CN1718665A - 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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- CN1718665A CN1718665A CN 200510035412 CN200510035412A CN1718665A CN 1718665 A CN1718665 A CN 1718665A CN 200510035412 CN200510035412 CN 200510035412 CN 200510035412 A CN200510035412 A CN 200510035412A CN 1718665 A CN1718665 A CN 1718665A
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Abstract
An organic Si-F water-proofing agent is composed of solvent and the organic Si-F resin prepolymer which is prepared from one or more alkyl siloxane coupling agents and hydroxy F-Si oil through catalytic hydrolysis reaction. Its preparing process is also disclosed. Its advantages are high water-proofing effect and high resistance to solvent, acid, alkali and ageing.
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 a phenyl in the formula, methyl, and ethyl, carbonatoms is less than 16 saturated chain alkyl; 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, tetramethyl-aqua ammonia; 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, a kind of 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 a phenyl in the formula, methyl, and ethyl, carbonatoms is less than 16 saturated chain alkyl; 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, a kind of preparation method of 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, tetramethyl-aqua ammonia.
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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| 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 |
| CN101646682B (en) * | 2007-03-06 | 2012-07-04 | 学校法人东京理科大学 | Silane coupling agents with heat resistance, durability, releasability, and antifouling property and process for producing these compounds |
| CN103555439A (en) * | 2013-10-25 | 2014-02-05 | 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 |
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| CN113004526A (en) * | 2021-04-20 | 2021-06-22 | 北京化工大学 | Alkoxy-terminated liquid fluorosilicone rubber, and preparation method and application thereof |
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| US5688864A (en) * | 1990-04-03 | 1997-11-18 | Ppg Industries, Inc. | Autophobic water repellent surface treatment |
| WO1995033001A1 (en) * | 1994-05-30 | 1995-12-07 | Daikin Industries, Ltd. | Fluorosilicone compound and composition containing the same |
| CA2175848C (en) * | 1995-06-05 | 2000-01-11 | Ppg Industries Ohio, Inc. | Water repellent surface treatment with integrated primer |
| JP2003160361A (en) * | 2001-09-14 | 2003-06-03 | Wilson:Kk | Two-pack type water repellent for glass surface |
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| 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 |
| CN103555439A (en) * | 2013-10-25 | 2014-02-05 | 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 |
| CN106753173A (en) * | 2016-12-15 | 2017-05-31 | 王礼 | A kind of preparation method of modified aqueous polyurethane pressure sensitive adhesive |
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| CN113004526A (en) * | 2021-04-20 | 2021-06-22 | 北京化工大学 | Alkoxy-terminated liquid fluorosilicone rubber, and preparation method and application 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 |
| CN116218370A (en) * | 2023-03-02 | 2023-06-06 | 东南大学 | Preparation method of fluorinated modified nano waterproof agent emulsion |
| CN116218370B (en) * | 2023-03-02 | 2024-05-17 | 东南大学 | Preparation method of fluorinated modified nano waterproof agent emulsion |
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