate, cyclic and/or crosslinked structures and which are obtainable from a reaction of at least one silane of the formulae II, IV or at least one hydrolysis, condensation or co-condensation product starting from silanes of the formula II and/or IV, water and at least one amino alcohol of the formula III and optionally the hydrolysis alcohol formed in this reaction is at least partly removed from the system, where at least one structure of said quaternary-amino alcohol-functional, organosilicon compounds corresponds in idealized form to the is represented by general formula I,
(R.sup.1O)[(R.sup.1O).sub.1−x−y(R.sup.2).sub.xSi(C.sup.+).sub.1+yO].sub.aR.sup.1 [a.(1+y)]Hal.sup.−  (I) where C.sup.+ in formula I is independently a group of the formula V
[—(R.sup.3).sub.nCH.sub.2—N.sup.+[(—CH.sub.2).sub.mOH].sub.z(R.sup.4).sub.3−z].sub.1+y   (V), wherein, in formula I, each R.sup.1 is, independently, hydrogen or a linear, branched or cyclic alkyl group having 1 to 8 C atoms, each R.sup.2 is, independently, a linear, branched or cyclic alkyl group having 1 to 8 C atoms or is an aryl, arylalkyl or acyl group, wherein, in formula V each R.sup.3 is, independently, a linear, branched or cyclic alkylene group having 1 to 18 C atoms, each R.sup.4 is, independently, a group comprising from 1 to 16 carbon atoms, wherein, in formulae I and V, independently, n is 0 or 1, m is an integer between 1 and 16 and z is 1 or 2 or 3, and Hal is chloro or bromo, and x is 0 or 1, y is 0 or 1 and (x+y) is 0 or 1, and a is greater than or equal to 1, where the silane of formula II is a haloalkylsilane,
(R.sup.10).sub.3−x−y(R.sup.2).sub.xSi[(R.sup.3).sub.nCH.sub.2Hal].sub.1+y   (II), and the silane of the formula IV is a quaternary-amino alcohol-functional silane:
(R.sup.10).sub.3−x−y(R.sup.2).sub.xSi[(R.sup.3).sub.nCH.sub.2—N.sup.+[—(CH.sub.2).sub.mOH].sub.z(R.sup.4).sub.3−z].sub.1+y.(1+y)[Hal.sup.−]  (IV), and the amino alcohol corresponds to the formula III,
[HO—(CH.sub.2).sub.m—].sub.zN(R.sup.4).sub.3−z   (III), wherein, in formulae II, III and IV, each R.sup.1 is, independently, a hydrogen, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an awl, arylalkyl or acyl group, each R.sup.2, independently, is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or is an aryl, arylalkyl or acyl group, R.sup.3, R.sup.4, Hal and also n, m and z, independently of one another, are as defined above, and x is 0, 1 or 2,y is 0, 1 or 2 and(x+y)is 0, 1 or 2.

2. (canceled)

3. The process composition as claimed in claim 17, wherein the reaction of component A and of component B is carried out in the presence of a defined amount of water, or component A is reacted with component B and the product is subsequently hydrolyzed in the presence of a defined amount of water.

4. The composition as claimed in claim 17, wherein component B is at least one member selected from the group consisting of N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and N-triethanolamine.

5. The composition as claimed in claim 17, wherein water is present in an amount of 0.5 to 500 mol of water per mole of silicon atoms present in component A.

6. The composition as claimed in claim 17, wherein the water is metered continuously or discontinuously to component A, optionally in a mixture with component B, or to the quaternary-amino alcohol-functional, organosilicon compound of formula IV
(R.sup.10).sub.3−x−y(R.sup.2).sub.xSi[(R.sup.3).sub.nCH.sub.2—N.sup.+[—(CH.sub.2).sub.mOH].sub.z(R.sup.4).sub.3−z].sub.1+y.(1+y)[Hal.sup.−]  (IV), that is formed, the water added discontinuously with stirring where in formula IV R.sup.1, R.sup.2, R.sup.3, R.sup.4, x, y, z, n and m have the above-defined definition.

7. The composition as claimed in claim 17, wherein portionwise in each case, the defined amount of water is 0.5 to 4.0 mol of water per mole of silicon atoms.

8. The composition as claimed in claim 17, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of an alcohol formed in the hydrolysis of the compound of the formula II ethanol, methanol, n-propanol, and isopropanol.

9. The composition as claimed in claim 17, wherein the reaction is carried out under a pressure of 1 mbar to 100 bar and at a temperature of 20 and 150° C.

10. The composition as claimed in claim 17, wherein the process further comprises removing volatile solvent and optionally groups which can be hydrolyzed to volatile solvent, to a level in the overall composition of below 12% by weight to 0% by weight wherein said removing can be carried out during the reaction, after the reaction, or both, and/or thereafter by distillation.

11. The composition as claimed in claim 17, wherein component A is at least one member selected from the group consisting of 3 chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylethoxysilane, 3-chloropropyldimethylmethoxysilane, and or of a hydrolysis or condensation product of the aforementioned alkoxysilanes.

12. The process composition as claimed in claim 17, wherein components A and B are present, in relation to the haloalkyl group of component A and to the tertiary nitrogen of component B, in a molar ratio of 2:1 to 1:100.

13. The composition as claimed in claim 17, wherein said reacting is carried out by a) introducing component A together with a solvent and adding a defined amount of water, thereafter adding component B, removing hydrolysis alcohol at least partly from the system, and adding water in defined amounts, or b) introducing component A and adding a solvent, thereafter adding a defined amount of water, therafter adding component B, removing hydrolysis alcohol at least partly from the system, and adding water in defined amounts, or c) introducing component A and adding a solvent, adding a defined amount of water, removing hydrolysis alcohol at least partly from the system, thereafter adding component B, and removing hydrolysis alcohol at least partly from the system, adding a defined amount of water and removing hydrolysis alcohol at least partly from the system, and adding water in defined amounts, or d) reacting component A with component B at elevated temperature, adding an additional amount of component B, and subsequently adding a defined amount of water, forming hydrolysis alcohol at least partly from the system, and adding water in defined amounts, or e) introducing component A and adding a solvent is added, adding a defined amount of water and removing hydrolysis alcohol at least partly from the system, subsequently adding component B and adding, at elevated temperature, a defined amount of water, and removing hydrolysis alcohol at least partly from the system, and optionally adding water in defined amounts, or f) introducing component A together with a solvent and adding a defined amount of water, removing hydrolysis alcohol at least partly from the system, adding component B, and removing hydrolysis alcohol at least partly from the system, and adding water in defined amounts.

14. The composition as claimed in claim 17, wherein the composition has a viscosity of less than 1500 mPa s.

15-16. (canceled)

17. A composition comprising a quaternary-amino alcohol-functional, organosilicon compound according to claim 1, and water, obtainable by a process that comprises: reacting, as component A (i) at least one haloalkyl-functional alkoxysilane of general formula II
(R.sup.10).sub.3−x−y(R.sup.2).sub.xSi[(R.sup.3).sub.nCH.sub.2Hal].sub.1+y   (II), wherein each R.sup.1 is identical or different and is a hydrogen, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl, arylalkyl or acyl group, each R.sup.2 is identical or different and is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or is an aryl, arylalkyl or acyl group, each R.sup.3 is identical or different and is a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, n is 0 or 1 and Hal is chloro or bromo, and x is 0, 1 or 2, y is 0, 1 or 2 and (x+y) is 0, 1 or 2, or (ii) a hydrolysis or condensation product of at least one alkoxysilane of the aforementioned general formula II or (iii) a mixture of at least one alkoxysilane of the aforementioned general formula II and a hydrolysis and/or condensation product of at least one alkoxysilane of the aforementioned general formula II with an amino alcohol of general formula III as component B,
[HO—(CH.sub.2).sub.m—].sub.zN(R.sup.4).sub.3−z   (III), in which each R.sup.4 is identical or different and is a group comprising 1 to 16 carbon atoms, m is an integer between 1 and 16 and z is 1 or 2 or 3, carrying out at least a part of the process in the presence of a defined amount of water, and optionally removing the resultant hydrolysis alcohol at least partly from the system.

18. The composition as claimed in claim 17, which has a solids content in the composition of 0.1% to 99.9% by weight with all of the constituents in the composition making 100% by weight in total.

19. The composition as claimed in claim 17, which has a total nitrogen content of 0.1% to 15% by weight for a viscosity of 1 to 100 mPa s, and optionally for a pH in the range from 5.0 to 11.0.

20. The composition as claimed in claim 17, wherein the composition further comprises at least one selected from the group consisting of a pigment, a filler, a binder, a crosslinker, an optical brightener, a coating auxiliary, and another auxiliary.

21. (canceled)

Description

EXAMPLES

[0107] Methods of Determination: Hydrolyzable chloride was titrated potentiographically with silver nitrate (for example, Metrohm, type 682 silver rod as indicator electrode and Ag/AgCl reference electrode or another suitable reference electrode). Total chloride content after Wurtzschmitt digestion. For this purpose, the sample is digested with sodium peroxide in a Wurtzschmitt bomb. After acidification with nitric acid, chloride is measured potentiographically with silver nitrate, as above.

[0108] In the case of a complete reaction of the chloroalkyl functionality with tertiary amines, the analytical values for hydrolyzable chloride and total chloride are identical and are therefore a measure of the completeness of the reaction, since the sum total of saltlike chloride (amine hydrochloride) and covalently bonded chlorine (chloroalkyl functionality) is determined by total chloride, and exclusively saltlike chloride or chloride which can be eliminated with water (amine hydrochloride in the present case) is determined by hydrolyzable chloride. At the beginning of the reaction, the value for hydrolyzable chloride is zero and increases at complete conversion to the value which is measured for total chloride. Therefore, these analyses are very useful in addition to .sup.1H and .sup.13C NMR spectroscopy for reaction monitoring.

[0109] The alcohol content after hydrolysis is determined by gas chromatography. For this purpose, a sample of a defined amount is hydrolyzed with sulfuric acid (5 g of sample, 25 ml of H.sub.2SO.sub.4, w=20%). 75 ml of distilled water are added. Thereafter, neutralization takes place with aqueous sodium hydroxide solution, and a steam distillation is performed. Internal standard: 2-butanol.

[0110] Determination of nitrogen, organically bound, ammonium, etc. organically bound nitrogen can be converted into ammonium by means of Kjeldahl digestion and determined acidimetrically as ammonia following addition of aqueous sodium hydroxide solution. Method: up to 5 g of sample are heated with 10 ml of sulfuric acid (concentrated) and a Kjeldahl tablet (Merck 1.15348) until the digestion solution is pale and clear apart from any precipitated silica. The digestion vessel is attached to a distillation apparatus, and ammonia released as a result of addition of aqueous sodium hydroxide solution (27%) is distilled over into the receiver. With addition of boric acid (2%), the ammonia content is titrated with sulfuric acid (c(H.sub.2SO.sub.4)=0.05 mol/l or 0.005 mol/l). V=consumption of sulfuric acid in ml, c=concentration of sulfuric acid in mol/l, z=number of equivalents of sulfuric acid=2, E=initial mass in mg.

[00001]$\mathrm{Evaluation}.Math.\text{:}$$N\left[\%\right]=\frac{100.Math.V.Math.c.Math.z.Math.14.01}{E}$

[0111] Determination of SiO.sub.2 takes place following decomposition using sulfuric acid and Kjeldahl catalyst, by determining the weight of the precipitated SiO.sub.2. Method: The 1 g sample is placed in a 250 ml glass beaker and a Kjeldahl tablet (e.g., Merck #15348) and 20 ml of sulfuric acid (concentrated) are added. The solution is slowly heated. The organic constituents are oxidized, until the digestion solution, with fuming of the sulfuric acid, remains clear and pale. After cooling and after cautious dilution to approximately 200 ml, the precipitated silica is removed by filtration on a white ribbon filter. The filter is washed with water until the pH of the wash water is >4, and then dried and incinerated in a platinum crucible. The residue is ignited at 800° C. and reweighed. After fuming with hydrofluoric acid (concentrated), ignition at 800° C. and reweighing are repeated. m=weight difference before and after fluorination in g; E=initial mass in g.

[00002]$\mathrm{Evaluation}.Math.\text{:}$${\mathrm{SiO}}_2\left[\%\right]=\frac{100.Math.m}{E}$

[0112] Shown below are the DIN standards used in determining the stated parameters:

[0113] Solids content: DIN 38409-1 (1987-01-00)

[0114] Refractive index: DIN 51423 (2010-02-00)

[0115] Density: DIN 51757 (1994-04-00)

[0116] Viscosity DIN 53015 (2001-02-00)

[0117] Color number DIN EN ISO 6271 (2005-03-00)

[0118] Cloudiness DIN EN ISO 7027 (2000-04-00)

Example 1

3-Chloropropyltriethoxysilane (CPTEO)/N,N-dimethylethanolamine

[0119] Apparatus:

[0120] 4 l stirred reactor with distilling device, pot thermometer, top thermometer, vacuum pump, manometer metering device, and pressure filter

[0121] Materials used

TABLE-US-00001 m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] Comment CPTEO 1283.0 5.328 28.79 M = 240.8 g/mol, bp = 230° C. N,N- 570.5 6.400 12.80 M = 116.21 g/mol Dimethylethanolamine bp = 133° C. Ethanol 160.0 3.59 Deionized water: 1.sup.st addition 143.9 7.992 3.23 2.sup.nd addition 143.9 3.23 3.sup.rd addition 143.9 3.23 4.sup.th addition 144.5 3.24 5.sup.th-12.sup.th addition 1866.1 41.88 Σ (inputs) 4455.8 100.00 m(Ethanol from hydrolysis) = 735.3 g

[0122] Final mass of product: 2438.5 g (theory: 2562.7 g)

[0123] Final mass of distillate: 2236.0 g

[0124] Procedure:

[0125] 1. Hydrolysis

[0126] A 4 l four-neck flask was charged with 1283.0 g of CPTEO (5.328 mol) and 160.0 g of ethanol. At RT, 143.9 g of deionized water (1.5 mol H2O/mol Si) were added dropwise over the course of 16 minutes. During this addition, the pot temperature rose to around 40° C.

[0127] 2. Quaternization Reaction

[0128] Subsequently 570.5 g (6.400 mol) of dimethylethanolamine were stirred in over the course of 6 minutes. During this addition, the pot temperature rose from 40° C. to around 48° C. This was followed by boiling at reflux for around 45 minutes (pot temperature around 85° C.).

[0129] 3. Distillation at RT/Quaternization Reaction

[0130] Under atmospheric pressure, 1706.6 g of water/ethanol/dimethylethanoldiamine were distilled off over the course of around 6 hours. During this time, 2038.3 g of water were stirred in in seven portions. After distillation for around 3 hours, a total of 432.4 g of deionized water were introduced in three portions (2.sup.nd to 4th water addition). A sample of the pot then showed itself to be readily soluble in deionized water.

[0131] 3. Distillation Under Reduced Pressure

[0132] Over the course of 1.7 hours, at a pot temperature of 50 to 55° C. and under an absolute pressure of around 140 mbar, 529.4 g of water/ethanol/dimethylethanol-diamine mixture were distilled off. At the end of the distillation, 560.17 g of deionized water were stirred in. This gave a slightly cloudy/slightly yellowish liquid of low viscosity. Yield: 2521.7 g

[0133] 4. Filtration

[0134] Filtration was carried out in a 2 l laboratory pressure filter at RT with an overpressure of around 0.5 bar of N2. The filter used was a cut-to-size filter plate (pilot plant, used for bubble filters) having a diameter of 135 mm. The filtration time was around 20 minutes. Filtration produced a clear, slightly yellowish liquid of low viscosity.

[0135] Analysis (Product):

TABLE-US-00002 Determination Unit Result Method Total N wt % 2.9 see above Total chloride wt % 7.4 see above Hydrolyzable chloride wt % 7.0 see above SiO.sub.2 wt % 12.5 see above Solids content wt % 47.5 DIN 38409-H1-1 Ethanol (after hydrolysis) wt % <0.1 see above pH 8.6 Refractive index (20° C.) 1.4146 DIN 51423 Density (20° C.) g/cm.sup.3 1.126 DIN 51757 Viscosity (20° C.) mPa s 12.3 DIN 53015 Flash point ° C. >95 DIN EN ISO 2719 Color number mg Pt—Co/l 55 ISO 6271 Turbidity TU/F 0.36 ISO 7027

[0136] 1H .sub.and .sup.13C NMR:

[0137] Purity of the target compound around 95.8 mol %. 4.2 mol % of free dimethylethanol-amine. No indications of any transesterification of the aminoethanol group to form SiOR.

[0138] .sup.29Si NMR:

[0139] 1% Si silane

[0140] 7% Si M

[0141] 45% Si D

[0142] 47% Si T structures

[0143] The new product is notable for even better processing and applications properties in the production of high-gloss inkjet photographic papers.

[0144] Comments on the Reaction of N,N-dimethylethanolamine with CPTEO

[0145] Differences in the process for the reaction of haloalkylalkoxysilanes with tertiary amines, as in PCT/EP2010/053626.

[0146] As set out in example 5, it proves advantageous if the CPTEO is prehydrolyzed prior to the reaction of CPTEO with N,N-dimethylethanolamine, and the hydrolysis alcohol released is removed by distillation.

[0147] If there is no prehydrolysis of CPTEO prior to reaction with N,N-dimethylethanol-amine, then it proves advantageous to operate with an excess of N,N-dimethyl-ethanolamine, in order to prevent significant precipitation of CPTEO (see example 3). If necessary, excess N,N-dimethylethanolamine can be separated off by distillation.

[0148] Incompletely reacted CPTEO with N,N-dimethylethanolamine can be precipitated in principle by addition of water (see example 2).

[0149] If the reaction of CPTEO with N,N-dimethylethanolamine is carried out at temperatures of 140 to 150° C., this leads to intense discoloration of the product (see example 4).

Example 2

[0150] A 500 ml four-neck flask was charged with 160.01 g of Dynasylan® CPTEO (0.664 mol). At RT, 20.73 g of ethanol were stirred in and then 18.09 g of deionized water (1.5 mol H.sub.2O/mol Si) were added dropwise with stirring over the course of 13 minutes. During this addition, the pot temperature rose from 20° C. to 33° C. Subsequently, over the course of two minutes, 59.34 g of N,N-dimethylethanolamine (0.665 mol) were stirred in, leading to an increase in the pot temperature to 42° C. This was followed by boiling under reflux at a pot temperature of around 87° C. for one hour. Thereafter, ethanol mixture was distilled off under atmospheric pressure. In the course of the distillation, the pot temperature reached a maximum temperature of 107° C. 46 minutes after the beginning of distillation, 36.08 g of deionized water were metered in over the course of three minutes. A further 184.88 g of deionized water were added during further distillation. A total of 184.5 g of liquid were removed by distillation. After a total of 7.5 hours, the batch was cooled to RT. The yield was 266.07 g (corresponding to 90.3% of theory) of clear, slightly yellowish liquid of low viscosity. Deposited on the stirrer were significant quantities of a gel-like substance (condensed silane hydrolysate), which was responsible for the relatively low yield (reduced yield as a result of gel deposits).

[0151] Analysis:

TABLE-US-00003 Determination Unit Result Method Total N wt % 3.0 see above Total chloride wt % 7.7 see above Hydrolyzable chloride wt % 7.6 see above Solids content wt % 51.5 DIN 38409-H1-1 Ethanol (after wt % 0.1 see above hydrolysis) pH 7.5 Refractive index (20° C.) 1.4180 DIN 51423 Density (20° C.) g/cm.sup.3 1.132 DIN 51757 Viscosity (20° C.) mPa s 14.2 DIN 53015 Color number mg Pt—Co/l 30 ISO 6271 Turbidity TU/F 0.23 ISO 7027

[0152] .sup.1H and .sup.13C NMR: 98.2 mol % purity of the quaternary target compound, about 1.8 mol % of free dimethylethanolamine

[0153] .sup.29Si NMR: 1% Si silane [0154] 7% Si M [0155] 47% Si D [0156] 45% Si T structures

Example 3

[0157] 20 mol % DMEA Excess, No Gel Deposits

[0158] A 500 ml four-neck flask was charged with 160.55 g of Dynasylan® CPTEO (0.667 mol). At RT, 20.12 g of ethanol were stirred in and then 18.05 g of deionized water (1.5 mol H.sub.2O/mol Si) were added dropwise with stirring over the course of 13 minutes. During this addition, the pot temperature rose from 21° C. to 28° C. 33.1 g of hydrolysis ethanol were distilled off under reduced pressure (140 to 94 mbar absolute pressure) at a pot temperature of around 35° C. over the course of 45 minutes. Subsequently, over the course of four minutes, 71.34 g of N,N-dimethylethanolamine (0.800 mol) were stirred in, leading to an increase in the pot temperature to 35° C. Thereafter, 80.08 g of ethanol mixture were distilled off over the course of 38 minutes under atmospheric pressure. Boiling under reflux was carried out for 20 minutes at a pot temperature of 96.0 to 92.2° C. Subsequently, 17.99 g of deionized water were metered in over the course of two minutes. A further 245.47 g of deionized water were added during further distillation. A total of 232.5 g of liquid were removed by distillation. After a total of 7.65 hours, the batch was cooled to RT. The yield was 325.9 g (corresponding to 96.0% of theory) of clear, slightly yellowish liquid of low viscosity. No gel deposits in the reaction vessel.

[0159] Analysis:

TABLE-US-00004 Determination Unit Result Method Total N wt % 2.7 see above Total chloride wt % 7.2 see above Hydrolyzable chloride wt % 7.0 see above Solids content wt % 47.2 DIN 38409-H1-1 Ethanol (after wt % <0.1 see above hydrolysis) pH 8.0 Refractive index (20° C.) 1.4121 DIN 51423 Density (20° C.) g/cm.sup.3 1.122 DIN 51757 Viscosity (20° C.) mPa s 10.9 DIN 53015 Color number mg Pt—Co/l 25 ISO 6271 Turbidity TU/F 1.0 ISO 7027

[0160] .sup.1H and .sup.13C NMR: 97.3 mol % purity of the quaternary target compound, about 2.7 mol % of free dimethylethanolamine

[0161] .sup.29Si NMR: −% Si silane [0162] 6% Si M [0163] 47% Si D [0164] 47% Si T structures

Example 4

[0165] CPTEO/N,N-dimethylethanolamine (DMAE) Reaction at 140 to 150° C.

[0166] A 500 ml four-neck flask was charged with 160.10 g of CPTEO (0.665 mol). At a pot temperature of 20° C., 59.35 g of N,N-dimethylethanolamine (0.666 mol) were stirred in. At a pot temperature of 140.6 to 151.8° C., stirring was carried out for 6.8 hours. After a reaction time of around 2.5 hours, GC analysis still indicated 14.0 area % of CPTEO and <0.1 area % of N,N-dimethylethanolamine in the pot. The pot contents had in the meantime undergone a change in color from slightly yellowish through orange to red. After a reaction time of 3.7 hours, GC analysis of the pot sample indicated a CPTEO content of 16.8 area %. At this point 13.98 g of N,N-dimethyl-ethanolamine (0.157 mol) were metered in. The pot contents changed color to brown. After a reaction time of a further 22 minutes, the GC analysis of the pot contents still indicated 7.4 area % of CPTEO. A further 13.99 g of N,N-dimethylethanolamine (0.157 mol) were metered in. After a reaction time of a further 13 minutes, GC analysis still indicated 3.2 area % of CPTEO in the pot contents. 127.55 g of deionized water were then metered in over the course of 31 minutes. After a total of 8 hours, the batch was cooled to RT. The pot contents were virtually clear and brown. The next day, free ethanol was distilled off under reduced pressure (300 mbar to 176 mbar absolute pressure) at a pot temperature of 61.1 to 76.9° C. In total, over around 4 hours, 230.28 g of liquid were removed by distillation. During the distillation, 223.8 g of deionized water were metered in. The yield was 348.19 g (corresponding to 95.4% of theory) of clear brown liquid of low viscosity. No gel deposits in the reaction vessel.

[0167] Analysis:

TABLE-US-00005 Determination Unit Result Method Total N wt % 3.1 see above Total chloride wt % 6.6 see above Hydrolyzable chloride wt % 6.3 see above Solids content wt % 45.7 DIN 38409-H1-1 Ethanol (after wt % <0.1 see above hydrolysis) pH 9.5 Refractive index (20° C.) 1.1429 DIN 51423 Density (20° C.) g/cm.sup.3 1.145 DIN 51757 Viscosity (20° C.) mPa s 11.1 DIN 53015 Color number Gardner 8 ISO 6271 Turbidity TU/F 1.6 ISO 7027

Example 5

[0168] CPTEO/DMAE 1:1 (mol), CPTEO Prehydrolyzed with 1.5 mol of H.sub.2O/mol of Si

[0169] A 4 l three-neck flask was charged with 829.30 g of CPTEO (3.444 mol) and 100.40 g of ethanol were stirred in at a pot temperature of 22° C. Subsequently, at room temperature and with intense stirring, 93.12 g of deionized water were metered in over the course of 8 minutes. During this addition, the pot temperature rose to 47° C. Under reduced pressure, the hydrolysis ethanol was then distilled off until the pot temperature was 62.2° C. and the absolute pressure was <1 mbar. Subsequently, 307.12 g (3.445 mol) of N,N-dimethylethanolamine were stirred in. During this addition, the pot temperature rose to a maximum of 58.5° C. The pot contents were subsequently heated to 109.4° C., and 93.05 g of water were metered in cautiously over the course of 11 minutes. After 12 minutes there was a further addition of water (92.75 g in 6 minutes). Distillative removal of ethanol was commenced, under atmospheric pressure. Subsequently more deionized water, in two portions (92.99 g and 93.01 g), was metered in, and then, under reduced pressure, residual free ethanol was distilled off. During the vacuum distillation and after the end of the distillation, a total of a further 956.36 g of deionized water were stirred into the reaction mixture. This gave 1773.2 g (97.0%) of slightly cloudy/yellowish liquid of low viscosity.

[0170] Analysis:

TABLE-US-00006 Determination Unit Result Method Total N wt % 2.6 see above Total chloride wt % 6.8 see above Hydrolyzable chloride wt % 6.5 see above Solids content wt % 43.9 DIN 38409-H1-1 Ethanol (after wt % <0.1 see above hydrolysis) pH 6.3 Refractive index (20° C.) 1.4059 DIN 51423 Density (20° C.) g/cm.sup.3 1.115 DIN 51757 Viscosity (20° C.) mPa s 8.7 DIN 53015 Color number mgPt—Co/l 60 ISO 6271 Turbidity TU/F 2.7 ISO 7027

[0171] Comparative Example for the Preparation of Dispersions:

[0172] Quaternary silane system (CPTEO/TMEDA), prepared from 3-chloropropyltriethoxy-silane (CPTEO) and tetramethylethylenediamine (TMEDA).

Comparative Example 1

[0173] Water-based, VOC-free solution of a quaternary silane system, prepared from 3-chloropropyltriethoxysilane (CPTEO) and tetramethylethylenediamine (TMEDA).

[0174] Apparatus: Stirred reactor with distilling device, pot thermometer, top thermometer, vacuum pump, manometer, and metering device

[0175] Materials Used:

TABLE-US-00007 N M (input) (inputs) w (inputs) Inputs [g] [mol] [%] Comment Chloropropyl- 3206.2 13.31 37.3 M = 240.8 g/mol triethoxysilane N,N,N′,N′- 1547.2 13.31 18.0 M = 116.21 g/mol Tetramethyl- ethylenediamine Deionized water: 1. Addition 1603.1 18.6 2. Addition 641.3 7.5 3. Addition 1600.0 18.6 Σ (inputs) 8597.8

[0176] m(ethanol from hydrolysis)=1836.8 g; final mass of product after filtration: 6521.4 g (theory: 6761.1 g); final mass of distillate: 2946.5 g

[0177] Procedure:

[0178] 1. Reaction (duration about 9.7 h): chloropropyltriethoxysilane was introduced initially and tetarmethylethylenediamine was added rapidly with stirring. This was followed by the 1.sup.st addition of water within around 20 minutes (volume flow rate around 4.8 l/h) under vigorous stirring. The pot contents were at this point distinctly cloudy, and were heated under reflux (around 87° C.) for 6 hours. The 2.sup.nd addition of water was made over the course of 10 minutes to the now clarified pot contents (volume flow rate around 3.9 l/h). After a further 1.5 hours of heating under reflux, the 3.sup.rd addition of water was made with stirring (over the course of around 20 minutes, volume flow rate around 4.8 l/h).

[0179] 2. Distillation (duration about 9 h): At a pot temperature of 49° C. to 54° C., hydrolysis ethanol was distilled off under reduced pressure (100-270 mbar). Following distillative removal of around 1700 g of ethanol/water mixture, 327 g of water were rapidly added. In order to remove the hydrolysis alcohol by distillation almost to completion, it was necessary to remove an at least 60% excess (based on the mass of hydrolysis ethanol) by distillation. The amount of water removed by distillation was returned at the end of the distillation.

[0180] 3. Filtration (duration around 1 h): Thereafter, the yellowish, slightly cloudy product was filtered via pressure filter (2 l) and Seitz 500 depth filter at an overpressure of 0.8 bar (filtration performance at d.sub.filter=14 cm: 18 l/h). A clear, slightly yellowish liquid was obtained.

[0181] Analyses:

TABLE-US-00008 Determination Result Theory Method Viscosity (20° C.) 70 DIN 53015 [mPa s] Density (20° C.) 1.107 DIN 51757 [g/ml] Refractive index 1.4224 DIN 51423 (20° C.) Color [mg Pt—Co/l] 75 Solids [%] 48.4 DIN 38409-1 pH 8.6 1:1 in Wasser, DIN 38404-C5 SiO.sub.2 [%] 11.8 11.8 see above Ethanol after 0.5 see above hydrolysis [%] Total N [%] 5.0 5.5 see above Total chloride [%] 7.2 7.0 see above Hydrolyzable 7.1 7.0 see above chloride [%]

[0182] NMR: .sup.13C NMR: around 15% of the TMEDA groups were present in the form of the bis adduct. Per 100 SiCH.sub.2 groups there was 8 mol % of free TMEDA.

[0183] .sup.29Si NMR: 2.5 Si-% silane; 14.6 Si-% M structures; 49.7 Si-% D structures; 33.3 Si-% T structures

[0184] Preparation of Dispersions

[0185] Dispersion examples D1 to D4 below were developed with the proviso that the dispersions should be able to be applied in low-viscosity form and should have similar performance in papercoating in respect of pore structure and pore volume. The measure which emerged for the porosity of the coating was the average aggregate size in the dispersion, measured by dynamic light scattering. For optimum results, an average aggregate size of 140 to 160 nm was desirable. Within a system, higher degrees of fill during dispersing resulted in a decrease in the average particle size. The examples show that by using the silane system of the invention it is possible to realize very high levels of fill while at the same time retaining the desired aggregate size.

Example D1

Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and Poly-Diallyldimethylammonium Chloride (p-DADMAC)

Comparative Example

[0186] 1350 g of deionized water were admixed with 60 g of p-DADMAC. Then 320 g of fumed silica were incorporated with stirring by means of a dissolver at 1500 to 4000 rpm, followed by further preliminary dispersing over a period of 5 minutes at 2000 rpm. Dispersion then continued with cooling (<30° C.) for ten minutes, now using a rotor-stator dispersing apparatus at 15 000 rpm. To conclude, the dispersion was filtered through a 500 μm sieve.

Example D2

Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and N-Butylaminopropyltrimethoxysilane

Comparative Example

[0187] 1200 g of deionized water were admixed with 425 g of fumed silica, incorporated by stirring by means of a dissolver at 1500 to 4000 rpm, followed subsequently by further predispersing over a period of 5 minutes at 2000 rpm. Dispersion then continued with cooling (<30° C.) for ten minutes, now using a rotor-stator dispersing apparatus at 15 000 rpm. Stirring was then carried out again with the dissolver at 2000 rpm, and a mixture of 21.3 g of N-butylaminopropyltrimethoxysilane, 67 g of methanol, and 20 g of formic acid (50 percent strength solution in water) was added, followed by final dispersion for 60 minutes in the rotor-stator system at 5000 rpm at 60° C. To conclude, the dispersion was cooled and filtered through a 500 μm sieve.

Example D3

Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and Quaternary Silane System (CPTEO/TMEDA)

Comparative Example

[0188] 509 g of fumed silica were incorporated by stirring with a dissolver at 1500 to 5000 rpm into a mixture of 1215 g of deionized water, 53.0 g of quaternary silane system (CPTEO/TMEDA system from comparative example 1), and 23.4 g of acetic acid (25 percent strength by weight solution in water), and dispersing was continued at 2000 rpm for 5 minutes. This was followed by final dispersing with a rotor-stator dispersing apparatus (Kinematica Polytron PT6100) over a period of 30 minutes at 10 000 rpm. To conclude, the dispersion was cooled and filtered through a 500 μm sieve.

Example D4

Inventive Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and the Solution from Example 1

[0189] 428 g of fumed silica were incorporated by stirring with a dissolver at 1500 to 5000 rpm into a mixture of 805 g of deionized water and 47.4 g of the solution from example 1, and dispersing was continued at 2000 rpm for 10 minutes. This was followed by dispersing with a rotor-stator dispersing apparatus (Kinematica Polytron PT6100) over a period of 30 minutes at 10 000 rpm. To conclude, the dispersion was filtered through a 500 μm sieve.

TABLE-US-00009 TABLE Physicochemical data of dispersions D1 to D4 Comparison Invention D1 D2 D3 D4 Solids content*.sup.) % by wt. 20.0 25.0 30.0 35.0 Particle diameter**.sup.) nm 157 154 156 148 Viscosity***.sup.) mPa s 47 80 122 142 *.sup.)after drying to constant weight at 125° C.; **.sup.)by dynamic light scattering (Horiba LB-500); ***.sup.)at 1000 1/s; 23° C.;

[0190] Dispersion examples D5 to D8 showed the maximum solids content possible with the respective cationizing additive, independently of the parameter of aggregate size. As expected, the dispersions had very high viscosities, but were still liquid and processable. On account of the small particle sizes, further processing to papercoating slips and inkjet papers was not undertaken.

Example D5

Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and Poly-Diallyldimethylammonium Chloride (p-DADMAC)

Comparative Example

[0191] 1190 g of deionized water were admixed with 60 g of p-DADMAC. Then 320 g of fumed silica were incorporated with stirring by means of a dissolver at 1500 to 4000 rpm, followed by further preliminary dispersing over a period of 5 minutes at 2000 rpm. Dispersion then continued with cooling (<30° C.) for ten minutes, now using a rotor-stator dispersing apparatus at 15 000 rpm. To conclude, the dispersion was filtered through a 500 μm sieve.

Example D6

Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and N-Butylaminopropyltrimethoxysilane

Comparative Example

[0192] 1035 g of water were introduced and 21.2 g of N-butylaminopropyltrimethoxysilane were stirred into the water. After a hydrolysis time of 30 minutes, the initial solution was adjusted to a pH of 4.2 using 63.7 g of acetic acid (25 percent strength by weight solution in water). Then 423.9 g of fumed silica were incorporated by stirring with a dissolver at 1500 to 4000 rpm, followed by further predispersing over a period of five minutes at 2000 rpm. After that, final dispersion took place with cooling (<30° C.) for 30 minutes, now using a rotor-stator dispersing apparatus at 10 000 rpm. To conclude, the dispersion was filtered through a 500 μm sieve.

Example D7

Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and Quaternary Silane System (CPTEO/TMEDA System from Comparative Example 1)

Comparative Example

[0193] 560 g of fumed silica were incorporated by stirring with a dissolver at 1500 to 5000 rpm into a mixture of 1156 g of deionized water, 58.3 g of quaternary silane system (CPTEO/TMEDA), and 25.7 g of acetic acid (25 percent strength by weight solution in water), and dispersing was continued at 2000 rpm for 5 minutes. This was followed by final dispersing with a rotor-stator dispersing apparatus (Kinematica Polytron PT6100) over a period of 30 minutes at 10 000 rpm. To conclude, the dispersion was cooled and filtered through a 500 μm sieve.

Example D8

Inventive Dispersion Based on Fumed Silica with a Specific Surface Area of 300 m2/g and the Solution from Example 1

[0194] 557 g of fumed silica were incorporated by stirring with a dissolver at 1500 to 5000 rpm into a mixture of 885 g of deionized water and 58 g of the solution from example 1, and dispersing was continued at 2000 rpm for 10 minutes. This was followed by dispersing with a rotor-stator dispersing apparatus (Kinematica Polytron PT6100) over a period of 30 minutes at 10 000 rpm. To conclude, the dispersion was filtered through a 500 μm sieve.

TABLE-US-00010 TABLE Physicochemical data of dispersions D5 to D8 Comparison Invention D5 D6 D7 D8 Solids content*.sup.) % by wt. 22.0 30 33 39 Particle diameter**.sup.) nm 132 125 121 114 Viscosity***.sup.) mPa s 5600 2800 3580 5380 *.sup.)after drying to constant weight at 125° C.; **.sup.)by dynamic light scattering (Horiba LB-500); ***.sup.)at 1000 1/s; 23° C.;

[0195] Besides fumed silica with a specific surface area (BET surface area 300 m2/g), it is also possible to prepare dispersions of the invention on the basis of other fumed silicas with a specific surface area, as shown by examples D9 to D12.

Examples D9 to D12

General Preparation Instructions (For Quantities see Table)

[0196] The fumed silica powder was incorporated by stirring with a dissolver at 1500 to 5000 rpm into a mixture of 885 g of deionized water and the corresponding amount of the solution from example 1, and dispersion continued at 2000 rpm for 10 minutes. Then a rotor-stator dispersing apparatus (Kinematica Polytron PT6100) was used for dispersing at 10 000 rpm over a period of 30 minutes. To conclude, the dispersion was filtered through a 500 μm sieve.

TABLE-US-00011 TABLE Preparation parameters and physicochemical data of dispersions D9 to D12 D9 D10 D11 D12 Fumed silica type m2/g 150 200 255 255 (BET) Quantity of fumed g 472 375 335 420 silica used Quantity of solution g 26.1 27.7 31.5 39.5 from example 1 used Solids content*.sup.) % by wt. 35 30.2 28 32.6 Particle diameter**.sup.) nm 159 150 145 140 Viscosity***.sup.) mPa s 68 58 45 125 *.sup.)after drying to constant weight at 125° C.; **.sup.)by dynamic light scattering (Horiba LB-500); ***.sup.)at 1000 1/s; 23° C.;

[0197] Production of Papercoating Slips

Example S1

Comparative Example

[0198] By means of a dissolver at 500 rpm, dispersion D1 was admixed with a 12 percent strength by weight solution of polyvinyl alcohol PVA 235, from Kuraray Europe, and the system was stirred for 10 minutes. The amount of PVA 235 added was such as to produce a ratio of silicon dioxide to PVA (dry) of 5:1 (or 6:1 for S9 and S10). To adjust the viscosity, water was added in an amount such as to give the solids content indicated in the table. Then a 7 percent strength by weight solution of boric acid in water was added. The amount of the boric acid was 12.5% by weight of the amount of the polyvinyl alcohol. Lastly, the glyoxal-containing composition “Cartabond TSI” from Clariant was added. The amount corresponded to 4.8% by weight of the amount of the polyvinyl alcohol.

[0199] The viscosity of the inkjet papercoating slip was measured using a Brookfield viscometer after 24 hours.

[0200] Examples S2, S3, S4, and S9 to S12 were produced in the same way as for S1, but using the respective dispersions D2, D3, D4, and D9 to D12. The solids contents and viscosities of the papercoating slips are reproduced in table 4.

TABLE-US-00012 TABLE 3 Solids contents and viscosities of papercoating slips S1 to S4 Comparative example as per invention S1 S2 S3 S4 from D1 D2 D3 D4 Solids % by wt. 17.5 22.6 23.1 24.3 content Viscosity*.sup.) mPa s 3680 5350 3410 3200 *.sup.)Viscosity (Brookfield) at 100 rpm and 20° C.; measured after 24 h

TABLE-US-00013 TABLE 4 Solids contents and viscosities of papercoating slips S9-S12 as per invention S9 S10 S11 S12 from D9 D10 D11 D12 Solids content % by wt. 25.1 24.3 22.9 23.1 Viscosity*.sup.) mPa s 4210 2860 3410 2200

[0201] Production of the Inkjet Coating

[0202] Inventive papercoating slips S4 and S9 to S12 were applied to a photographic base paper (thickness 300 μm) using a profiled doctor bar. The wet film thickness of the papercoating slip was 80 μm. The coating was dried at 105° C. over a period of 8 minutes. The application weight achieved was a uniform 22 g/m.sup.2. The coated papers were printed on a Canon PIXMA iP6600D inkjet printer with very high resolution. The evaluation of the print outcomes is reproduced in table 5.

TABLE-US-00014 TABLE 5 Evaluation*.sup.) of the print outcomes S1 S2 S3 S4 S9 S10 S11 S12 Slip intensity 2 2 2 2 3 2.5 2 2 Resolution 2.5 2 2 2 3 3 2.5 2 Slip flow**.sup.) 1.5 1 1 1 3 2.5 2 2.5 Slip shift 1.75 1.5 1.5 1.5 3 2.5 1.75 1.5 Gloss***.sup.) 45.1 43.5 43.1 45.3 30.1 39.8 42.3 45.3 *)Best score 1, worst score 6; **)bleeding; ***)at 60° viewing angle