DE3913485A1 - FLUOROUS SILVER COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE - Google Patents

Abstract

N-alkyl-N-[3-(substituted-silyl) propyl] -perfluoroalkylsulfonamide compounds, such as C8 F17 SO2 N(C3 H7) CH2 CH2 CH2 Si (OCH3)3, are obtainable by (i) hydrosilylation of the corresponding alkyl sulphonamide or (ii) reaching appropriate perfluoroalkylsulphonamide and aminoalkylsilane compounds. The compounds have excellent water- and oil-repellency and serve as surface property improvers for various material e.g. fillers, pigments, paper, glass and metal.

Description

The invention relates to a class of novel N-alkyl-N- [3 substituted-silyl) propyl] -perfluoralkylsulfonamidverbindungen, Process for their preparation and their use. The Compounds of the invention can be used as surface modifiers be used for different substances.

Silane compounds having a perfluoroalkyl group or groups are known. Their use as release agents is discussed.

It is desirable to improve the water and oil repellent Properties and non-tackiness of the resins and inorganic substances. The traditional silane compounds  show that there are no satisfactory water and oil-repellent properties and not sufficient Non-tackiness in their use to improve the Surface properties.

Silane compounds having a perfluoroalkyl group or groups have good water and oil repellent properties, however, are still not satisfactory in terms of the adhesion to substrates and their thermal and chemical Resistance. Some of them have the disadvantage that the starting materials for their production during decompose the hydrosilylation for the purpose of their synthesis, which leads to a low product yield.

On this side, extensive investigations have been carried out been to eliminate the problems described and It has been found that certain silane compounds with a perfluoroalkyl group and a sulfonamide group in the molecule these problems are eliminated and suitable for the purpose of the invention.

The invention relates to a class of novel N-alkyl-N- [3 (Subst.-silyl) propyl] -perfluoroalkylsulfonamides of the formula

C _n F _{2 n +1} SO₂NR¹CH₂CH₂CH₂SiR² _{3 m} A _m (I)

wherein R¹ is C _1-5 alkyl, R² is C _1-5 alkyl, A is chloro, bromo or C _1-5 alkoxy, n is an integer from 4 to 12 and m is an integer from 1 to 3.

R¹ is preferably C _1-3 alkyl, R² is C _1-3 alkyl, A represents methoxy, ethoxy or chlorine, n is 6 to 10 and m 3.

More preferably R¹ is n-propyl, R² is methyl or ethyl, A is methoxy or ethoxy, n is 8 and m is 3.

The invention also relates to methods of preparation the mentioned N-alkyl-N [3- (substituted silyl) propyl] perfluoroalkylsulfonamides.

The compounds of the invention are prepared by reacting an N-allyl-N-alkyl-perfluoroalkylsulfonamide the formula

C _n F _{2n + 1} SO₂NR¹CH₂CH = CH₂ (II)

wherein R¹ and n have the above meanings, with a halo, alkoxy or haloalkoxysilane of the formula

HSiR²₃- _m A _m (III)

wherein R², A and m have the above meanings, in the presence of a addition catalyst and further reaction of the resulting addition product with a C _1-5 -alcohol, preferably when A is chlorine or bromine.

The compounds of formula II are prepared by Reaction of a perfluoroalkylsulfonyl fluoride prepared by electrolytic fluorination with an N-alkylallylamine, or by reacting a perfluoroalkylsulfonyl fluoride with an N-alkylamine to an N-alkyl perfluoroalkylsulfonamide and subsequent reaction with an allyl halide in the presence an alkali.

These compounds are manufactured by New Akita Chemical Co., Ltd. (Shin-Akita Kasei Kabushiki Kaisha) and becomes N-n-propyl-N-perfluorooctyl-allyl-sulfonamide distributed by this company.  

The compounds of general formula III are also commercially available, for. From the company Tokyo Kasei Kabushiki Kaisha.

The preferred addition catalysts for the mentioned Processes are chloroplatinic acid, azo-bis-isobutyronitrile, Benzoyl peroxide, an octacarbonyl complex of cobalt, platinum and rhodium.

In the process according to the invention, the reaction of the addition product, wherein A is chlorine or bromine, with a C _1-5 -alcohol is preferably carried out by blowing dry air into the reaction mixture or under reduced pressure. The evacuation should be chosen so that the hydrogen halide formed is removed, but it must not be too strong, so as not to cause loss of the alcohol used.

The reaction of the addition product, wherein A is chlorine or Bromine is, with the alcohol can preferably be in presence a base such as an organic amine become.

The compounds of the invention in which AC _1-5 - alkoxy, can also be prepared by reacting the addition product of the compound of formula II and the compound of formula III with a corresponding metal alkoxide.

The compounds according to the invention in which AC is _1-5 -alkoxy can also be prepared by reacting the addition product of the compound of the formula II and the compound of the formula III with an orthoformic acid ester of the corresponding alcohol.

The compounds of formula I wherein AC is _1-5 alkoxy can be prepared by reacting a compound of formula

C _n F _{2 n +1} SO ₂ Y (IV)

wherein Y is fluorine, chlorine or bromine and n has the above meanings, with an aminosilane of the formula

NR¹CH₂CH₂CH₂SiR² _{3 m} A _m (V)

wherein R¹, R², A and m have the above meanings.

In the compounds I according to the invention, the alkyl R¹ straight or branched chain.

The compound III is used in an amount of 1 molar equivalent or more, preferably 1.3 to 1.5 moles per mole Compound II. The reaction of a compound II with a Compound III is at 30 to 150 ° C, preferably 40 to 80 ° C, with stirring.

The amount of catalyst is usually from 1 × 10 ^-5 to 1 × 10 ^-2 wt .-%, preferably 1 × 10 ^-4 to 5 × 10 ^-4 wt .-%, of the amount of the compound of formula II.

The reaction of a compound I in which A is chlorine or bromine with a C _1-5 -alcohol can be easily carried out by blowing a dry inert gas into the reaction mixture at 5 to 40 ° C, preferably 10 to 20 ° C, or by stirring the Reaction mixture be carried out under reduced pressure.

The gas should be inert to the compound I in which A is chlorine or bromine and to the C _1-5 -alcohol.

Preferably, nitrogen, helium, argon, etc. are in the dried State.

The blowing of the dry inert gas is carried out to the liberated hydrogen chloride or hydrogen bromide to remove, this effect also by evacuation is achieved. If the pressure is greatly reduced, it may result from evaporation to a loss of alcohol.

If the compounds of the formula I in which AC _1-5 -alkoxy is prepared by the reaction of a perfluoroalkylsulfonyl chloride (compound of the formula IV) and an aminosilane (compound of the formula V), the compound IV is preferably employed in an amount of more than 1 Molar equivalent, preferably 1.05 to 1.2 mol, based on the amount of compound V, a.

The reaction of compound IV with compound V becomes for removing the hydrogen halide formed, preferably in the presence of an organic base such as pyridine, Triethylamine, etc. performed.

Although a solvent is not required, can nevertheless a solvent which is inert to the reaction mixture not used on special solvents is limited. Concrete examples of such Solvents are ethers such as THF, isopropyl ether, etc. Although the reaction temperature varies depending on the one used Solvent can be different, it moves nevertheless usually between room temperature and 100 ° C and is preferably 20 to 50 ° C.

The sulfonamide portion of the compounds of the invention improves the yield in the hydrosilylation in their Synthesis and leads to a better alignment of the perfluoroalkyl group  when used as a means of change the surface properties than with carboxylic acid or Carboxylic acid amide compounds is the case and causes it an improvement of the water and oil repellent properties and the non-tackiness of the substrate.

In addition, the alkyl group attached to the nitrogen atom favors the miscibility with organic solvents.

The compounds of the invention can be as water and oil repellents, agents for modifying surface properties and used for various other purposes become. The invention provides filler powder or Short fiber filler ready with one surface connected silane compounds are connected or attach to them.

The invention also provides fluororesin compositions ready containing an inorganic filler containing with one of the mentioned silane compounds was treated.

The invention also provides water and oil repellent Paper and glass ready with the described silane compounds or substances containing them were.

The invention also provides weather-resistant building materials prepared their surface with the described silane compounds was treated.

The invention also provides water and oil repellent and non-solderable electrically conductive metal materials ready to have its surface with one of the described Silane compounds was treated.  

The invention also provides inorganic pigments and Filler prepared with the described silane compounds were treated and a high dispersibility in have organic solvents and coating materials (Paints) of lower viscosity.

The water and oil repellent properties and the Non-tackiness of the compounds of the invention are based on their perfluoroalkyl group and that their halogen and alkoxy groups with water to form of hydroxysilyl groups which react with the hydroxy groups on the surface of inorganic Substances by dehydration condensation, hydrogen bonding etc. connect.

If the compound of the invention on the surface applied or incorporated into a material, It is usually used as a solution in an organic solvent used. The method of application and mixing is not limited. Preferably, the compound becomes in an anhydrous chlorinated or fluorinated Solvent, in acetone, THF, hexane, an alcohol and the like, or a mixture thereof, wherein a small amount of an aqueous solution of an amine or an acid is added and the solution is applied to the surface of the object according to a known method, such as by spraying, Immersion, etc. is applied.

The invention will be described below by embodiments illustrated:

Example 1

Into a 500 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a reflux condenser,  108.1 g (0.200 M) of N-n-propyl-N-perfluorooctylsulfonamide ("EF-111" from New Akita Chemical Co.), 15.4 g Add 85% KOH (0.0233 M) and 200 mL of acetone, then This mixture, 30.71 g (0.254 M) of allyl bromide at room temperature be dropped over 10 minutes. After that will stirred for 4 hours. Then the reaction mixture filtered off and the filtrate was concentrated by distillation until the volume is reduced to 100 ml. After that it will be in poured a 5% aqueous ammonium chloride solution. The organic Layer is collected and vacuum distillation subjected to N-n-propyl-N-allyl perfluorooctylsulfonamide receives.

Then in a 100 ml three-necked flask equipped with a magnetic stirrer, thermometer and reflux condenser, 96.9 g (0.167 M) of Nn-propyl-N-allyl perfluorooctylsulfonamide and 5 mg of a 0.1 M isopropanol solution of chloroplatinic acid hexahydrate (9.67 x 10 ^-3 mmol) and 25.3 ml (0.250 M) of trichlorosilane was added dropwise over 30 minutes.

After completion of the addition of trichlorosilane is stirred for 2 hours. The vacuum distillation of the reaction mixture gives 110.3 g (0.1539 M) of Nn-propyl-N- [3- (trichlorosilyl) propyl] perfluorooctylsulfonamide.
Yield: 92.3%; Bp 153 ° C / 2.0 mmHg. The compound was identified as

by NMR analysis, MS analysis and IR spectrophotometric Analysis.  

Conditions and Results of NMR and MS Analysis:

H-NMR analysis:
Solvent Flon-113 (1,1,2-trichloro-2,2,1-trifluoroethane), internal standard: benzene
δ 1.30 (t, 3H, Ha), δ 1.6-2.5 (m, 6H, Hb, d, e), δ 3.5-4.0 (m, 4H, Hc, f)
MS analysis:
Ionization voltage: 70eV
m / e, relative intensity and fragment and their order: 554, 60.5%, M⁺-⁺CH₂CH₂SiCl₃; 133, 15.0%, ⁺SiCl₃, 69, 100%, ⁺CF₃

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130 (cm ^-1 ).

example 2

Into a 300 ml four-necked flask equipped with a mechanical stirrer, a trap, a thermometer and a reflux condenser and a water aspirator connected thereto were added 48.1 g (0.0671 M) Nn-propyl-N- [3- (trichlorosilyl) - Propyl] -perfluoroctylsulfonamide and added dropwise 50 ml of methanol for 2 hours at 15 to 20 ° C under reduced pressure. Thereafter, 40.1 g (0.057 M) of Nn-propyl-N- [3- (trimethoxysilyl) propyl] perfluorooctylsulfonamide are obtained by vacuum distillation.
Yield: 85.0%; Bp 134 ° C / 0.25 mmHg. The compound was identified as:

by NMR analysis, MS analysis and IR spectrophotometric Analysis.  

Conditions and results of the analyzes:

H-NMR analysis:
Solvent: Flon-113, internal standard: benzene
δ 0.9 (t, 2H, He), δ 1.25 (t, 3H, Ha), δ 1.6-2.5 (m, 6H, Hb, e, f), δ 3.5-4 , 0 (m, 4H, Hc, g), w 3.8 (s, 9H, Hd)

MS analysis:
Ionization voltage: 70 eV
m / e, relative intensity and fragment and their order: 672, 22.6%, M⁺-⁺OCH₃;
554, 1.8%, M⁺-⁺CH₂CH₂Si (OCH₃) ₃, 121, 100%, ⁺Si (OCH₃) ₃; 69, 23%, ⁺CF₃

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130, 1090 (cm ^-1 ).

example 3

Into a 300 ml four-necked flask with a magnetic stirrer, a Thermometer and a reflux condenser with an associated Trap and a nitrogen inlet tube are 50.2 g (0.070M) M-n-propyl-N- [3- (trichlorosilyl) propyl] perfluorooctylsulfonamide given, after which at 10 to 15 ° C during 5 hours 50 ml of methanol dripped and through the soil the piston is injected with nitrogen gas intensively. To Completion of the addition of the methanol becomes the reaction mixture further stirred for 5 hours. Then you get by removal of the excess methanol by vacuum distillation 38.2 g (0.054 M) of N-n-propyl-N- [3- (trimethoxysilyl) - propyl] -perfluoroctylsulfonamid. Yield: 77%.  

example 4

Into a 500 ml three-necked flask with a mechanical stirrer, a thermometer, a reflux condenser and a Dropping funnels are 143.3 g (0.20 M) powdered N-n- Propyl-N- [3- (trichlorosilyl) propyl] -perfluoroctylsulfonamid and 121.2 g (1.2 M) of triethylamine, after which for 2 hours at 15 to 20 ° C 96 g (3.0 M) of methanol Dripped with stirring, the flask through ice-water is cooled.

After the addition of the methanol, the resulting salt is filtered off. By vacuum distillation gives 130.9 g (0.186M) N-n-Propyl-N- [3- (trimethoxysilyl) -propyl] perfluorosulfonamide. Yield: 92.0% bp. 134 ° C / 0.25 mmHg.

example 5

Into a 300 ml three-necked flask with a mechanical stirrer, a reflux condenser and a dropping funnel 71.7 g (0.10 M) of N-n-propyl-N- [3- (trichlorosilyl) propyl] - perfluorooctylsulphonamide, followed by 15 to 20 ° C during 2 hours 75 g of a 28% methanol solution of CH₃ONa added dropwise.

After the addition of the methoxide, the resulting salt is filtered off. By vacuum distillation, 65.4 g (0.093 M) N-n-propyl-N- [3- (trimethoxysilyl) propyl] -perfluoroctylsulfonamid receive. Yield: 93.0%.

example 6

In a 300 ml four-necked flask with a mechanical stirrer and a reflux condenser, 83.6 g (0.10 M) of N-ethyl N- [3- (tribromosilyl) propyl] perfluorooctylsulfonamide and Add 133.2 g (0.9 M) of ethyl orthoformate. This mixture 3.0 g of aluminum chloride are added as catalyst, after which the mixture is reacted at 80 ° C for 12 hours leaves.  

Upon completion of the reaction, 55.6 g (0.076 M) are obtained. N-Ethyl-N- [3- (triethoxysilyl) propyl] -perfluoroctylsulfonamid by vacuum distillation. Yield: 76.1%, bp. 146 ° C / 0.18 mmHg.

example 7

Into a 100 ml three-necked flask equipped with a magnetic stirrer, thermometer and reflux condenser are added 53.1 g (0.10 M) of Nn-propyl perfluoroheptylsulfonamide from New Akita Chemical Co., and 10 mg (1.9 x 10 ^-5 M) of chloroplatinic acid, followed by dropping 14.9 g (0.11 M) of trichlorosilane for one hour at 60 ° C via a dropping funnel. After further stirring for 1 hour, the excess trichlorosilane is removed by distillation to obtain 61.3 g of Nn-propyl-N- [3- (trichlorosilyl) propyl] perfluoroheptylsulfonamide. Yield: 92%. The compound was identified as:

by 1 HNMR analysis, MS analysis and IR spectrophotometric Analysis.

Conditions and results of the analyzes:

H-NMR analysis:
Solvent: Flon-113, Internal Standard: Benzene
δ 1.25 (t, 3H, Ha), w 1.6-2.5 (m, 6H, Hb, d, e), δ 3.5-4.0 (m, 4H, Hc, g), δ (s, 9H, Hd)

MS analysis:
Ionization voltage: 70eV
m / e, relative intensity and fragment and their order: 504, 68.1%, M⁺-⁺CH₂CH₂SiCl₃; 133, 21.1%, ⁺SiCl₃; 69, 100%, ⁺CF₃.

IR photospectrometry:
Sample: pure
3350, 2950, 1390, 1260-1130 (cm ^-1 )

example 8

In a 500 ml three-necked flask with a magnetic stirrer, a Thermometer and a reflux condenser are 133.3 g (0.20 M) N-n-propyl-N- [3- (trichlorosilyl) propyl] -perfluorheptylsulfonamid New Akita Chemical Co., according to which 200 ml of methanol are added dropwise through a dropping funnel for 5 hours at 35 ° C under reduced pressure of 70 mmHg admitted. After the addition of the methanol is obtained by Vacuum Distillation 105.8 g of N-n-propyl-N- [3- (trimethoxysilyl) - propyl] -perfluorheptyl-sulfonamide.

Yield: 81%. The compound was identified as:

by 1 HNMR analysis, MS analysis and IR spectrophotometric Analysis.

Conditions and results of the analyzes:

H-NMR analysis:
Solvent: Flon-113, internal standard: benzene
δ 0.9 (t, 2H, He), δ 1.25 (t, 3H, Hc), δ 1.6-2.5 (m, 6H, Hb, f), δ 3.5-4.0 (m, 4H, Hc, g), δ 3.8 (s, 9H, Hd)

MS analysis:
Ionization voltage: 70eV
m / e, relative intensity and fragment and their order: 622, 24.5%, M⁺-⁺OCH ^d 3; 504, 3.4%, M⁺-⁺CH₂CH₂Si (OCH₃) ₃; 121, 100% ⁺Si (OCH₃) ₃; 69, 100%, ⁺CF₃

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130, 1090 (cm ^-1 )

example 9

Into a 300 ml three-necked flask equipped with a magnetic stirrer, thermometer and reflux condenser are added 73.4 g (10.20 M) of N-ethyl-N-allyl perfluorobutylsulfonamide and 5 ml of 0.1 M isopropanol solution of chloroplatinic acid (9.67 g) × 10 ^-3 mmol), followed by dripping at 60 ° C for 1 hour 27.6 g (0.24 M) of methyldichlorosilane. After completion of the addition, stirring is continued for 1 hour at the same temperature. The unreacted N-ethyl-N-allylperfluorobutylsulfonamide and methyldichlorosilane are distilled off to obtain 73.1 g of N-ethyl-N- [3- (dichloromethylsilyl) -propyl] -perfluorobutylsulfonamide. Yield: 76%. The compound was identified as

by 1 HNMR analysis, MS analysis and IR spectrophotometric Analysis.

Conditions and results of these analyzes:

H-NMR analysis:
Solvent: Flon-113, internal standard: benzene
δ 0.10 (s, 3H), δ 1.30 (t, 3H), δ 1.65-2.5 (m, 4H), δ 3.5-4.0 (m, 4H)

MS analysis:
Ionization voltage: 70eV
m / e and relative intensity: 339, 56.2%, 113, 24.6%; 69, 100%

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130 (cm ^-1 ).

example 10

Into a 300 ml three-necked flask with a magnetic stirrer, a thermometer and a reflux condenser are 48.2 g (0.10M) N-ethyl-N- [3- (dichloromethylsilyl) propyl] -perfluorobutylsulfonamide, 40.4 g (0.40 M) of triethylamine and 150 ml Isopropyl ether was added, followed by 30 ml during 2 hours Ethanol, the flask being cooled by ice-water becomes. Thereafter, it will be at the same temperature for 1 hour further stirred. The resulting salt is filtered off and the excess ethanol, the isopropyl ether and the triethylamine are distilled off, giving 38.6 g of N-ethyl N- [3- (diethoxymethylsilyl) propyl] -perfluorbutylsulfonamid receives. Yield 77%. The compound was identified when:

by 1 HNMR analysis, MS analysis and IR analysis.

Conditions and results of the analyzes:

H-NMR analysis:
Solvent: Flon-113, internal standard: benzene δ 0.10 (s, 3H), δ 1.31 (t, 3H), δ 1.42 (t, 6H), δ 1.6-2.5 (m , 4H), δ 3.5-4.1 (m, 8H)

MS analysis:
Ionization voltage: 70eV
m / e and relative intensity in order: 370, 58.9%; 131, 100%, 69, 84.1%

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130, 1090 (cm ^-1 )

example 11

Into a 200 ml three-necked flask with a magnetic stirrer, a thermometer and a reflux condenser are 18.9 g (0.20 M) N-ethyl-N [3- (monoethoxydimethylsilyl) propyl] amine, 15.8 g (0.20 M) of pyridine and 100 ml of isopropyl ether, followed by 30.2 g (0.10 M) at 20 ° C. for 1 hour Perfluorobutylsulfonyl fluoride dropped through a dropping funnel. The reaction mixture is for 2 hours at this Stirred and then for 1 hour at 40 ° C. further stirred. Thereafter, the resulting salt is filtered off and the excess pyridine and the isopropyl ether distilled off to give 18.4 g of N-ethyl-N- [3- (monoethoxydimethylsilyl) propyl] -perfluorbutylsulfonamid. yield 39%. The compound was identified as:

by 1 HNMR analysis, MS analysis and IR spectrophotometric Analysis.

Conditions and results of the analyzes:

H-NMR analysis:
Solvent: Flon-113, internal standard: benzene
δ 0.1 (s, 6H), w 0.9 (t, 2H), δ 1.3d (t, 3H), δ 1.6-2.5 (m, 2H), δ 3.5-4 , 1 (m, 4H), δ 3.8 (s, 3H)

MS analysis:
Ionization voltage: 70eV
m / e and relative intensity: 426, 12.3%; 103, 62.2%; 69, 100%

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130, 1090 (cm ^-1 )

example 12

In a 50 ml three-necked flask equipped with a magnetic stirrer, thermometer and reflux condenser are added 20.4 g (30 mM) of Nn-propyl-N-allyl perfluorodecylsulfonamide from New Akita Chemical Co., and 5 mg (1.0 × 10 -4) ^{. 6} M) of chloroplatinic acid, after which 4.5 g (33 mM) of trichlorosilane are added dropwise through a dropping funnel for 20 minutes at 80 ° C. Thereafter, stirring is continued for 1 hour at the same temperature. The excess trichlorosilane is distilled off to give 22.8 g of Nn-propyl-N- [3- (trichlorosilyl) propyl] perfluorodecylsulfonamide. Yield: 93%. The compound was identified as:

by 1 HNMR analysis, MS analysis and IR spectrophotometric Analysis.

Conditions and results of the analyzes:

H-NMR analysis:
Solvent: Flon-113, internal standard: benzene
δ 1.31 (t, 3H), δ 1.7-2.6 (m, 6H), δ 3.6-4.1 (m, 4H)

MS analysis:
Ionization voltage: 70eV
m / e and relative intensity in their order:
654, 72.3%; 133, 24.6%; 69, 100%

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130 (cm ^-1 ).

example 13

In a 100 ml three-necked flask with a magnetic stirrer, a thermometer and a reflux condenser are 16.3 g (20 mM) N-n-propyl-N- [3- (trichlorosilyl) propyl] perfluorodecylsulfonamide given, after which at 40 ° C under reduced Pressure (60 mmHg) dropwise during 1 hour, 20 ml of methanol. By distilling off the excess methanol to obtain 12.1 g of N-n-propyl-N- [3- (trimethoxysilyl) propyl] - perfluordecylsulfonamid. Yield: 75%. The connection was identified as:

by 1 HNMR analysis, MS analysis and IR spectrophotometric Analysis.

Conditions and results of the analyzes:

H-NMR analysis:
Solvent: Flon-113, internal standard: benzene
δ 0.9 (t, 2H), δ 1.24 (t, 3H), δ 1.63-2.52 (m, 6H), δ 3.4-3.9 (m, 4H), δ 3 , 8 (s, 9H)

MS analysis:
Ionization voltage: 70eV
m / e and relative intensity in order: 772, 29.4%; 654, 5.6%; 121, 100%, 69, 89.1%.

IR spectrophotometry:
Sample: pure
3350, 2950, 1390, 1260-1130, 1090 (cm ^-1 ).

The fluorine-containing silane compounds according to the invention have excellent water and oil repellent properties.

example 14

An ordinary glass plate (24 mm × 75 mm) will during Immersed in a solution of 1.0 g for 30 sec

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂Si (OCH₃) ₃,

100 g of ethanol and 0.5 g of a 10% aqueous HCl solution consists. The glass plate is dried at room temperature, after which the contact angle of the plate was measured becomes. For water it is 110 ° and for liquid paraffin 75 °.

Comparative Example 1

The procedure of Example 14 will be repeated, but only 1.0 g instead of the fluorine-containing silane compound CH₃Si (OCH₃) ₃ used. The contact angle is for Water 35 ° and for liquid paraffin 37 °.

Comparative Example 2

The procedure of Example 14 will be repeated, but only 1.0 g instead of the fluorine-containing silane compound NH₂CH₂CH₂NHCH₂CH₂CH₂CH₂Si (OCH₃) ₃ used. The Contact angle is 27 ° for water and liquid Paraffin 34 °.  

example 15

An ordinary glass plate (25 mm × 75 mm) is left for 1 min dipped in a solution consisting of 1.0 g of N-ethyl-N- [3- (triethyloxysilyl) propyl] perfluorohexylsulfonamide, 200 ml of ethanol and 0.5 g of a 10% HCl solution. The glass plate will dried at room temperature.

The contact angle of the thus treated plate is for water 110 ° and for liquid paraffin 76 °.

Comparative Example 3

The procedure of Example 15 will be repeated, but only 1.0 g of trimethoxymethylsilane instead of the fluorine-containing silane compound used. The contact angle is for water 35 ° and for liquid paraffin 37 °.

Comparative Example 4

The procedure of Example 15 will be repeated, but only in place of the fluorine-containing silane compound, 1.0 g of 3-trimethoxysilylpropyl perfluoroheptyl carbonate used. The contact angle is 81 ° for water and for liquid paraffin 49 °.

example 16

3 g of N-n-propyl-N- [3- (trimethoxysilyl) propyl] -perfluorobutylsulfonamide are used with 100 g of epoxy resin as a primer (a melamine-curable epoxy resin from Tokyo Paint Kabushiki Kaisha), followed by mixing on a steel test plate (50 mm × 100 mm × 1 mm) of the company Nippon test panel Kabushiki Kaisha to a thickness of 0.1 mm and cures at 120 ° C for 20 min. The contact angle of the surface is used as an index for the water and oil repellent properties measured. The angle is 112 ° for water and for liquid paraffin 85 °.  

Comparative Example 5

The epoxy resin used in Example 16 is applied to a Steel test plate (50 mm × 100 mm × 1 mm) from Nippon Test panel Kabushiki Kaisha up to a thickness of 0.1 mm applied without the addition of the fluorine-containing silane compound and cured at 120 ° C for 20 min. The test on water and oil-repellent properties will be among them Conditions performed as in Example 16. The contact angle is 33 ° for water and for liquid paraffin 12 °.

Comparative Example 6

The procedure of Example 16 was repeated with 3 g of 2-trifluoromethyl Repeats 1-trimethoxysilylethane. The contact angle is 45 ° for water and for liquid paraffin 23 °.

Are inorganic fillers such as glass fibers, glass beads, Alumina, graphite, carbon fibers, molybdenum disulfide, metal powder such as bronze powder, lead powder, etc. with the invention fluorine-containing silane compound treated easily with fluorine resins such as polytetrafluoroethylene, Polychlorotrifluoroethylene, poly (vinylidene fluoride), poly (vinyl fluoride), Hexafluoroethylene-hexafluoropropene copolymer, Tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether Copolymer, chlorotrifluoroethylene-ethylene Copolymer, etc. are mixed with good affinity, wherein the obtained resin mixture excellent printing and Abrasion resistance shows.

Usually, 0.1 to 20% by weight of the fluorine-containing silane compound, based on the filler weight used.

example 17

50 g glass fibers (diameter approx. 3 μm and length approx. 50 μm)  are dissolved in 500 ml of an ethanol solution of 2.5 g

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃

dipped with 1% by weight of a 10% aqueous HCl solution, then the mixture with an electric shaker is stirred vigorously for 10 min at room temperature. The thus treated with the fluorine-containing silane compound Glass fibers are made with polytetrafluoroethylene powder mixed at a weight ratio of 50:50, followed by the mixture by a pressure of 400 kg / cm² a diameter of 172 mm and a thickness of 10 mm compacting piece is compacted. The piece will then baked at 370 ° C for 1 hour, whereby polytetrafluoroethylene reinforced glass fibers.

The compressive strength (compression speed 3 mm / min) as well as the friction and abrasion resistance. The compressive strength becomes at a compression speed measured at 3 mm / min, the friction and Abrasion properties are measured using the abrasion tester measured by Suzuki. The results are together with the results of the following comparative example in Table 1 summarized.

Comparative Example 7

The methodology of Example 17 was repeated, the same Glass fibers were used, but not with the fluorine-containing silane compound had been treated. In this way you get a glass fiber reinforced piece made of polytetrafluoroethylene. With this piece of resin, the Tests performed. The results are summarized in Table 1.  

Table 1

example 18

In a 1 liter three-necked flask with a thermometer, a Stirrer and a reflux condenser are 50 g of graphite powder after which, while stirring, 100 ml a 10 wt .-% solution of the same fluorine-containing silane compound as in Example 17 dropped. After that it will be Mixture heated to 100 ° C to remove the solvent. The graphite powder obtained in this way is with the same polytetrafluoroethylene resin, after which performs the same tests. The results are in table 2 summarized.  

Comparative Example 8

The procedure and tests of Example 17 are with untreated Graphite powder repeated. The results are summarized in Table 2.

Table 2

Are inorganic fillers such as silica, tin oxide, Titanium oxide, aluminum oxide, silicon nitride, graphite, zinc oxides, Iron oxides, mica, glass fibers, carbon fibers, asbestos etc. with the fluorine-containing silane compound of the invention treated, one receives products with excellent water and oil repellent properties and non-tackiness.

Usually, based on the weight of the filler, 0.1 to 20 wt .-% of the fluorine-containing silane compound.

example 19

50 g of silica powder (diameter about 1 micron) are with 500 ml ethanol solutions, each 0.1, 1, 5 and 10% by weight C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃, based on the weight of the filler, and 1% by weight of a 10% aqueous HCl solution, mixed, after which the mixture with the help of an electric shaking device  Stirred vigorously for 10 minutes at room temperature.

The mixture is carried through to remove the solvent Evaporated to 100 ° C heated, which gives the with the fluorine-containing silane compound treated silica powder receives. In essence, the entire amount is liable added fluorine-containing silane compound on the silica powder.

The IR absorption spectra of the thus treated silica powders are measured by the powder reflection method. It is found to be absorbed by the CH bond at 2850-2950 cm ^-1 due to the sulfonamide bond at 1390 cm ^-1 and due to the CF bond at 1100-1300 cm ^-1 . It is thus found that the fluorine-containing silane compound is present on the surface of the silica powder.

Measured then the water-repellent properties the treated silica powder. These are with Mixed 500 ml of water and with an electric shaker Strong for 15 minutes at room temperature touched. The water-repellent properties are with evaluated to the naked eye.

Comparative Example 9

Repeat the procedure of Example 19 using from

The results are shown in Table 3 together with those Example 19 summarized.  

Table 3

example 20

In a 1 liter three-necked flask with a thermometer, a Stirrer and a reflux condenser are 50 g alumina powder (Diameter about 1 micron), after which one during a With stirring 50 ml of the solutions (5, 10, 20 and 25 % By weight) of the same fluorine-containing silane compound. Thereafter, each mixture to remove the solvent heated to 100 ° C. In this way you get with alumina powder treated with the same fluorine-containing silane compound.

It has been proved that the fluorine-containing silane compound adheres to the surface of the alumina powder, wherein the IR absorption spectra according to the powder reflection method as determined in Example 19.  

Comparative Example 10

Repeat the procedure of Example 19 using of CF₃CH₂CH₂CH₂Si (OCH₃) ₃ as a silane compound. The results are shown in Table 4 together with those of Example 19 indicated.

Table 4

example 21

50 g of silica powder (diameter about 10 microns) are with 500 ml ethanol solutions, each 0.1, 1, 5 and 10% by weight C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃, based on the weight of the filler, and 1% by weight of a 10% aqueous HCl solution, mixed, after which the mixture with the help of an electric shaker 20 min stir vigorously at room temperature.

The mixture is heated by evaporation to 100 ° C to remove the ethanol, thereby obtaining the siliceous powder treated with the fluorine-containing silane compound. The IR absorption spectra of the thus treated silica powders are measured by the powder reflection method. It is found that it comes due to the CH bond at 2850-2950 cm ^-1 for absorption, due to the SO₂N bond at 1390 cm ^-1 and due to the CF bond at 1100-1300 cm ^-1 . It is thus found that the fluorine-containing silane compound is present on the surface of the silica powder.

The silica powders treated in this way become with 50 wt .-% epoxy resin as a primer (one with melamine curable epoxy resin from Tokyo Paint Kabushiki Kaisha) mixed, after which the mixture is applied to the surface of Test plates made of steel up to a thickness of 100 microns applies. The coatable test plates are then at 140 ° C cured for 20 minutes and then water resistance checked, d. H. the plates will be in during 2 hours heated in an autoclave, the water under a pressure of Contains 5 bar. Thereafter, the water content of the coating measured. The results are summarized in Table 5.

Comparative Example 10

Repeat the procedure of Example 21 using of CH₃Si (OCH₃) ₃.

The results are summarized in Table 5.

Table 5

Example 22

In a 1 liter three-necked flask with a thermometer, a Stirrer and a reflux condenser are 50 g alumina powder (Diameter about 10 microns), after which during 1 With stirring 50 ml of the same fluorine-containing silane compound as in Example 21 (5, 10, 20 and 25% by weight) added dropwise. Thereafter, the mixture for separating the solvent heated to 100 ° C. Proof of presence the fluorine-containing silane compound on the surface the treated silica powder is passed through the IR absorption spectra using the powder reflection method obtained as described in Example 21. Also will the same water resistance test was carried out as in Example 21.

The results are summarized in Table 6.

Comparative Example 11

The method and the tests of Example 22 are under Use of CH₃Si (OCH₃) ₃ repeatedly, in Comparative Example 10 is used as the silane compound. The results are in comparison with those of Example 22 in Table 6 summarized.

Table 6

example 23

The procedure of Example 22 is repeated using alumina powder (Diameter approx. 5 μm) repeated. The results are summarized in Table 7.

Comparative Example 12

The procedure of Example 23 is repeated using NH₂ (CH₂) ₃Si (OCH₃) ₃ repeated as a silane compound. The Results are in Table 7 for comparison with Example 23 summarized.

Table 7

example 24

The procedure of Example 22 is repeated with 50 g of alumina powder  (Diameter not greater than 5 microns) repeated. The results are summarized in Table 8.

Comparative Example 13

The procedure of Example 22 is repeated using NH₂ (CH₂) ₃Si (OCH₃) ₃ repeated as a silane compound. The results are in Table 8 for comparison with Example 24 summarized.

Table 8

example 25

50 g glass fibers (diameter about 3 microns and average Length approx. 50 μm) are mixed with 500 ml acetone solutions, the different amounts

(C₈F₁₇SO₂N (C₂H₅) CH₅) CH₂CH₂CH₂Si (OCH₃) ₃

and 1% by weight of a 10% aqueous HCl solution, after which the mixture is stirred for 20 minutes at room temperature. The concentrations of the fluorine-containing silane compound in these solutions are 0.1, 1, 5 and 10 wt .-%, based on the weight of the glass fibers. After 30 minutes, the acetone is removed by heating to 100 ° C, after which the treated glass fibers are tested for their IR spectrum by the diffusion reflection method. Thereby, absorptions at 2859-2950 cm ^-1 (CH), 1390 cm ^-1 (SO₂N) and 1100-1300 cm ^-1 (CF) are detected, confirming that the fluorine-containing silane compound is present on the surface of the glass fibers. The glass fibers thus treated are mixed with an acrylic resin-based self-curing paint base made by Tokyo Paint Kabushiki Kaisha in an amount of 50% by weight, after which the mixture is poured into a mold (10 cm × 10 cm × 10 cm) and at 150 ° C is cured for 30 min. The piece of acrylic resin thus obtained is subjected to a water resistance test with steam at 5 bar for 2 hours as described in Example 21. The water content is then measured. The results are summarized in Table 9.

Comparative Example 14

The procedure of Example 25 is repeated using CH₃Si (OCH₃) ₃ repeated as a silane compound and the Results are summarized in Table 9.

Table 9

Are metal materials such as copper, aluminum, iron, lead, Zinc, tin, titanium, cobalt, nickel, chromium, etc., alloys such as stainless steels, Hastelloy®, Incone®, Stellite® etc., magnetic alloys such as Sm-Co alloy, Nd-Fe-B alloy etc. with the fluorine-containing silane compound of the invention treated, you get excellent water and oil repellent properties. The metallic materials can in the form of sheets, balls, ribbons, etc. be used.

Are organic resin substances such as phenol, furan, xylene Formaldehyde, ketone-formaldehyde, urea, melamine, Aniline, epoxy, poly (vinyl acetate), polyacrylic, poly, methacrylic, poly (vinyl chloride), poly (vinylidene chloride), Polyacrylonitrile, polyvinyl ether, polycarbonate, polyamide, Polyurethane resin, etc. including almost all Hydrocarbon resins with the fluorine-containing invention Silane compound treated, take these substances excellent water and oil repellent properties on. The resins can be in the form of sheets, films or fibers or in another form. Adhesion and the effect of the compounds of the invention not affected by the shape of the substrates.

Is also paper with the novel fluorine-containing Treated silane compound, it takes excellent water and oil repellent properties. The term includes "Paper" machine made or handmade Paper, cardboard, corrugated cardboard, etc.

The fluorine-containing silane compound of the present invention can be used for Awarded excellent water and oil repellent Properties are applied to glass.  

The fluorine-containing silane compound of the present invention can be used when it is intended to add paper to the pulp become.

The fluorine-containing silane compound of the present invention can the surface of different substances by mixing with one Resin coating mixture are applied.

Example 26

A 0.5% acetone solution of C₈F₁₇SO₂N (C₄H₉) CH₂CH₂CH₂- Si (OC₂H₅) ₃ with 0.5 wt .-% of a 10% aqueous acetic acid solution is applied to an aluminum plate (100 mm × 50 mm × 1 mm) applied.

The contact angles of this plate for water and liquid Paraffin are used for the evaluation of their water and oil repellent Measured properties. The results are in table 10 summarized.

Comparative Example 15

An aluminum plate according to Example 26 is provided with a self-hardening paint base on acrylic resin basis of the company Tokyo Paint Kabushiki Kaisha, up to a coating weight coated by 3 wt .-%.

The water and oil repellent properties are measured the aluminum plate. The results are summarized in Table 10 summarized with the results of Example 26.  

Table 10

example 27

A 5% acetone solution of C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃ with 1% by weight of a 10% aqueous HCl solution is applied to a copper plate (100 mm × 50 mm 1 mm).

The plate is dried at 80 ° C for one hour. The coated copper plate is examined by IR spectrophotometry to find absorption of the CF bond at 1100-1300 cm ^-1 , confirming the adhesion of the fluorine-containing silane compound.

The plate is dipped in a 5% aqueous saline solution, after which one measures the weight loss.

Comparative Example 16

The same copper plate as in Example 27, not with the fluorine-containing silane compound was treated, is opened same way tested. The results of Example 27 and of Comparative Example 16 are summarized in Table 11.

Table 11

Example 28

A 5% aqueous ethanol solution of

C₈F₁₇SO₂N (C₂H₅) CH₂CH₂CH₂Si (OC₂H₅) ₃

with 0.5% by weight of a 10% aqueous n-propylamine solution is applied to a steel plate (100 mm × 50 mm × 1 mm).

The plate is allowed to stand outdoors, after which the staining rated.

Comparative Example 17

The procedure of Example 28 is repeated using a untreated steel plate repeated. The results are summarized in Table 12.

Table 12

example 29

5 g of C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OCH₃) ₃ are with 100 g of epoxy resin as primer (a melamine curable Epoxy resin from Tokyo Paint Kabushiki Kaisha). The paint is applied to a test plate (100 mm × 50 mm × 1 mm) the company Nippon test panel Kabushiki Kaisha, up to one Thickness of 0.1 mm applied, after which the plate during 20 is cured at 120 ° C min. The evaluation of the water and Oil-repellent properties are made by measuring the contact angle for water and oil.

Comparative Example 18

Using the epoxy resin paint substrate accordingly Example 29, but without F-containing silane compound becomes a Test plate prepared, which is tested as in Example 29. The results are summarized in Table 13.

Table 13

example 30

The epoxy resin color base used in Example 29 becomes on a test plate (100 mm × 50 mm × 1 mm) from Nippon Test panel Kabushiki Kaisha up to a thickness of 0.1 mm applied, after which the plate for 30 minutes at 80 ° C precured becomes.

This plate is placed in a 10 wt% Flon-113 solution of

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃

immersed for 10 seconds and cured at 120 ° C for 20 min. The thus-treated plate is examined by IR spectrophotometry, whereby absorption of the CF bond at 1100-1300 cm ^{-1 is} detected. The water and oil repellency properties of this panel are tested in the same way.

Comparative Example 19

The procedure of Example 30 is repeated using the F-containing surfactant C₈F₁₇SO₃Na repeated. The water- and oil-repellent properties are the same way checked.

Table 14

example 31

An acrylic resin base (self-curing acrylic resin the company Tokyo Paint Kabushiki Kaisha) is on a Test plate (100 mm × 50 mm × 1 mm) from Nippon Test Panel Kabushiki Kaisha, to a thickness of 0.1 mm applied, then cured at 170 ° C for 20 min becomes. This plate is poured into a 10 wt .-% acetone solution from

C₈F₁₇SO₂N (C₂H₅) CH₂CH₂CH₂Si (OCH₃) ₃

immersed for 30 seconds and dried at room temperature. The thus-treated plate is examined by IR spectrophotometry, whereby absorption of the CF bond at 1100-1300 cm ^{-1 is} detected. The adhesion of the F-containing silane compound is detected.

Comparative Example 20

The procedure of Example 31 is repeated using a F-containing surfactant C₇F₁₅CO₂K instead of the F-containing Silane compound repeated. By IR spectrometry no C-F bond is detected.

The water and oil repellent properties are on the same Way tested. The results are summarized in Table 15.

Table 15

example 32

Commercially available DIN A4 stationery from Kokuyo Kabushiki Kaisha is added to a 3% by weight acetone solution

C₈F₁₇SO₂N (C₃F₇) CH₂CH₂CH₂Si (OCH₃) ₃

Dipped for 5 minutes and then dried for 2 hours at room temperature. In this way, a paper impregnated with the F-containing silane compound is obtained. This is checked by IR spectrophotometry, which shows an absorption of the CF bond at 1100-1300 cm ^-1 . This proves the adhesion of the F-silane compound.

After dripping with water and liquid paraffin on the Paper is measured and evaluated for absorption.

Comparative Example 21

The procedure of Example 32 is repeated with the same paper, which was not treated, repeated. The results from Example 32 and Comparative Example 21 are in Table 16 summarized.

Table 16

Example 33

Based on the weight of the pulp, this 2%

C₈F₁₇SO₂N (C₂H₅) CH₂CH₂CH₂Si (OCH₂CH₅) ₃

added, after which paper is made.

Infrared spectrophotometrically, an absorption of CF bond at 1100-1300 cm ^{-1 is} observed.

In the same way as in example 32, the water and oil-repellent properties.

Comparative Example 22

The procedure of Example 33 is repeated, but without the F-silane compound. The results from Example 33 and Comparative Example 22 are summarized in Table 17.  

Table 17

example 34

Commercially available corrugated cardboard from Kashiwaya Shiki Kogyo Kabushiki Kaisha, is added to a 5 wt% benzene solution from

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃

Dipped for 3 minutes and then for 1 hour at 50 ° C dried.

The cardboard is examined by IR spectrophotometry, which shows an absorption of the CF bond at 1100-1300 cm ^-1 . This confirms the presence of the F-containing compound.

Water and oil repellent properties are on the same Worth way.

Comparative Example 23

The procedure of Example 34 is repeated using

C₈F₁₇SO₂N (C₂H₅) CH₂CH₂PO (ONa) ₂

repeated in place of the F-containing silane compound. The results from Example 34 and Comparative Example 23 are in  Table 18 summarized.

Table 18

Will be colored ceramics such as tiles, pottery, porcelain etc. treated with the F-silane compound, they get excellent Color fastness and increased chemical resistance. Washing out the pigments or pigment elements (such as z. B. cadmium, lead u. a.) becomes effective in this way prevented. In the case of tiles, the growth of Mold and moss on the surface effectively prevented.

example 35

Colored tiles are made by trading available colorless half porcelain tiles with a Coated paste, which is prepared by mixing 5 parts by weight of cadmium pigment, 95 parts by weight of a no Lead containing low-temperature glaze of boric acid (SKO10a), 0.2 parts by weight of methylcellulose and 60 parts by weight Water and by milling the mixture for 30 min in a ball mill and firing the coated tiles at 1000 ° C after drying.

The colored tiles made in this way become with N-n-propyl-N- [3- (trimethoxy) silylpropyl] perfluorooctylsulfonamide coated with ethanol up to the in table 19 concentration was diluted, and  dried. Each of the tiles treated in this way is left in 300 ml of a 4% acetic acid solution for 24 hours dipped. Thereafter, using an atomic absorption spectrometer measured the amount of cadmium dissolved out. In addition, the tiles are dried and applied to the Alkali deposit on the surface (efflorescence) tested. The results are summarized in Table 19.

example 36

Colored tiles are made by placing in the Commercially available colorless semi-porcelain tiles a paste that is prepared by mixing of 0.68 parts by weight of iron (II) oxide, 0.32 parts by weight Cobalt oxide, 100 parts by weight of a lead-free Low-temperature glaze (SK010a), 0.2 parts by weight of methylcellulose and 60 parts by weight of water and by milling of the mixture for 30 minutes in a ball mill and firing the coated tiles at 1050 ° C after drying.

The colored tiles made in this way become with N-n-propyl-N- [3- (trichloro) silylpropyl] perfluorooctylsulfonamide coated with ethanol until the diluted in Table 19, and dried. Each of the tiles treated in this way is left in 300 ml of a 4% acetic acid solution for 24 hours dipped. Thereafter, using an atomic absorption spectrometer the amount of dissolved out Lead measured. In addition, the tiles are dried and checked for alkali deposition on the surface. The results are summarized in Table 19.

example 37

Colored tiles are made by placing in the Commercially available colorless semi-porcelain tiles  a paste that is prepared by mixing of 2 parts by weight of manganese oxide, 98 parts by weight of a no Lead-containing medium-temperature glaze (SK4), 0.3% by weight Divide methylcellulose and 60 parts by weight of water and through Milling the mixture for 30 minutes in a ball mill and firing the coated tiles at 1200 ° C after the Dry.

The colored tiles made in this way become with N-n-propyl-N- [3- (trichloro) silylpropyl] perfluorooctylsulfonamide coated with ethanol to a concentration of 5% was diluted. The way this way treated tiles are immersed in water to the middle, then let them stand to the growth of To observe mold and mosses. After 3 months was one Growth of mold and mosses not observed.

Comparative Example 24

The colored tiles produced according to Example 35 become without surface treatment in a 4% acetic acid solution dipped for 24 hours, after which the amount dissolved out Cadmium is measured by atomic absorption spectrometry. In addition, it is tested for alkali deposition.

Comparative Example 25

The colored tiles produced according to Example 36 become on the dissolved amount of lead and alkali deposit as tested in Comparative Example 24. The results are summarized in Table 19.  

Table 19

Example 38

Colored tiles are made by trading available colorless half porcelain tiles with a paste which is prepared by mixing 2 parts by weight Manganese oxide, containing 92 parts by weight of no lead Medium temperature glaze (SK4), 0.2 parts by weight of methylcellulose and 60 parts by weight of water and by grinding the mixture while in a ball mill for 30 min and burning the coated tiles at 1200 ° C after drying.

The colored tiles made in this way become with N-n-propyl-N- [3- (trichloro) silylpropyl] perfluorooctylsulfonamide coated with ethanol to a concentration of 5% was diluted. The treated in this way Tiles are immersed in water to the middle, then let them stand to the growth of To observe mold and mosses. After 3 months was one Growth of mold and mosses not observed.

Comparative Example 26

The colored tiles produced according to Example 37 become on the growth of mold and mosses in the absence of Surface treatment tested according to Example 37.  Within 1 month, mosses grew.

Become organic building materials such as fabrics for the disposal of walls, air containing lightweight concrete slabs (ALC), Slates, calcium silicate boards, molded cement materials, hardened cement mortar, concrete, etc. with the F-silane compound treated, one receives products with improved water and oil repellent properties, increased Stain and weather resistance, good adhesion of the Coating materials, etc. as well as with frost resistance and resistance to mold growth and mosses, etc. These building materials may be before treatment with the F-silane compound with other coating materials be coated.

If these substances are treated with the F-silane compound, This is usually with a suitable organic Solvents in a concentration of 0.001 to 20, preferably diluted to 0.1 to 10 wt .-%.

example 39

A material is made available by walls, by adding 100 parts by weight Portland cement, 300 parts by weight Sand, 0.2 parts by weight of methylcellulose and 60 parts by weight Water mixed together. This material will then on a concrete block (30 cm × 30 cm × 5 cm) up to a Thickness of 5 mm applied with the help of a trowel.  

After the distribution of the block is in moist air for 2 weeks long hardened, after which a 5% ethanol solution of C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OCH₃) ₃ on the material is applied, after which it is finally dried. The test block is then placed 5 cm deep in water and in a room at 35 ° C and at a relative humidity of 95% 3 months left. A growth of Mold and moss is not observed.

Comparative Example 27

On the surface of the test block prepared according to Example 39 is a 5% ethanol solution of CH₃Si (OCH₃) ₃ after which the block was tested as in Example 39 becomes. After 3 months mold forms.

example 40

An emulsion paint is prepared by adding 40 parts by weight an acrylic emulsion coating ("! EC720") from Dai Nippon Ink Kogyo Kabushiki Kaisha, 25 parts by weight titanium oxide, 0.2 part by weight of sodium oleate and 0.3 part by weight of methyl cellulose mixed together. This painting will be on the Surface of a slate (150 × 50 × 3 mm) applied. After drying the paint is applied to the painted Surface of the slate once a 0.1% ethanol solution of C₈F₁₇SO₂N (C₂H₅) CH₂CH₂CH₂Si (OCH₃) ₃ on brought.

The edges and the back of this test plate are protected, after which the plate for 1 year under free Leaves sky. Blistering, peeling, and staining on the surface are not observed afterwards.

Comparative Example 28

On the painted surface of the test slate, made according to example 40, a 5% ethanol solution of

CH₃CONHC₃H₆Si (OCH₃) ₃

applied and dried. The plate is left for 1 year in the same way as in Example 40 in the open air stand. Although it does not cause blistering and peeling, however, the surface shows severe staining.

Comparative Example 29

On the painted surface of the test slate, made according to Example 40, a 5% ethanol solution the known compound

C₈F₁₇COO- (CH₂) ₃Si (OCH₃) ₃

applied and dried. The plate is left for 1 year in the same way as in Example 40 in the open air stand. Although it does not cause blistering and peeling, however, the surface shows little staining.

example 41

A silica is prepared by adding 20 parts by weight colloidal silica ("Snow Tex") from Nissan Kagaku Kabushiki Kaisha, 10 parts by weight titanium oxide, 20 parts by weight Parts of calcium carbonate, 0.2 parts by weight of sodium oleate, 0.4 Parts by weight of methyl cellulose and 50 parts by weight of water with each other mixed. This painting will be on the surface a slate (150 mm × 50 mm × 3 mm) applied. After drying the paint is applied to the painted Surface of the slate once a 5% Ethanol solution of

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃

applied.

The edges and the back of this test plate are protected  and the bottom half of the plate is in water dipped. After 3 months, blistering and peeling not detect. Also shows up in height of the water level almost no staining.

Comparative Example 30

On the surface of the coated with the Kieselerdefarbe Slate plate, prepared according to Example 41, is a 5% ethanol solution of

applied and dried. The lower half of the plate is immersed in water. After 3 months the color layer is flaking in the vicinity of the water level.

example 42

An ALC block (150 mm × 40 mm × 40 mm) becomes impregnated in a 10% ethanol solution of

C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OC₂H₅) ₃

dipped and dried. The test block is completely in Water immersed and a freezing and thawing cycle with Cool to -20 ° C for 2 hours and heat at 30 ° C for 2 hours. Become a day 2 cycles performed. After 50 cycles there is none Cracking and also no breakage.

Comparative Example 31

The same ALC block as in Example 42 becomes a 10% Ethanol solution of

C₈F₁₇CH₂CH₂CH₂Si (OCH₃) ₃

dipped and dried for impregnation. The block will  subjected to the same test as in Example 42. After 20 Freezing and thawing cycles are not cracking and breakage However, after 40 cycles it comes to the crack and at 50 cycles the block breaks.

Comparative Example 32

The same ALC block as in Example 42 becomes impregnated in a 10% ethanol solution of

C₃H₇Si (OCH₃) ₃

dipped and dried. The block will be the same exam as in Example 42 subjected. After 20 freezing and thawing cycles jump off the block pieces and after 30 cycles it comes to break.

example 43

On the surface of a slate (300 mm × 300 mm × 5 mm) is once a 10% ethanol solution of

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂SiCl₃

applied, after which it is dried. The water permeability This slate plate will be made according to the method tested according to JISA6910. Even after 24 hours will be no water absorption detected.

Comparative Example 33

The same slate as in Example 43 will pass the test according to Example 43, but without treatment with the F-silane compound subjected. After one hour were over 30 ml Absorbed water.

example 44

A cement block is made by mixing 100 wt. Portland cement, 200 parts by weight sand and 40 parts by weight Divide water and subsequent molding. The block will Cured for 1 day at room temperature. A 5% ethanol solution  from

C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OCH₃) ₃

is applied to the surface of the block and dried. The side surfaces and the back surfaces are protected and let the block at 5 ° C and at a relative humidity of 95%. Even after Alkali deposit can not be detected for 1 month.

Comparative Example 34

The same cement block as in Example 44 is tested Example 44, but without treatment with the F-silane compound subjected. After 1 week it comes to alkali deposition on the surface.

Will the surface of metals such as copper, a typical electrically conductive material, gold, silver, iron, Aluminum and various types of alloys with the Treated F-silane compound, this molten solder has and solder paste back and loses their solderability. These can easily be removed by removal, eg. B. by scraping the Layer of F-silane compound are recovered, which is why Such a treated metal plate for the production used by integrated circuits can.

example 45

A 0.5% ethanol solution of

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃

with 0.3 wt .-% of a 10% H₂SO₄ solution is applied to a Copper plate (100 × 50 × 1 mm) applied. On the surface The copper plate thus treated becomes molten Tin lead dropped. After cooling, the sticks  Lottropfen the copper plate does not and can be at easy to remove light touch.

Be treated with the F-silane compound treated inorganic Pigments incorporated in coatings become the pigments well dispersed and gives consistent coatings. With the F-silane compound treated inorganic Pigments show a higher in the case of white pigment Whiteness, color intensity and hiding power. The treatment inorganic pigments with the F-silane compound is above been declared.

example 46

While 100 parts by weight of titanium oxide pigment at high speed be stirred with the help of a Henschel mixer, a solution of 0.1% by weight of the pigment is added dropwise to the pigment. Share by

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃

in 10 parts by weight of acetone added. After completion of the addition The mixture is at 150 ° C to remove the solvent held. The pigment is in a liquid jet mill pulverized again, yielding a titanium oxide pigment which is treated with the F-silane compound is. The titanium oxide pigment will be listed below Substances (Formulation 1) mixed, whereby one gets a white color.

Formulation 1 component Parts by weight Treated titanium oxide pigment 30 "Lumiflon LF-200C" (a fluororesin solution from Asahi Glass Co., solid content 60%) 142.9 xylene 35.7 methyl isobutyl ketone 107.1 Isocyanate (hardener) 13.3

The coating mixture is applied to a test paper to determine the opacity to a thickness of 0.00254 cm. The paper coated in this way is used as a sample, measuring the L , a , b values of the white portion. The whiteness is calculated

when

The 60 ° gloss of the white part is combined with a Glossmeter measured and the opacity ratio (reflection of the black part / reflection of the white part) with measured by a reflectometer. Also, instead of 30 parts by weight of titanium white a black color of the same formulation prepared with 1.5 parts by weight of carbon black. 30 parts by weight of the black paint are mixed with 100 parts by weight the described white color mixed, after which the Color strength of the white color is checked. The results are summarized in Table 20.

Comparative Example 35

A white color of formulation 1 is prepared with untreated titanium oxide. According to example 46 the whiteness, the 60 ° gloss, the opacity and the Color strength tested. The results are in Table 20 summarized.

example 47

In a solution of 10 parts by weight of

C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OCH₃) ₃

in 300 parts by weight of ethanol, 100 parts by weight of titanium oxide in the same manner as in Example 46 dispersed  and the titanium oxide thus prepared is combined with the F-silane compound treated. A white painting is made according to the formulation and the method Example 46. The coated with this paint Samples are subjected to the test of Example 46. The results are summarized in Table 20.

Comparative Example 36

In this way as in Example 47, a white paint prepares only as a surface treatment agent the fluorine-free compound

CH₃CONH (CH₂) ₃Si (OCH₃) ₃

is used. The coated with this paint Samples are subjected to the test of Example 46. The results are summarized in Table 20.

example 48

30 parts by weight of titanium oxide are in 114.2 parts by weight of toluene dispersed, after which the dispersion 6 parts by weight

C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OC₂H₅) ₃

are added, after which the mixture is mixed and 60 min is stirred for a long time. After addition of 171.5 parts by weight of a Fluorine resin solution ("Lumiflon LF-100" from Asahi Glass Co., solids content 50%), the mixture becomes 60 minutes long touched. Then, 5.2 parts by weight of melamine are added, followed by the mixture is stirred for 15 minutes to give getting a white painting. A candidate is thereby made that one polished this painting on a Steel plate up to a thickness of 70 g / m² applies and the coated plate then at 200 ° C for 5 minutes hardened. Measured are then the whiteness, the 60 ° gloss, the opacity and color strength. The results are summarized in Table 20.  

reference example

100 parts by weight of calcium carbonate powder are dissolved in a solution of 5 parts by weight

C₇F₁₅CO₂ (CH₂) ₃Si (OCH₃) ₃

dispersed in 300 parts by weight of ethanol, after which the Stirred dispersion for 60 min. By filtration and drying then one obtains the treated with the F-silane compound Calcium carbonate powder. By mixing this powder with the following substances (formulation 2) you get a white coat.

Formulation 2 component Parts by weight Treated calcium carbonate powder 25 titanium oxide 5 "Lumiflon LF-100" (a fluorine resin solution from Asahi Glass Co., solids content 50%) 171.2 toluene 114.2 Melamine (hardener) 5.2

This white paint is brought to the surface of a Paper for the opacity test, after which the Cured paper at 130 ° C for 40 min. The whiteness, the 60 ° Gloss, opacity and color intensity of this coating are measured in the same way as in Example 46th  

Table 20

example 49

Red iron oxide is treated with

C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OCH₃) ₃

in the same manner as in Example 48 and with the following mixed substances (Formulation 3) you get the one coat of paint.

Formulation 3 component Parts by weight Treated pigment 2 calcium carbonate 10 toluene 50 "Lumiflon LF-100" (a fluorine resin solution from Asahi Glass Co., solids content 50%) 40 Isocyanate (hardener) 3.7

The paint is applied to a slate (50 mm x 150 mm) to a thickness of 150 g / cm². The sample obtained in this way is tested with a colorimeter for measuring the L , a and b values. The color difference Δ E between the sample with added titanium oxide and the sample without this is calculated as follows:

A paint is prepared as described above except that untreated red iron oxide is used. The color difference Δ E ' is measured from a sample prepared in the same manner as above. The value Δ I / Δ E 'as it is shown in Table 21, is a measure of the color strength of the treated pigment. If this value is less than 1, ie if it is smaller, the color intensity is also lower. The Δ E / Δ E 'value of this pigment is 0.85, as Table 21 shows.

example 50

A coat of paint is prepared as in the reference example, except that black iron oxide, treated with 10%

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃,

used and then tested in the same way. The Δ E / Δ E 'value is 0.95.

Comparative Example 37

A coat of paint is prepared as in the reference example, except that red iron oxide, treated with 0.1%

C₃H₇Si (OCH₃) ₃,

used and then tested in the same way. The Δ E / Δ E 'value is 0.98.

Comparative Example 38

A coat of paint is prepared as in the reference example, except that black iron oxide, treated with 10%

CH₃CONH (CH₂) ₃Si (OCH₃) ₃,

used and then tested in the same way. The Δ E / Δ E 'value is 0.95.

The results of Example 49 to Comparative Example 38 are summarized in Table 21.

Table 21

example 51

Finely divided silica powder ("Aerosil No. 200" from the company Nippon Aerosil Kabushiki Kaisha), which is a painting addition with thickening effect becomes more stable at 3.0% by weight F = Silane compound as in Example 47, d. H. With

C₈F₁₇SO₂N (CH₃) CH₂CH₂CH₂Si (OCH₃) ₃

treated. Thereafter, a paint is prepared using the following materials (Formulation 4).

Formulation 4 component Parts by weight Treated finely divided silica powder 2 titanium oxide pigment 10 "Lumiflon LF-300" (a low-viscosity fluororesin solution from Asahi Glass Co.) 30 toluene 60 Isocyanate (hardener) 2.8

This painting is the same test as in Example 46 carried out. The results are summarized in Table 20.

Comparative Example 39

A paint is made in the same manner as in Example 51 prepares, except that untreated finely divided silica powder is used. The paint is tested as in Example 51. The paint of Example 51 is better than the from the comparative example, by 2.3% with respect to the whiteness, by 3.6% with respect to the 60 ° gloss and around 8.4% in terms of coverage.

These paints are centrifuged, after which they are allowed to stand, to test for precipitate. The one with the finely divided Silica powder treated with the F-silane compound was prepared, produced paint falls during centrifugation at 1000 rpm for 30 min not off. The with the untreated finely divided silica powder Paints precipitate under the same conditions. It is demonstrated that the finely divided silica powder, treated with the F-silane compound, better thickening properties has as the untreated finely divided silica powder.  

Improve the F-containing silane compounds of the invention the water and oil repellent properties, the stain resistance as well as the resistance to added Solvents for wax. For this purpose will be the compounds are added to the wax in an amount of 0.1 to 20, preferably 1 to 5 wt .-%, based on the weight of the wax, added. Usually the connections become mixed with the wax in the form of a melt. you However, they can also be in the form of a solution in a suitable Solvent be mixed with the wax.

example 52

3.5 g

C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂Si (OCH₃) ₃

are mixed with a melt of 100 g of a commercially available wax ("Hoechst Wax S" Fa. Nippon Hoechst Kabushiki Kaisha), after which the mixture on the surface a 5 mm thick slide is applied. The contact angles for water and liquid are then measured Paraffin. These are 123 or 82 °. The angles for pure wax are 91 and 28 °.

Comparative Example 40

Example 52 is repeated using instead of the F-silane compound a commercially available F-surfactant ("EFTOP-201") Fa. New Akita Chemical Co.). The contact angle of the wax modified in this way is 101 ° for water and 45 ° for liquid paraffin.

Claims (29)

1. N-alkyl-N- / 3- (substituted silyl) propyl / perfluoroalkylsulfonamide of the formula C _n F _{2 n + 1} SO₂NR¹CH₂CH₂CH₂SiR 2 _{3 m} A _m where R is C₁₂₅-alkyl, R is C _1-5 -alkyl, A a group selected from chlorine, bromine and C _1-5 alkoxy, n is an integer from 4 to 12 and m is an integer from 1 to 3. 2. A compound according to claim 1, characterized that A is methoxy, ethoxy or chlorine. 3. A compound according to claim 1 or 2, characterized in that n is an integer from 6 to 10. 4. A compound according to claim 3, characterized in that n is 8. 5. A compound according to any one of claims 1 to 4, characterized characterized in that R¹ is propyl. 6. A compound according to any one of claims 1 to 4, characterized characterized in that R² is methyl or ethyl is. 7. A compound according to any one of claims 1 to 6, characterized in that m is 3. 8. N-n-Propyl-N- / 3- (trichlorosilyl) propyl / perfluorooctylsulfonamide.   9. N-n-Propyl-N- [3- (trimethoxysilyl) propyl] perfluorooctylsulfonamide. 10. A process for the preparation of N-alkyl-N- [3- (substituted silyl) propyl] perfluoroalkylsulfonamide of the formula C _n F _{2 n +1} SO₂NR¹CH₂CH₂CH₂SiR² _{3 m} A _m (I) where R¹ is an alkyl group with 1 to 5 C atoms, R² is an alkyl group having 1 to 5 C atoms, A is a group selected from chlorine, bromine and an alkoxy group having 1 to 5 C atoms, n is an integer from 4 to 12 and m is an integer from 1 to 3 according to one of Claims 1 to 9, characterized in that a compound of the formula C _n F _{2 n +1} SO₂NR¹CH₂CH = CH₂ (II) in which R¹ and n have the meanings given above, is reacted with a compound of the formula HSiR²₃- _m A _m (III) wherein R 2, A and m have the above meanings, in the presence of an addition catalyst. 11. The method according to claim 10, characterized that the addition catalyst is a compound is selected from the group chloroplatinic acid, Azo-bis-isobutyronitrile, benzoyl peroxide, octacarbonyl complex of cobalt, platinum or rhodium. 12. The method according to claim 10 or 11, characterized in that, when A is chlorine or bromine, the addition product is also reacted with a C _1-5 -alcohol. 13. The method according to claim 12, characterized that the reaction of the addition product with the alcohol by blowing in dry air in the reaction mixture. 14. The method according to claim 2, characterized that the reaction of the addition product with the alcohol under reduced pressure. 15. The method according to claim 10 or 11, characterized in that, when A is chlorine or bromine, the addition mixture is also reacted with an alkoxide of a C _1-5 -alcohol. 16. The method according to claim 10 or 11, characterized in that, when A is chlorine or bromine, the addition product is also reacted with Orthoameisensäureester a C _1-5 alcohol. 17. A process for the preparation of N-alkyl-N- [3- (substituted silyl) propyl] perfluoroalkylsulfonamide of the formula C _n F _{2 n +1} SO₂NR¹CH₂CH₂CH₂SiR²₃- _m A _m (I) wherein R¹ is an alkyl group having 1 to 5 C atoms, R² is an alkyl group having 1 to 5 C atoms, A is an alkoxy group having 1 to 5 C atoms, n is an integer from 4 to 12 and m is an integer from 1 to 3, according to any one of claims 1 to 9, characterized in that the reaction of a compound of the formula C _n F _{2 n +1} SO₂Y (IV) wherein Y is fluorine, chlorine or bromine and n has the meaning indicated above, with a compound of formula NR¹CH₂CH₂CH₂SiR² _{3 m} A _m (V) wherein R¹, R², m and A are as defined above. 18. The method according to claim 17, characterized that the reaction is in the presence performs an organic base. 19. The method according to claim 18, characterized that is pyridine as the organic base or triethylamine. 20. The method according to any one of claims 17 to 19, characterized characterized in that the compound of Formula IV in an amount of more than 1 molar equivalent, based to the amount of the compound of the formula (V) used. 21. The method according to any one of claims 17 to 19, characterized characterized in that the compound of Formula IV in an amount of 1.05 to 1.2 mol equivalent, based to the amount of the compound of the formula (V) used. 22. water and oil repellent agent for inorganic substances, that is a compound according to any one of claims 1 to 9 contains. 23. Fluororesin composition containing one with 0.1 to 10  % By weight of a compound according to any one of claims 1 to Contains 9 treated inorganic filler. 24. Inorganic fiber powder whose surface is 0.1 to 20% by weight of a compound according to any one of claims 1 to 9 is treated. 25. Metallic material whose surface is connected is treated according to one of claims 1 to 9. 26. Paper material whose surface is connected is treated according to one of claims 1 to 9. 27. Glass material whose surface is connected is treated according to one of claims 1 to 9. 28. Inorganic building material whose surface is covered with a A compound according to any one of claims 1 to 9 is treated. 29. Coating composition containing a pigment, with 0.1 to 20 wt .-% of a compound according to one of Claims 1 to 9 is treated.