CN100396751C - Organic silicon fluoro water proofing agent and its preparation method - Google Patents
Organic silicon fluoro water proofing agent and its preparation method Download PDFInfo
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- CN100396751C CN100396751C CNB200510035412XA CN200510035412A CN100396751C CN 100396751 C CN100396751 C CN 100396751C CN B200510035412X A CNB200510035412X A CN B200510035412XA CN 200510035412 A CN200510035412 A CN 200510035412A CN 100396751 C CN100396751 C CN 100396751C
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- fluoro
- water proofing
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 34
- 239000010703 silicon Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000004078 waterproofing Methods 0.000 title claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 125000005376 alkyl siloxane group Chemical group 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 29
- DODVWSSKXYVHOR-UHFFFAOYSA-N fluoro(hydroxy)silicon Chemical compound O[Si]F DODVWSSKXYVHOR-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000001143 conditioned effect Effects 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000009969 flowable effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 229920002545 silicone oil Polymers 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 229920002050 silicone resin Polymers 0.000 description 9
- 239000012296 anti-solvent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 2
- -1 octyl group Trimethoxy silanes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical class CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical class CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The present invention discloses an organic silicon fluoro waterproof agent which is composed of an active component and a solvent, wherein the active component is organic silicon fluoro resin prepolymer. The organic silicon fluoro resin prepolymer is prepared by hydrolysis reaction via an alkylsiloxane coupling agent or a mixture of a plurality of alkylsiloxane coupling agents, hydroxyl-fluoro silicone oil, and acidic or alkaline catalyst. The present invention also discloses a preparation method of the organic silicon fluoro waterproof agent. By adopting hydroxyl-fluoro silicone oil, the surface of a protected material has low surface energy in the condition of not changing the good air permeability of organic silicon resin, and the water absorption ratio of the surface of the protected material is reduced. Meanwhile, the organic silicon fluoro waterproof agent enlarges the gamma (R/Si) of the material and enhances the elasticity of products, so the waterproof life time of the products is prolonged. With the introduction of organic fluoro groups, the solvent resistance, the acid resistance, the alkali resistance, the aging resistance, the dirt resistance, etc. of the waterproof agent are enhanced.
Description
Technical field
The present invention relates to a kind of building surface water-resisting agent, the invention still further relates to the preparation method of a kind of building surface with water-resisting agent.
Background technology
Silicone resin has excellent properties such as high-low temperature resistant, ageing-resistant, hydrophobic, electrical insulating property, difficult combustion and nontoxic no corrosion; especially its unique hydrophobic nature and ventilation property; be considered to the ideal waterproof paint, and be widely used in building and the waterproofing protection of material surface.The organosilicon waterproof agent for building by with the building material surface react with, form the insoluble silicone resin film of one deck few molecules thick at substrate surface, make the surface tension of material of construction be reduced to organosilyl surface tension, increase realizes " anti-capillary effect " with the contact angle of water, anti-sealing enters material of construction with liquid state, therefore, has hydrophobic nature; Air and steam can unhinderedly infiltrate by the organosilicon impregnate layer simultaneously, can keep the ventilative normally effect of buildings.At present, the waterproofing agent of organosilicon on the market can be divided into four classes by its composition: alkylsilanol salt is [as RSi (OH)
2OM, M are Na, K], silane is [as RSi (OR ')
3, R ' is methyl or ethyl], silicon resin solution, silicone resin emulsion.The R of common water-resisting agent is methyl or chain alkyl, after the curing, and the chemical-resistant reagent of silicone resin, performance such as antifouling is shortcoming to some extent all.Simultaneously, solidify the silicone resin γ (R/Si) that the back forms and in most cases be the alkyl number of 1[γ (R/Si) for connecting on average each Siliciumatom], cause the silicone resin film degree of crosslinking height of formation, elasticity is bad, easily crisp, this also is not long major cause of such water-resisting agent waterproof life-span.
In waterproofing agent of organosilicon, introduce the organic fluorine group, when not changing waterproofing agent of organosilicon inherent excellent properties, not only can further reduce the surface energy of silicone resin, improve its water resistance, and can improve performances such as the oil resistant of silicone resin, anti-solvent, chemical-resistant resistance.Because fluorine-containing silane coupling agent selling at exorbitant prices is many on theoretical aspect to its research at present, also has a certain distance from the scale application.Therefore, under prerequisite cheaply, the fluorine-containing waterproofing agent of organosilicon of processability excellence will inevitably have vast market prospect.
Summary of the invention
The purpose of this invention is to provide a kind of good springiness, anti-solvent, acid-and base-resisting, ageing-resistant, bear dirty, organic silicon fluoro water proofing agent that the waterproof life-span is long.
Another object of the present invention provides the preparation method of above-mentioned organic silicon fluoro water proofing agent, and this preparation method's technology is simple, product productive rate height.
A kind of organic silicon fluoro water proofing agent provided by the invention, by activeconstituents and solvent composition, wherein activeconstituents is the organic silicon-fluorine resin prepolymer, this organic silicon-fluorine resin prepolymer be by the mixture of alkylsiloxane coupling agent or several alkylsiloxane coupling agents and hydroxyl fluorosilicon oil in the presence of acidity or basic catalyst, the generation hydrolysis reaction makes, wherein:
Alkylsiloxane coupling agent structural formula is R-Si (OR ')
3, R is phenyl or carbonatoms less than 16 saturated chain alkyl in the formula; R ' is methyl or ethyl;
The hydroxyl fluorosilicon oil is the hydroxy-end capped poly-methyl of silicon (3,3, a 3-trifluoro propyl) siloxane fluid, and the hydroxyl value of hydroxyl fluorosilicon oil is greater than 3%;
The ratio γ (R/Si) of alkyl and Siliciumatom is 1.05~1.9, wherein γ (R/Si)=(a
Coupling agent+ 2b)/(a
Coupling agent+ b), a is the mole number of alkylsiloxane coupling agent, b is the mole number of hydroxyl fluorosilicon oil, b=m
The hydroxyl fluorosilicon oil/ 156, m
The hydroxyl fluorosilicon oilQuality for the hydroxyl fluorosilicon oil.
The present invention also provides the preparation method of above-mentioned organic silicon fluoro water proofing agent, this preparation method is at room temperature with the alkylsiloxane coupling agent, the hydroxyl fluorosilicon oil, solvent places reaction flask, stir and add acidity or basic catalyst and water down, heat temperature raising was to reflux temperature reaction 2~12 hours, conditioned reaction system pH to 6~8 after reaction finishes, distillation removes and desolvates, the alcohol that unreacted water and reaction generate, temperature is elevated to more than 110 ℃ again, continue reaction 0.15~4 hour, be cooled to room temperature then, obtain low viscosity, flowable organic silicon-fluorine resin prepolymer, add dissolution with solvents, filtration obtains silicon resin solution, is organic silicon fluoro water proofing agent.
Among the above-mentioned preparation method, an acidic catalyst can be selected hydrochloric acid, sulfuric acid, acetate, phosphoric acid, trifluoroacetic acid, three fluosulfonic acid or Phenylsulfonic acid; Basic catalyst can be selected sodium hydroxide, ammoniacal liquor, potassium hydroxide, triethylamine or Tetramethylammonium hydroxide; Solvent is chosen as hypotoxic methyl alcohol, ethanol, Virahol, sherwood oil, ethyl acetate, toluene or acetone.
Organic silicon fluoro water proofing agent provided by the invention is water white neutral solution, has low viscosity.Active ingredient has good perviousness and film forming ability.According to People's Republic of China's building material industry standard, building surface is tested with waterproofing agent of organosilicon (JC/T 902-2002), and the result is: have satisfactory stability, placed 6 months under the room temperature, and not stratified, no obvious sediment; Water at the contact angle of film coated surface greater than 128 °; Its water-intake rate ratio is less than 12%; Under conditions such as standard state and heat, low temperature, ultraviolet ray, acid, alkali, perviousness is less than 1mm, and anhydrous mark does not have variable color.
Compare with existing water-resisting agent, the present invention has the following advantages:
(1) because the activeconstituents of water-resisting agent provided by the invention is the organic silicon-fluorine resin prepolymer; under the prerequisite that does not change its ventilation property; introduce the organic fluorine group; make protected material surface have lower surface energy after the curing; reduced the water-intake rate ratio of material, improved silicone resin anti-solvent, acid-and base-resisting, ageing-resistant, performance such as bear dirty.
(2) owing to adopted the hydroxyl fluorosilicon oil, not only introduced the organic fluorine group, and γ (R/Si) increases, when its water resistance is further improved, also improve the elasticity of product, improved its waterproof life-span, and when γ (R/Si) greater than 1.5 the time, adopt the hydroxyl fluorosilicon oil to substitute the dialkyl dialkoxy silicane of correspondence, during hydrolysis, can avoid owing to generating the shortcoming that cyclic oligomer brings water resistance to descend and solidifies " anti-sticking " of back generation.
(3) water-resisting agent provided by the invention is a colourless transparent solution, does not change the color of material surface after the use, and its ageing products is a silicon-dioxide, has and the good consistency of material of construction.
Embodiment
Enumerating embodiment below specifically describes the present invention; be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention, the those of ordinary skill in this field still belongs to protection scope of the present invention according to the foregoing invention content to some nonessential improvement and the adjustment that the present invention makes.Following all umbers are mass parts.
Embodiment 1
With 100 parts of Union carbide A-162s, 88 parts of hydroxyl values are 5% hydroxyl fluorosilicon oil under the room temperature, and 120 parts of ethanol place reaction flask, stir down to add 1 part 10
-5The dilute hydrochloric acid of mol/L is catalyzer and 12 parts of water, heat temperature raising to 80 ℃ reaction 3 hours.Reaction finishes, and adds 1 part 10
-5The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes ethanol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 110 ℃, continues reaction 0.5 hour, be cooled to room temperature, adds 140 parts of dissolve with ethanol, filter, must 280 parts concentration be 50% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.5.According to JC/T 902-2002, the water-intake rate ratio that records is: 8.9%, and contact angle is 134 °; And the γ (CH under the same terms
3/ Si) be 1.0 methyl silicon resin water-intake rate than and contact angle be respectively: 24.6%, 112 °.Above data show that water-resisting agent provided by the invention has better water resistance.When soak time is extended for 48h, the water-intake rate ratio that records is 19.8%, and the water-intake rate ratio of corresponding methyl silicon resin water-resisting agent is 65.4%, and this has reflected that water-resisting agent provided by the invention has the longer waterproof life-span.
Embodiment 2
With 100 parts of Union carbide A-162s, 22 parts of hydroxyl values are 6% hydroxyl fluorosilicon oil under the room temperature, and 80 parts of ethanol place reaction flask, stir down to add 1 part 10
-5The dilute hydrochloric acid of mol/L is catalyzer and 15 parts of water, heat temperature raising to 80 ℃ reaction 3 hours.Reaction finishes, and adds 1 part 10
-5The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes ethanol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 110 ℃, continues reaction 0.5 hour, be cooled to room temperature, adds 120 parts of dissolve with ethanol, filter, must 200 parts concentration be 40% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.2.According to JC/T 902-2002, the water-intake rate ratio that records is: 11.5%, and contact angle is 131 °
Embodiment 3
With 100 parts of Union carbide A-162s, 790 parts of hydroxyl values are 4% hydroxyl fluorosilicon oil under the room temperature, 100 parts of ethanol, and 500 parts of acetone place reaction flask, stir down to add 1 part 10
-5The dilute hydrochloric acid of mol/L is catalyzer and 12 parts of water, heat temperature raising to 80 ℃ reaction 5 hours.Reaction finishes, and adds 1 part 10
-5The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes ethanol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 110 ℃, continues reaction 1.5 hours, be cooled to room temperature, add the dissolving of 350 parts of ethanol and 500 parts of acetone mixed solvent, filter, 1700 parts of concentration are 50% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.9.According to JC/T902-2002, the water-intake rate ratio that records is: 10.4%, and contact angle is 132.5 °.
Embodiment 4
With catalyzer with 10
-5The sodium hydroxid aqueous solution of mol/L replaces 10
-5The dilute hydrochloric acid of mol/L, reaction finishes, in and the time with 10
-5The dilute hydrochloric acid of mol/L replaces Me
3SiNHSiMe
3Ethanolic soln, the charging capacity of other raw material and solvent and reaction conditions and treatment step be with embodiment 2, concentration is 50% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.5.According to JC/T 902-2002, the water-intake rate ratio that records is: 9.4%, and contact angle is 133.5 °.
Embodiment 5
With 100 parts of propyl trimethoxy silicanes, 63 parts of hydroxyl values are 6% hydroxyl fluorosilicon oil under the room temperature, and 80 parts of ethanol place reaction flask, stir down to add 1 part 10
-4The dilute hydrochloric acid of mol/L is catalyzer and 15 parts of water, heat temperature raising to 80 ℃ reaction 3 hours.Reaction finishes, and adds 10 part 10
-5The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes methyl alcohol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 110 ℃, continues reaction 0.5 hour, be cooled to room temperature, adds 130 parts of dissolve with ethanol, filter, must 260 parts concentration be 50% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.4.According to JC/T 902-2002, the water-intake rate ratio that records is: 5.6%, and contact angle is 135.5 °.
Embodiment 6
With 100 parts of octyl group Trimethoxy silanes, 100 parts of hydroxyl values are 7% hydroxyl fluorosilicon oil under the room temperature, and 120 parts of ethanol place reaction flask, stir down to add 1 part 10
-3The dilute hydrochloric acid of mol/L is catalyzer and 10 parts of water, heat temperature raising to 80 ℃ reaction 4 hours.Reaction finishes, and adds 1 part 10
-3The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes methyl alcohol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 120 ℃, continues reaction 0.5 hour, be cooled to room temperature, adds 260 parts of dissolve with ethanol, filter, must 430 parts concentration be 40% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.6.According to JC/T 902-2002, the water-intake rate ratio that records is: 6.0%, and contact angle is 134 °.
Embodiment 7
With 100 parts of dodecyl Trimethoxy silanes, 215 parts of hydroxyl values are 5% hydroxyl fluorosilicon oil under the room temperature, 60 parts of ethanol, and 90 parts of acetone place reaction flask, stir down to add 1 part 10
-3The dilute hydrochloric acid of mol/L is catalyzer and 15 parts of water, heat temperature raising to 80 ℃ reaction 5 hours.Reaction finishes, and adds 1 part 10
-3The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes methyl alcohol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 110 ℃, continues reaction 1 hour, be cooled to room temperature, adds 100 parts of ethanol, 200 parts of acetone solutions filter, must 600 parts concentration be 50% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.8.According to JC/T 902-2002, the water-intake rate ratio that records is: 8.1%, and contact angle is 133 °.
Embodiment 8
With 100 parts of Union carbide A-162s, 20 parts of phenyl triethoxysilanes, 43 parts of hydroxyl values are 6% hydroxyl fluorosilicon oil under the room temperature, and 100 parts of ethanol place reaction flask, stir down to add 1 part 10
-5The dilute hydrochloric acid of mol/L is catalyzer and 15 parts of water, heat temperature raising to 80 ℃ reaction 3 hours.Reaction finishes, and adds 1 part 10
-5The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes ethanol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 110 ℃, continues reaction 0.5 hour, be cooled to room temperature, adds 110 parts of dissolve with ethanol, filter, must 220 parts concentration be 50% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.3.According to JC/T 902-2002, the water-intake rate ratio that records is: 11.4%, and contact angle is 131.5 °.
Embodiment 9
With 100 parts of octyl group Trimethoxy silanes, 40 parts of phenyl triethoxysilanes, 93 parts of hydroxyl values are 6% hydroxyl fluorosilicon oil under the room temperature, and 120 parts of ethanol place reaction flask, stir down to add 1 part 10
-3The dilute hydrochloric acid of mol/L is catalyzer and 15 parts of water, heat temperature raising to 80 ℃ reaction 3 hours.Reaction finishes, and adds 1 part 10
-3The Me of mol/L
3SiNHSiMe
3Ethanolic soln transfers pH value of reaction system to neutral; Distillation removes ethanol and the unreacted water that desolvates and react generation under 90 ℃.Temperature is elevated to 110 ℃, continues reaction 1 hour, be cooled to room temperature, adds 210 parts of dissolve with ethanol, filter, must 420 parts concentration be 50% organic silicon-fluorine resin pre-polymer solution, be organic silicon fluoro water proofing agent, its γ (R/Si) is 1.5.According to JC/T 902-2002, the water-intake rate ratio that records is: 5.7%, and contact angle is 135 °.
Claims (5)
1. organic silicon fluoro water proofing agent, it is characterized in that by activeconstituents and solvent composition, wherein activeconstituents is the organic silicon-fluorine resin prepolymer, this organic silicon-fluorine resin prepolymer be by the mixture of alkylsiloxane coupling agent or several alkylsiloxane coupling agents and hydroxyl fluorosilicon oil in the presence of acidity or basic catalyst, the generation hydrolysis reaction makes, wherein:
Alkylsiloxane coupling agent structural formula is R-Si (OR ')
3, R is phenyl or carbonatoms less than 16 saturated chain alkyl in the formula; R ' is methyl or ethyl;
The hydroxyl fluorosilicon oil is the hydroxy-end capped poly-methyl of silicon (3,3, a 3-trifluoro propyl) siloxane fluid, and the hydroxyl value of hydroxyl fluorosilicon oil is greater than 3%;
The ratio γ (R/Si) of alkyl and Siliciumatom is 1.05~1.9, wherein γ (R/Si)=(a
Coupling agent+ 2b)/(a
Coupling agent+ b), a is the mole number of alkylsiloxane coupling agent, b is the mole number of hydroxyl fluorosilicon oil, b=m
The hydroxyl fluorosilicon oil/156, m
The hydroxyl fluorosilicon oilQuality for the hydroxyl fluorosilicon oil.
2. the preparation method of an organic silicon fluoro water proofing agent as claimed in claim 1, it is characterized in that under the room temperature the alkylsiloxane coupling agent, the hydroxyl fluorosilicon oil, solvent places reaction flask, stir and add acidity or basic catalyst and water down, heat temperature raising was to reflux temperature reaction 2~12 hours, conditioned reaction system pH to 6~8 after reaction finishes, distillation removes and desolvates, the alcohol that unreacted water and reaction generate, temperature is elevated to more than 110 ℃ again, continue reaction 0.15~4 hour, be cooled to room temperature then, obtain low viscosity, flowable organic silicon-fluorine resin prepolymer adds dissolution with solvents, filtration obtains silicon resin solution, is organic silicon fluoro water proofing agent.
3. the preparation method of organic silicon fluoro water proofing agent according to claim 2 is characterized in that described an acidic catalyst is hydrochloric acid, sulfuric acid, acetate, phosphoric acid, trifluoroacetic acid, three fluosulfonic acid or Phenylsulfonic acid.
4. the preparation method of organic silicon fluoro water proofing agent according to claim 2 is characterized in that described basic catalyst is sodium hydroxide, ammoniacal liquor, potassium hydroxide, triethylamine or Tetramethylammonium hydroxide.
5. the preparation method of organic silicon fluoro water proofing agent according to claim 2 is characterized in that described solvent is hypotoxic methyl alcohol, ethanol, Virahol, sherwood oil, ethyl acetate, toluene or acetone.
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EP2133354A4 (en) * | 2007-03-06 | 2012-02-08 | Univ Tokyo Sci Educ Found | Silane coupling agents with heat resistance, durability, releasability, and antifouling property and process for producing these compounds |
CN101402827B (en) * | 2008-11-03 | 2011-07-20 | 广州市白云文物保护工程有限公司 | Organosilicon fluorine material for sealing and protecting irony cultural relics and method of producing the same |
CN103555439B (en) * | 2013-10-25 | 2015-03-18 | 江苏雪豹日化有限公司 | Concentrated cleaning agent for outdoor glass |
CN104437141A (en) * | 2014-11-17 | 2015-03-25 | 清华大学 | Preparation method of solvent resistant nanofiltration membrane |
CN105505033A (en) * | 2016-01-22 | 2016-04-20 | 田毅 | Waterproof impermeable spray |
CN106543810A (en) * | 2016-10-31 | 2017-03-29 | 安徽博泰氟材料科技有限公司 | Organic fluorine waterproof agent is used in a kind of PU leatherware processing |
CN106753173B (en) * | 2016-12-15 | 2020-05-01 | 佛山市顺德区国精合成材料有限公司 | Preparation method of modified water-based polyurethane pressure-sensitive adhesive |
CN109401616A (en) * | 2018-11-06 | 2019-03-01 | 深圳市溯元科技有限公司 | A kind of anti-doodling paint and preparation method thereof |
CN113004526B (en) * | 2021-04-20 | 2022-04-22 | 北京化工大学 | Alkoxy-terminated liquid fluorosilicone rubber, and preparation method and application thereof |
CN116218370B (en) * | 2023-03-02 | 2024-05-17 | 东南大学 | Preparation method of fluorinated modified nano waterproof agent emulsion |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08333545A (en) * | 1995-06-05 | 1996-12-17 | Ppg Ind Inc | Water-repellent surface treatment integrated with priming |
US5688864A (en) * | 1990-04-03 | 1997-11-18 | Ppg Industries, Inc. | Autophobic water repellent surface treatment |
US5734001A (en) * | 1994-05-30 | 1998-03-31 | Daikin Industries, Ltd. | Fluorosilicone compound and composition containing the same |
JP2003160361A (en) * | 2001-09-14 | 2003-06-03 | Wilson:Kk | Two-pack type water repellent for glass surface |
-
2005
- 2005-06-21 CN CNB200510035412XA patent/CN100396751C/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5688864A (en) * | 1990-04-03 | 1997-11-18 | Ppg Industries, Inc. | Autophobic water repellent surface treatment |
US5734001A (en) * | 1994-05-30 | 1998-03-31 | Daikin Industries, Ltd. | Fluorosilicone compound and composition containing the same |
JPH08333545A (en) * | 1995-06-05 | 1996-12-17 | Ppg Ind Inc | Water-repellent surface treatment integrated with priming |
JP2003160361A (en) * | 2001-09-14 | 2003-06-03 | Wilson:Kk | Two-pack type water repellent for glass surface |
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