CN101580355B - Water-based organic silicon waterproof agent - Google Patents
Water-based organic silicon waterproof agent Download PDFInfo
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- CN101580355B CN101580355B CN2009100327101A CN200910032710A CN101580355B CN 101580355 B CN101580355 B CN 101580355B CN 2009100327101 A CN2009100327101 A CN 2009100327101A CN 200910032710 A CN200910032710 A CN 200910032710A CN 101580355 B CN101580355 B CN 101580355B
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- succinic acid
- half ester
- ester sulfonate
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Abstract
The invention relates to a water-based organic silicon waterproof agent by taking sodium methylsilanolate as a main raw material, and is particularly suitable for moving penetration waterproof processing of a porous structure, such as bricks, stone materials, concrete, mortar, cement slurry and the like.
Description
Invention field
The present invention relates to a kind of building materials use waterproofing agent of organosilicon, specifically, relating to a kind of is the water-based organic silicon waterproof agent of main raw material with the methyl silicon sodium alcoholate.
Background technology
Concrete and masonry structure buildings often do not reach design service life because of weather resistance is not enough.Cause the factor of concrete performance deterioration that steel bar corrosion, freeze-thaw damage, chemical erosion and alkali etc. are arranged.In the physical damage and process of chemical attack that concrete structure suffered, water plays important effect.If cement-based material is exposed in the water, a series of corrosion reactions will take place.Under concrete one or more factor effects therein, can reduce work-ing life.
Water can be divided into 4 aspects to concrete corrosive nature: (1) with during cement matrix contacts for a long time, water is as solvent, and by hydrolysis, adhesive bond calcium hydroxide and CSH-gel dissolve gradually, and its dissolution rate can reflect concrete long durability under the wet environment; (2) gas in the environment dissolves in the concrete hole solution.For example carbonic acid gas and sulfurous gas are dissolved in the water, and rapidly with the alkaline matter generation chemical reactions such as hydrated product calcium hydroxide of cement, concrete generation carbonization or vitriol reaction destroy rebar passivation film or the generation volumetric expansion, cause concrete destruction; (3) water is as a kind of conveying medium, by the capillary sorption dissolved compounds such as villaumite are transported in the pore structure of cement-based material, if the chlorine ion concentration of rebar surface reaches threshold concentration, will destroy the passivation protection film of rebar surface, make reinforcing bar corrosion gradually; (4) water can cause material generation frost and thawing, if invading of being subjected to for a long time that water in air divides is wet, will make that wall is done, wet alternate heavily stressed, cause surface cracking, water can make the mouldy and accelerated weathering of wall.In addition, water can also be carried pollutent and dust secretly, and it is dirty that buildings is subjected to.Annual concrete and Steel Concrete are because the direct or indirect loss that corrosion brings accounts for the 3.5-5% of gross national product (GDP).Therefore, reducing the recovery project expense is one of important means of increasing investment returns.
Above corrosive nature is all from the structural part surface.The transportation of concrete surface properties decision water in concrete.One of effective ways that improve concrete durability are that concrete is carried out WATER REPELLENT.
Organosilicon material makes shipwreck to sprawl on organosilicon membrane owing to have very low surface tension (20-21mN/m); And can be coated on base material equably or sneak on the base material (siliceous substrates such as cement, granite, clear water brick etc.), and do not seal the ventilative micropore of base material, and can reduce the surface energy of base material simultaneously, make it have hydrophobic nature.Therefore, contain organosilyl water-resisting agent and have excellent waterproof, antifouling and anti-dust performance, it is the water-proof material of building materials such as a kind of ideal concrete, mortar, masonry, can effectively improve waterproof, contamination resistance energy and the endurance quality of building materials, thereby the organosilicon waterproof agent for building is widely used on the building materials such as concrete member, brick and tile, stone inscription.
Waterborne organic silicon dilutes silicoorganic compound because of having avoided the employing all kinds of SOLVENTS, the deficiencies such as toxicity, volatility and inflammableness of solvent have been avoided, and have performances such as good waterproof and resistance to chemical attack, obtained to use widely as waterproof agent for building such as concrete waterproofer in recent years.At present, the water-based organic silicon waterproof agent of using in concrete mainly contains methyl silanol (sodium) salts solution, methyl silanol salt is easily decomposed by weak acid, when running into carbon dioxide in air, just resolve into methyl siliconic acid, and polymerization generates the poly-methyl silicon ether with water resistance soon, thus can substrate surface form one deck as thin as a wafer polysiloxane film and have water repellency.
The advantage of methyl silicon sodium alcoholate waterproof agent for building is, low price is easy to use; Nonflammable, free from environmental pollution in the use; Brick, stone, concrete etc. there is stronger seepage force.Shortcoming is that slower with carbon dioxide reaction speed, 24 hours ability of need is solidified, because the water-resisting agent of using remains water miscible within a certain period of time, therefore, is fallen by rain drop erosion easily.Methyl silanol salt is too strong because of its alkalescence, and there are shortcomings such as rapid hardening, poor durability in agent as cement concrete water proof.
For example, CN1218081A discloses a kind of waterproofing agent of organosilicon for building and has contained sodium methyl silicate 3.0-4.0%, Tai-Ace S 150 0.0-0.06% and water 96-97%; CN1664047A discloses a kind of hydrophobic water-proof material and preparation method thereof, and it is starting material with monomethyl water glass, ethanol, alkali and water.Product of the prior art does not still just overcome the existing defective of methyl silicon sodium alcoholate aqua.Therefore, still just need better methyl silicon sodium alcoholate salt water-repellent,, overcome its deficiency to keep its advantage.
The present inventor has obtained the product that performance is improved fully, so finished the present invention by the methyl silicon sodium alcoholate water-resisting agent is carried out modification.
Summary of the invention
The purpose of this invention is to provide a kind of is the building materials use waterproofing agent of organosilicon of main raw material with the methyl silicon sodium alcoholate.
Another object of the present invention provides the preparation method of described water-based organic silicon waterproof agent.
A further object of the present invention provides the application of described water-based organic silicon waterproof agent on building materials.
Specifically, the invention provides a kind of is the building materials use waterproofing agent of organosilicon of raw material with methyl silanol salt, and (%g/ml) is as follows for the composition of described water-resisting agent and content:
Methyl silicon sodium alcoholate 30-60%
Silane coupling agent 2-5%
Fatty alcohol-polyoxyethylene ether Succinic Acid half ester sulfonate,
Alkylphenol polyoxyethylene Succinic Acid half ester sulfonate
Or alkylphenol polyoxyethylene formaldehyde condensation products Succinic Acid half ester sulfonate 1.5-3.0%
Alum 2.5-6.0%
Phosphoric acid an amount of (pH transfers to 7.0-7.5)
Water is mended to 100%
In preferred embodiments, the composition of water-resisting agent of the present invention and content (%g/ml) are as follows:
Methyl silicon sodium alcoholate 30-60%
γ-An Bingjisanyiyangjiguiwan 2-5%
Fatty alcohol-polyoxyethylene ether Succinic Acid half ester sulfonate,
Alkylphenol polyoxyethylene Succinic Acid half ester sulfonate
Or alkylphenol polyoxyethylene formaldehyde condensation products Succinic Acid half ester sulfonate 1.5-3.0%
Alum 2.5-5.0%
Polyoxyethylene glycol 0.5-2.5%
Phosphoric acid an amount of (pH transfers to 7.0-7.5)
Water is mended to 100%
In the most preferred embodiment, (%g/ml) is as follows for the composition of water-resisting agent of the present invention and content:
Methyl silicon sodium alcoholate 40-60%
γ-An Bingjisanyiyangjiguiwan 3-5%
SSOPA 1.5-3.0％
Alum 2.5-5.0%
Macrogol 2000-6000 0.5-2.0%
Phosphoric acid an amount of (pH transfers to 7.0-7.5)
Water is mended to 100%
Methyl silicon sodium alcoholate is commercially available industrial goods.
Silane coupling agent is selected from a kind of in γ-An Jibingjisanyiyangjiguiwan, γ-epoxypropyl triethoxyl silane, γ-glycidoxy butyl trimethoxy silane and the glycidoxy Union carbide A-162, preferred γ-An Jibingjisanyiyangjiguiwan (KH-550).The introducing of silane coupling agent can make poly-methyl silicon ether network more closely knit, and promotes poly-methyl silicon ether to engage more firm with silicate in the concrete.The hydrophobic nature of silane coupling agent helps improving the initial resistance of rainwater washing against performance of preparation equally.
Alum mixes the double salt of forming by vitriolate of tartar and Tai-Ace S 150; it is a kind of inorganic waterproof material; it is one of composition in the silicate-type expansive cement; itself has certain anti-permeability performance; and can be filled in the concrete capillary-size pore; eliminate hole, form protective layer from inside to outside, prevent that moisture from infiltrating.Among the present invention, alum is also as Al
3+The supplier, be used for and Ca
2+And RCOO
-Form the title complex network.
Fatty Alcohol(C12-C14 and C12-C18)/alkylphenol polyoxyethylene (formaldehyde condensation products) Succinic Acid half ester sulfonate is represented fatty alcohol-polyoxyethylene ether Succinic Acid half ester sulfonate, alkylphenol polyoxyethylene Succinic Acid half ester sulfonate and alkylphenol polyoxyethylene formaldehyde condensation products Succinic Acid half ester sulfonate, be commercially available industrial goods, for example SSOPA, Protowet 4951, Protowet 4196, Servoxyl VLB 1123, Servoxyl VLE 1159.In the present invention, select for use Fatty Alcohol(C12-C14 and C12-C18)/alkylphenol polyoxyethylene (formaldehyde condensation products) Succinic Acid half ester sulfonate that has carboxylate salt as auxiliary agent, this auxiliary agent has emulsification, wetting and infiltration function, can help composition emulsification, dispersion and stable in the preparation, its wetting and infiltration function can promote the water-resisting agent product to infiltrate in the concrete again, when handling, surface waterproofing can promote to infiltrate concrete layer, simultaneously wherein contained Succinic Acid half salt or RCOO
-The supplier, can impel RCOO
-With Al
3+And Ca
2+Form the title complex network structure.
Polyoxyethylene glycol (PEG) can adopt PEG 2000-6000.Polyoxyethylene glycol has wetting action and can work the viscosity effect of regulating.Add polyoxyethylene glycol and help improving stability of formulation, polyoxyethylene glycol can also improve the initial resistance of rainwater washing against performance of product of the present invention simultaneously, improves its weathering resistance.
Select phosphoric acid as the pH regulator agent,, concrete is had reinforcement and do not have destruction because of it is a kind of weak acid and good with the concrete blending.Phosphoric acid is used to regulate the pH value of water-resisting agent to neutrality or weakly alkaline (pH7-7.5).Commercially available methyl silicon sodium alcoholate water-resisting agent often is strong basicity at present, and the pH value reaches 13-14.In use, the slightly acidic of Carbon Dioxide in Air makes speed of response slow excessively, adds phosphoric acid and regulates pH to neutrality or weakly alkaline, can improve the speed of response of water-resisting agent.
Water-resisting agent product of the present invention uses the back to form dual-network in building materials.The one,, methyl silicon sodium alcoholate is at water and CO
2The three-dimensional cross-linked netted poly-methyl silicon ether that effect is condensed into down.The adding of silane coupling agent can make poly-methyl silicon ether be easier to concrete on base material generation chemical action, be bonded on the interface of concrete material, thus with the cement matrix mortise, give full play to the effect of its waterproof.The 2nd,, the salt water-resisting agent of being made up of alum and Fatty Alcohol(C12-C14 and C12-C18)/alkylphenol polyoxyethylene (formaldehyde condensation products) Succinic Acid half ester sulfonate (wherein comprises Na
+, Al
3+And RCOO
-Deng) the title complex network that forms.After the dissolving of Fatty Alcohol(C12-C14 and C12-C18)/alkylphenol polyoxyethylene (formaldehyde condensation products) Succinic Acid half ester sulfonate, RCOO
-Ca in group one end and the contained hardening accelerator of concrete (gypsum)
2+Absorption connects, the other end then with Al
3+Connect, form network-like structure and be adsorbed on the concrete.Like this, negative adsorption extremely strong RCOO
-Can while and Ca
2+And Al
3+The absorption coordination, the result forms one deck by the network-like film of title complex that the organic molecule adsorbing metal ions constitutes at contact surface, is filled into the hole that stays after the cement-earth aquation.Mix when handling in water-resisting agent of the present invention is done, above-mentioned filling effect can improve concrete anti-permeability performance, and improves its intensity.Conventional blending means is adopted in the preparation of product of the present invention, for example by prescription of the present invention, methyl silicon sodium alcoholate, silane coupling agent, alum and fatty alcohol-polyoxyethylene ether Succinic Acid half ester sulfonate or alkylphenol polyoxyethylene Succinic Acid half ester sulfonate or alkylphenol polyoxyethylene formaldehyde condensation products Succinic Acid half ester sulfonate stirred be dissolved in a small amount of hot water, use the phosphoric acid adjust pH to neutrality or weakly alkaline afterwards, add water at last and mend to 100%.Preferably, under whipped state, earlier with Fatty Alcohol(C12-C14 and C12-C18)/alkylphenol polyoxyethylene (formaldehyde condensation products) Succinic Acid half ester sulfonate for example SSOPA and polyoxyethylene glycol, be dissolved in a small amount of hot water (about 60 ℃), add alum, silane coupling agent and methyl silicon sodium alcoholate afterwards, evenly, to 7.0-7.5, add water at last and mend to 100% with the phosphoric acid adjust pH.
Product of the present invention can be handled as surface waterproofing.The concrete structure that general requirement is newly-built, WATER REPELLENT will carry out after 28 days at least; Used concrete structure, will remove surface blot before the WATER REPELLENT,, carried out WATER REPELLENT after the cleaning at least in dry 7 days again with 80-90 ℃ of high pressure water clean surface.The relative humidity of environment should not surpass 65% during WATER REPELLENT, and temperature should be at 5-35 ℃, and concrete surface is dried more, and the WATER REPELLENT effect is good more.Can obviously improve surperficial concrete impermeability after the WATER REPELLENT, objectionable impuritiess such as opposing chlorion are invaded, and can improve the performance of concrete surface.
When water-resisting agent product of the present invention is done the surface processing, can adopt spraying, brushing or impregnation method as required, general recommendations is diluted with water to concentration spraying or the brushing that organosilicon concentration is 2-3% with water-resisting agent, the concentration dipping of 1-5%, and application effect is better.After the surface treatment, water-resisting agent can reach 7-10mm to the concrete surface penetration degree of depth, is much better than commercially available similar water-resisting agent.
In can also being used as, water-resisting agent product of the present invention mixes WATER REPELLENT.Product of the present invention can be used as concrete admixture, mixes wherein as mortar or concrete a kind of composition, concrete structure integral body is imposed interior waterproof handle, and can significantly reduce water regain and chloride permeability amount like this, but the cost height; Perhaps, water-resisting agent product of the present invention is mixed in the cement, make the waterproof type cement based and be applied to the concrete outside surface.This waterproof layer can be used as effective chlorion and water sealing coat, simultaneously, and for concrete provides good curing condition.According to the difference of waterproof requirement, incorporation is the 0.1-1% of mortar or amount of concrete when using.
Product Main Feature of the present invention is as follows:
1, nontoxic, non-volatile, non-stimulated, nonflammable, pollution-free, can be miscible with water, meet the health environment-friendly requirement fully;
2, water resistance excellence, and good weather-proof and weather resistance is arranged;
3, seepage force is strong, can infiltrate concrete surface 7-10mm;
4, anti-permeability performance is strong, improves more than 5 times than Portland cement;
5, wear resisting property is superior, can improve work-ing life more than 6 times;
6, to the effect of reinforcing bar non-corroding;
7, construction safety is easy, and cost is reasonable.
Water-soluble organic silicon water-resisting agent of the present invention is specially adapted to the osmosis type WATER REPELLENT that vesicular structure is run to and fro, for example fragment of brick, stone material, concrete blocks, mortar and grout etc.
Embodiment
The invention will be further described hereinafter to adopt indefiniteness embodiment.Content in the product of the present invention except as otherwise noted is weight/volume content (w/v%).
Embodiment 1
Under the whipped state, earlier 20g SSOPA and 20g polyoxyethylene glycol (PEG 6000) are dissolved in the about 60 ℃ hot water of 100ml, add 40g alum, 25g silane resin acceptor kh-550 and 375g methyl silicon sodium alcoholate afterwards, evenly after, with phosphoric acid adjust pH to 7.5, add water at last and mend to 1000ml.
Embodiment 2
Under the whipped state, earlier 20g SSOPA and 20g polyoxyethylene glycol (PEG 4000) are dissolved in the about 60 ℃ hot water of 100ml, add 40g alum, 30g silane resin acceptor kh-550 and 470g methyl silicon sodium alcoholate afterwards, evenly after, with phosphoric acid adjust pH to 7.5, add water at last and mend to 1000ml.
Embodiment 3
Under the whipped state, earlier 20g SSOPA and 20g polyoxyethylene glycol (PEG 6000) are dissolved in the about 60 ℃ hot water of 100ml, add 40g alum, 25g silane resin acceptor kh-550 and 475g methyl silicon sodium alcoholate afterwards, evenly after,, add water at last and mend to 7.O with the phosphoric acid adjust pH to 1000ml.
Embodiment 4
Under the whipped state, earlier 25g SSOPA and 25g polyoxyethylene glycol (PEG 4000) are dissolved in the about 60 ℃ hot water of 100ml, add 30g alum, 25g silane resin acceptor kh-550 and 475g methyl silicon sodium alcoholate afterwards, evenly after, with phosphoric acid adjust pH to 7.0, add water at last and mend to 1000ml.
Embodiment 5
Under the whipped state, earlier 25g Protowet 4196 and 25g polyoxyethylene glycol (PEG2000) are dissolved in the about 60 ℃ hot water of 100ml, add 35g alum, 25g silane resin acceptor kh-550 and 525g methyl silicon sodium alcoholate afterwards, evenly after, with phosphoric acid adjust pH to 7.0, add water at last and mend to 1000ml.
Embodiment 6
Under the whipped state, earlier 25g SSOPA is dissolved in the 100ml water, adds 25g alum, 25g silane resin acceptor kh-550 and 475g methyl silicon sodium alcoholate afterwards, evenly after, with phosphoric acid adjust pH to 7.0, add water at last and mend to 1000ml.
The water resistance experiment
The consumption of mixing water determines by the mortar slump test that according to the test method of JC 474-1999 and JGJ 56-1984 regulation water cement ratio is 0.40 under its empty mortar, is mixed with that water cement ratio is 0.35 under the water-based organic silicon waterproof agent.
Mortar specimen preparation and test: the cement with accurate weighing mixes with the iso standard sand that meets the GB/T17671-1999 regulation earlier, press the regulation of cement gel Strength Testing Methods GB 177-85 then, adding contains the mixing water of setting water-based organic silicon waterproof agent and stirred 3 minutes.Mortar carries out moulding according to the regulation of GB 177-85, maintenance demoulding after 24 hours under the condition of temperature (20 ± 3 ℃), relative humidity (95 ± 5) %, then maintenance 28 days in the air of temperature (20 ± 3 ℃), relative humidity (65 ± 10) %.Carry out the mortar compressive strength determination according to the regulation of GB 177-85 and GB 11972-89 respectively.
Table 1, mix embodiment 4 water-resisting agents examined the mortar water resistance
| 28d shrinkage ratio (%) | ≤12.5 | ≤135 | 106 |
| Action of rust to reinforcing bar | Do not have | Do not have | Do not have |
Water-intake rate is measured
Water-intake rate is another important indicator that characterizes the water resistance of water-resisting agent.Conventional cement mortar is dried cement briquette to constant weight in baking oven after 28 days in standard chamber maintenance in accordance with regulations.With the cement briquette after the oven dry of the water-resisting agent of the embodiment of the invention 4 dipping, untreated cement briquette is as blank, with two kinds of test blocks middle immersion that discharges water, regularly detects its quality change situation, calculates water-intake rate.
Test shows, after the ortho-water clod immerses in the water, can clearly observe because moisture enters test block, and the air in the kapillary is displaced the bubble that forms, and about 5 minutes, the moisture in the test block is saturated, and water ratio reaches 9-11%.And the test block after the water-resisting agent processing of the present invention, water ratio only reaches 3% after 5 days, soaked 20 days, and water-intake rate less than 4%, and the water ratio of conventional cement mortar test block under physical environment is at 2-4%.After test block fractureed, the checking face was inner dry, and observing the water stain degree of depth is about 1mm, and the water-resisting agent depth of penetration reaches about 7mm.
The abrasion resistance energy
Conventional cement mortar is dried cement briquette to constant weight in baking oven after 28 days in standard chamber maintenance in accordance with regulations.Adopt the cement briquette after the water-resisting agent coating oven dry of the 10g embodiment of the invention 4 and 6 respectively, soaked 1 hour with clear water after 24 hours, measure the methyl silicon sodium alcoholate amount that leaches in the water, embodiment 4 and 6 methyl silicon sodium alcoholate solubility rate are respectively 2.6% and 4.4%.
Though the present invention adopts and above done detailed description, those skilled in the art can make various improvement or modification on above-described basis, and these technical schemes that do not depart from spirit of the present invention are all within protection scope of the present invention.
Claims (6)
1. one kind is the building materials use waterproofing agent of organosilicon of raw material with methyl silanol salt, and (%g/ml) is as follows for the composition of described water-resisting agent and content:
Methyl silicon sodium alcoholate 30-60%
Silane coupling agent 2-5%
Fatty alcohol-polyoxyethylene ether Succinic Acid half ester sulfonate,
Alkylphenol polyoxyethylene Succinic Acid half ester sulfonate
Or alkylphenol polyoxyethylene formaldehyde condensation products Succinic Acid half ester sulfonate 1.5-3.0%
Alum 2.5-6.0%
Phosphoric acid is transferred pH to 7.0-7.5
Water is mended to 100%.
2. according to the water-resisting agent of claim 1, wherein, (%g/ml) is as follows for the content of each composition:
Methyl silicon sodium alcoholate 30-60%
γ-An Bingjisanyiyangjiguiwan 2-5%
Fatty alcohol-polyoxyethylene ether Succinic Acid half ester sulfonate,
Alkylphenol polyoxyethylene Succinic Acid half ester sulfonate
Or alkylphenol polyoxyethylene formaldehyde condensation products Succinic Acid half ester sulfonate 1.5-3.0%
Alum 2.5-5.0%
Polyoxyethylene glycol 0.5-2.5%
Phosphoric acid is transferred pH to 7.0-7.5
Water is mended to 100%
3. according to the water-resisting agent of claim 2, wherein, (%g/ml) is as follows for the content of each composition:
Methyl silicon sodium alcoholate 40-60%
γ-An Bingjisanyiyangjiguiwan 3-5%
SSOPA 1.5-3.0％
Alum 2.5-5.0%
Macrogol 2000-6000 0.5-2.0%
Phosphoric acid is transferred pH to 7.0-7.5
Water is mended to 100%.
4. method for preparing the water-resisting agent of claim 1, it comprises the steps, methyl silicon sodium alcoholate, silane coupling agent, alum and fatty alcohol-polyoxyethylene ether Succinic Acid half ester sulfonate or alkylphenol polyoxyethylene Succinic Acid half ester sulfonate or alkylphenol polyoxyethylene formaldehyde condensation products Succinic Acid half ester sulfonate stirred be dissolved in a small amount of hot water, use the phosphoric acid adjust pH to neutrality or weakly alkaline afterwards, add water at last and mend to 100%.
5. method for preparing arbitrary water-resisting agent of claim 2 or 3, it comprises the steps, under the whipped state, earlier SSOPA and polyoxyethylene glycol are dissolved in a small amount of hot water, add alum, silane coupling agent and methyl silicon sodium alcoholate afterwards, evenly, to 7.0-7.5, add water at last and mend to 100% with the phosphoric acid adjust pH.
6. according to the application of arbitrary water-resisting agent of claim 1-3, described building materials are fragment of brick, stone material, concrete blocks, mortar and grout.
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|---|---|---|---|
| CN2009100327101A CN101580355B (en) | 2009-06-26 | 2009-06-26 | Water-based organic silicon waterproof agent |
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|---|---|---|---|
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| CN101580355B true CN101580355B (en) | 2011-06-15 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050639B (en) * | 2010-08-25 | 2011-12-21 | 潍坊绿城低碳建筑科技有限公司 | Seepage-proof agent of filling system for building |
| CN102020449B (en) * | 2010-09-27 | 2015-06-10 | 东莞市恒和节能科技有限公司 | Composite silicate heat preservation mortar |
| CN102173637B (en) * | 2011-02-18 | 2012-09-26 | 鞍山市鹏程混凝土外加剂有限公司 | Antiseptic and rust resistant high-performance concrete waterproofer |
| CN102219551B (en) * | 2011-04-27 | 2012-10-03 | 河南省交通科学技术研究院有限公司 | Organic silicon waterproof agent with respiratory function and preparation method thereof |
| CN102391836B (en) * | 2011-07-08 | 2013-03-13 | 江苏德一新型建筑材料科技有限公司 | Capillary crystalline type waterproofing agent |
| CN102491679B (en) * | 2011-12-02 | 2013-04-24 | 大连化工研究设计院 | Method for preparing defoamer for cement mortar containing rubber emulsion |
| CN103571327B (en) * | 2012-08-05 | 2016-04-20 | 厦门诺恩斯科技有限公司 | Methyl silicate stone protectant and manufacture method |
| CN103113076B (en) * | 2013-02-22 | 2014-08-13 | 厦门大学 | Organosilicon macromolecular composite waterproof gypsum and preparation method thereof |
| CN107974520A (en) * | 2017-11-07 | 2018-05-01 | 广东菲安妮皮具股份有限公司 | A kind of high-performance environment protection type waterproofing agent |
| CN108585946B (en) * | 2018-04-28 | 2020-12-08 | 山西潞安工程有限公司 | Environment-friendly water-based underground concrete surface protection liquid and preparation method thereof |
| CN108841212A (en) * | 2018-06-20 | 2018-11-20 | 罗国球 | A kind of fluorine silicon emulsion water-proof agent and preparation method thereof |
| CN108911572A (en) * | 2018-06-20 | 2018-11-30 | 河南阳光防水科技有限公司 | Modified penetrant crystalline waterproofing agent of organosilicon |
| CN109400208B (en) * | 2018-11-02 | 2021-06-22 | 华南农业大学 | Alkali-reducing treatment method for ecological concrete |
| CN109867533A (en) * | 2019-04-09 | 2019-06-11 | 吴金良 | A kind of renovation of concrete anti-collision wall and means of defence |
| CN113443880B (en) * | 2021-09-02 | 2021-11-30 | 佛山市东鹏陶瓷发展有限公司 | Light waterproof insulation board and preparation process thereof |
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