CN115124564B - Silicon-containing anionic surfactant and preparation and application thereof - Google Patents

Silicon-containing anionic surfactant and preparation and application thereof Download PDF

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CN115124564B
CN115124564B CN202110265884.3A CN202110265884A CN115124564B CN 115124564 B CN115124564 B CN 115124564B CN 202110265884 A CN202110265884 A CN 202110265884A CN 115124564 B CN115124564 B CN 115124564B
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permeation
agent
modified
water
organosilicon
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CN115124564A (en
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倪红薇
陈冠军
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Hangzhou Bald Advanced Materials Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42Organo-silicon compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • C07F7/1872Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40Surface-active agents, dispersants

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a silicon-containing anionic surfactant and preparation and application thereof, wherein the silicon-containing anionic surfactant is synthesized, and is matched with polyether modified organosilicon penetrant and anionic surfactants such as fatty alcohol polyoxyethylene ether sodium sulfate or sodium sulfonate salt, and the prepared organosilicon modified penetration enhancer can promote inorganic silicate, water glass and other components to permeate into a cement concrete structure, so that the cement concrete has high strength and high compactness, has a very good permanent waterproof and anti-seepage effect, and can be used for reinforcing low-grade concrete structures or repairing and reinforcing concrete damaged by fine cracks. A large number of practices prove that the water-proof anti-permeability agent is obviously superior to the existing water-proof anti-permeability agent, and has great market competitiveness.

Description

Silicon-containing anionic surfactant and preparation and application thereof
Technical Field
The invention relates to the field of building materials, in particular to a silicon-containing anionic surfactant, and preparation and application thereof.
Background
Cement concrete materials are the largest building engineering materials today. In particular, in recent years, as the domestic construction industry has been actively developed, demands for the water resistance and durability of cement concrete materials used in the construction process have been continuously increased. However, the impervious water resistance and durability of the current cement concrete materials can not meet the demands of social development, and further research and improvement are needed.
Cement concrete materials require a certain amount of water during the stirring and casting process, and the water consumption of cement is very small. The residual water forms capillary holes after evaporation, and the pores left in the drying shrinkage process are generally large in pore diameter and open in communication, so that the capillary holes are the main cause of concrete leakage.
In order to improve the sealing impermeability of the cement concrete, the through pores can be inhibited and reduced by additives (such as air entraining agent, water reducing agent and sealing agent) to improve the impermeability; organic polymer materials (such as asphalt, rubber and resin) are also used as the surface treatment materials of the base materials to seal and prevent leakage. However, the former only reduces and inhibits capillary pores, and can not really play a role in sealing and waterproofing; the latter is subject to long-term effects of sunlight, ultraviolet rays, temperature and water, and is liable to undergo aging and peeling, thereby losing the anti-leakage function. It is therefore highly desirable to find a way to truly achieve a permanent seal against water.
At present, extensive researches are carried out at home and abroad on how to improve the impermeability and the water resistance of the cement concrete material, wherein the adoption of an organosilicon material for impermeability and water resistance treatment of the cement concrete is an effective measure in the concrete water-proof engineering. The organic silicon material is a waterproof material which is formed by taking Si-O bonds as main chains and has good weather resistance, ageing resistance and hydrophobic property, and the material can effectively play a good role in impermeability and waterproofing.
In addition, the organic silicon material is mainly used for the surface treatment of cement-based materials, namely, the aims of impermeability and waterproofing are achieved by using an external coating or dipping mode. The external coating or dipping is limited to the surface layer of the cement-based material and the protective layer formed in a few mm in the surface layer, and meanwhile, in order to ensure better waterproof effect, the usage amount of the organic silicon is large, so that the engineering cost is greatly improved. And the waterproof and impervious effect is easily damaged by the external severe environment because the protective layer is formed in a few mm on the surface layer, so that the impervious and waterproof effect is invalid and the durability is poor.
CN105272014a discloses an organosilicon polymer mortar, but it belongs to an internal doped mortar mixed with cement mortar in advance, and cannot penetrate into a cured cement concrete material, and the strength and compactness of a waterproof mortar sample obtained by pouring the mortar are still low, and the organosilicon hydrophobic group of the mortar is formed in concrete too early, so that the strength of the concrete is affected, therefore, the waterproof concrete mortar is more suitable for small-sized structures such as bathroom, and has a great risk for large-sized pouring. CN107805040a discloses a water-based high friction coefficient concrete penetration hardening agent, which adopts organosilicon such as sodium methyl silanol to form a netlike chemical adsorption film, but has poor penetration effect, only forms a protective layer on the surface, and is difficult to penetrate into the concrete to realize permanent waterproof, impervious and reinforcing effects.
The silicon-containing anionic surfactant is generally applied to the prevention and treatment of emulsifying agents, defoamers, waterproofing agents, lubricants, finishing agents, mildewcides, superfine fiber sizing agents and the like in the printing and dyeing industry, or emulsifying agents in the daily chemical industry, and is also used as emulsifying agents in pesticides, but no report on the use of the silicon-containing anionic surfactant as a penetration enhancer in the construction industry exists at present.
Disclosure of Invention
The invention provides a novel silicon-containing anionic surfactant and application thereof in preparing an organosilicon modified permeation promoter, wherein the organosilicon modified permeation promoter is prepared by adopting the silicon-containing anionic surfactant, a polyether modified organosilicon permeation agent and anionic surfactants such as sodium fatty alcohol polyoxyethylene ether sulfate or sodium sulfonate and the like to carry out synergistic compatibility, so that inorganic silicate, water glass and other components can be promoted to permeate into a cement concrete structure, the cement concrete has high strength and high compactness, has very good permanent waterproof and permeation resistance, and can be used for reinforcing a low-grade concrete structure or repairing and reinforcing the concrete damaged by fine cracks. A large number of practices prove that the water-proof anti-permeability agent is obviously superior to the existing water-proof anti-permeability agent, and has great market competitiveness.
In one aspect, the present invention provides a silicon-containing anionic surfactant having a structural formula as shown in formula I:
R’ n Si(OR) 4-n-m X m
i
Wherein n is more than or equal to 1, and m=0 to 3; r' is methyl or ethyl; OR is any one of methoxy, ethoxy OR butoxy; x is-OH.
In another aspect, the present invention provides a method for preparing a silicon-containing anionic surfactant as described above, comprising the main steps of: is obtained by reacting alkoxy silane with amino activity with maleic anhydride under the condition of alcohol solvent, and then reacting with sodium alkoxide.
Further, the chemical reaction formula of the preparation process of the silicon-containing anionic surfactant is as follows:
in yet another aspect, the present invention provides the use of a silicon-containing anionic surfactant having the structural formula shown in formula i:
R’ n Si(OR) 4-n-m X m
i
Wherein n is more than or equal to 1, and m=0 to 3; r' is methyl or ethyl; OR is any one of methoxy, ethoxy OR butoxy; x is-OH.
Further, the silicone modified permeation enhancer comprises a: a silicon-containing anionic surfactant; b: polyether modified organosilicon penetrant; c: anionic surfactants.
Further, the structural formula of the B (polyether modified organosilicon penetrant) is shown as a formula II or a formula III:
wherein n=1 to 20; r ' is a blocking group, R ' is a side chain group, and R ' are any one of EO (ethylene oxide) or EO (ethylene oxide)/PO (propylene oxide) polyether modified MQ silicone resin, MT silicone resin or MTQ silicone resin.
Further, the preparation method of the B (polyether modified organosilicon penetrant) comprises the following steps:
the preparation steps of the formula I are as follows: taking hexamethyldisiloxane, vinyl double-end socket and octamethyl cyclotetrasiloxane, carrying out equilibrium telomerization reaction to obtain monovinyl terminated polysiloxane, and then carrying out addition reaction with unsaturated polyether and MQH resin with H content of 0.8%;
the preparation steps of the formula II are as follows: and (2) taking hexamethyldisiloxane, octamethyl cyclotetrasiloxane and tetramethyl tetravinyl cyclotetrasiloxane, carrying out equilibrium telomerization reaction to obtain polysiloxane with vinyl groups in side chains, and carrying out addition reaction with unsaturated polyether and MQH resin with H content of 0.8%.
Further, the chemical reaction formula of the preparation process of the polyether modified organic silicon penetrating agent is as follows:
the chemical reaction formula in the preparation process of the formula I is as follows:
①MM+ViVi+D 4 →A
(2) A+MQH+unsaturated polyether → product
The method comprises the steps of carrying out a first treatment on the surface of the The chemical reaction formula in the preparation process of the formula II is as follows:
①MM+D 4 +D 4 Vi→A’
(2) a' +MQH+unsaturated polyether → product
Wherein MM is hexamethyldisiloxane, viViVi is vinyl double-seal head, D 4 Is octamethyl cyclotetrasiloxane, D 4 Vi is tetramethyl tetravinyl cyclotetrasiloxane.
Further, the C is sodium fatty alcohol polyoxyethylene ether sulfate or sodium sulfonate.
The research group has surprisingly found that the reagent obtained by adopting the silicon-containing anionic surfactant and polyether modified organic silicon penetrating agent provided by the invention and combining the silicon-containing anionic surfactant and the polyether modified organic silicon penetrating agent with the anionic surfactant such as fatty alcohol polyoxyethylene ether sodium sulfate or sodium sulfonate salt can promote inorganic silicate to permeate into a concrete structure, the permeation depth can reach more than 7 days and 3cm, so that the sealing impermeability of the cement concrete is obviously improved, meanwhile, the concrete structure also has a reinforcing effect on the concrete structure, the concrete structure obtained after permeation is very hard and compact like stone, and can be used for sealing and waterproofing of the cement concrete, forming a waterproof layer with more perfect structure and better sealing property, and also can be used for reinforcing the low-grade concrete structure or repairing and reinforcing the concrete with fine crack damages.
The components such as inorganic silicate solution are usually strong alkali components, so that the penetration enhancer capable of promoting penetration of the inorganic silicate solution must have the characteristic of being very stable in strong alkali environment (pH is 12-14), and meanwhile, the surface tension of the components such as inorganic silicate solution can be obviously reduced, the affinity between the inorganic silicate solution and a cement concrete structure can be improved, the curing time after brushing can be prolonged, and the inorganic silicate solution can be completely penetrated into the concrete structure and then cured.
According to the organosilicon modified penetration enhancer provided by the invention, the organosilicon-containing anionic surfactant is matched with the polyether modified organosilicon penetrant, so that the surface tension of inorganic silicon is reduced by utilizing organosilicon, meanwhile, the sodium sulfonate anionic surfactant is matched, so that the system of the penetration enhancer is more stable, when all components are in balance with inorganic strong alkali silicate, a new modified product can be formed, after the penetration enhancer is permeated into cement concrete, the gel is formed through silanol condensation reaction, capillary holes of the cement concrete are closed, the modified silicate structure contains alkoxy (-OR) which is incompletely reserved after hydrolysis, the silanol group can react with water attached to the surface of inorganic substrates such as cement concrete and the like to form a strong hydrogen bond with the surface of hydroxylated cement concrete, and can further react with the hydroxyl on the surface of cement, so that a high-strength compact impervious body is formed, and a permanent compact cement stone is formed.
Reactive silane synthesis involves several chemical reaction steps, such as organofunctional silane synthesis, silanol mediated, partial hydrolysis, etc. In the test process, the determination of the R' group and the process parameters of the hydroalcoholic medium are selected.
Negative-containing organosilicon anionic surfactants can form equilibrium products with inorganic silicates under certain conditions. The condensation and gelation properties of the modified product have a certain similarity to those of the inorganic silicate alone. Because the organosilicates are multifunctional, they are crosslinked by silanol group condensation.
The organic siloxane group is used for surface hydrophobic treatment, so that the synergistic effect is achieved. The chemical stability of the siloxane effectively changes the comprehensive performance of the building construction, so that the building construction has the comprehensive effects of water resistance, impermeability, corrosion resistance, pollution resistance and the like.
Meanwhile, the organic silicon is used for modification, and the inorganic silicate is used as a main body, so that the silicate can be used as a stabilizing agent of silicate, and gel can be generated when the silicate permeates into capillary pores to block capillary channels, and a sealing effect is achieved. Organosilicon is a compound that is intermediate between inorganic and organic, and has chemical affinity with silicate materials. The material can raise the impervious performance of concrete to form compact cement stone with permanent performance.
The organosilicon modified penetration enhancer provided by the invention has very good stability, can be stored for a long time at room temperature, and has a shelf life of more than 6 months.
Further, the mass ratio of A, B, C is 20-40% to 1-15% to 45-75%.
The proportion of A, B, C in the penetration promoter is also adjusted according to the different components of the base material (such as inorganic silicate or water glass) to be penetrated. The proportion of the components can be adjusted according to the requirements of the processed materials, and proper gelation time can be selected according to the requirements, so that the ideal state of penetration depth of the waterproof agent and water-resistant pressure of the waterproof layer is realized (the gelation time is too short, the penetration is possibly not enough, solidification is started, and the gelation time is too long, the accumulation amount in a cement concrete capillary tube is possibly insufficient, so that the water-resistant pressure capability is poor).
The gel test procedure is exemplified by:
ca (OH) 2 (reactive alkaline substances used in simulated Cement) 0.5g was placed at 15In ml of water, stirring for 2 minutes, slowly adding 20ml of the anti-permeability waterproof agent prepared by the permeation enhancer, stirring for 15 minutes, and recording initial setting time and final setting time. When in use, the product is subjected to comprehensive reaction or gelation under the condition of changing pH or in the presence of a catalyst, so that the impervious waterproof layer with more perfect structure and better sealing property is formed.
The preparation method of the organosilicon modified penetration enhancer provided by the invention comprises the following steps: the A, B, C three components are mixed according to the mass ratio of 20-40 percent to 1-15 percent to 45-75 percent.
In some embodiments, A, B, C is formulated as a by first diluting each with water: 35%, B:35%, C:30% aqueous solution. And A, B, C, and mixing according to a certain proportion.
In yet another aspect, the present invention provides a use of a silicon-containing anionic surfactant having a structural formula as shown in formula i:
R’ n Si(OR) 4-n-m X m
i
Wherein n is more than or equal to 1, and m=0 to 3; r' is methyl or ethyl; OR is any one of methoxy, ethoxy OR butoxy; x is-OH.
The sealing impervious waterproof agent consists of an organosilicon modified penetration enhancer and a penetration base material; the silicone modified permeation enhancer comprises a: a silicon-containing anionic surfactant; b: polyether modified organosilicon penetrant; c: anionic surfactants.
Further, the penetrating base material is any one or more of inorganic silicate, water glass, silica sol, tetrasilicate, calcium hydroxide solution, cement leaching solution and the like.
The organic silicon modified sealing impervious waterproof agent disclosed by the invention can permeate into a building base material to form a compact waterproof layer to resist water pressure permeation. The organosilicon sealing impervious waterproof agent has stronger permeability and can form gel to block gaps in silicate materials and seal capillary pore channels after penetrating into the interior (such as concrete and mortar). Forming an ideal durable waterproof layer. The product is suitable for repairing concrete culvert pipe leakage, reinforcing airport runway concrete, preventing water and seepage of high-rise building basements, preventing moisture regain of industrial factory building large-area terraces and the like, can also be used for treating anti-corrosion engineering concrete base layers, can inhibit neutralization and salt damage, protects chemical force from deteriorating, and has lasting protection effect.
Further, the permeable binder is an inorganic silicate.
When the permeable base material is inorganic silicate, the prepared sealing impervious waterproof agent contains special organic silicon modified inorganic silicate, and can be mixed in cement concrete mixture to form compact cement stone; the coating can be coated on the surface of a concrete construction, permeates into the substrate, reacts with silicate materials to generate new calcium silicate components, and blocks internal gaps and capillary channels, thereby playing a role in sealing and impermeability. The test results show that the organic silicon sealing anti-seepage waterproof agent can permeate into the broken concrete cracks to generate new calcium silicate components, so that the cracks are blocked, capillary holes are closed, the compactness of the concrete test piece is improved, and a reinforcing effect is generated.
Further, the mass ratio of the penetration enhancer to the inorganic silicate is 1.2-1.5:100.
The proportion relation between the penetration enhancer and the inorganic silicate is regulated according to the requirement of the processed material, and the proportion relation after final optimization is determined by a gelation test. The optimization aims at selecting proper gelation speed, so that the penetration depth of the sealing anti-seepage waterproof agent and the water-resistant pressure of the waterproof layer reach ideal states (the gelation time is too short, which can lead to the fact that the sealing anti-seepage waterproof agent begins to solidify before penetration, and the gelation time is too long, which can lead to insufficient accumulation amount in a cement concrete capillary tube and poor water-resistant pressure capability).
Further, the mass ratio of A, B, C in the permeation enhancer is 30:10:50.
In still another aspect, the present invention provides a use of a siliceous anionic surfactant for preparing compact set cement mortar, wherein the siliceous anionic surfactant has a structural formula as shown in formula i:
R’ n Si(OR) 4-n-m X m
i
Wherein n is more than or equal to 1, and m=0 to 3; r' is methyl or ethyl; OR is any one of methoxy, ethoxy OR butoxy; x is-OH.
The compact cement mortar consists of an organosilicon modified penetration enhancer, a penetration base material and cement concrete; the silicone modified permeation enhancer comprises a: a silicon-containing anionic surfactant; b: polyether modified organosilicon penetrant; c: anionic surfactants.
The sealing impervious waterproof agent can be used as a spraying agent. Can also be formulated under conditions such as: the sodium silicate is halved, and sodium lignin sulfonate or molasses is added by 0.2%, and the sodium silicate can also be used as an admixture, so that the sodium silicate sealing compound is suitable for construction operations with different sealing, impermeability and waterproofing requirements. When used as an admixture, the sealing impervious waterproof agent can be mixed with cement concrete to prepare cement mortar, and the cement mortar has excellent performances of reinforcement, corrosion resistance, water resistance, frost crack resistance and the like due to the addition of an organosilicon additive.
Further, the mass ratio of the sealing impervious waterproof agent to the cement concrete is 1:10-1:50.
The mass ratio of the sealing impervious waterproof agent to the cement concrete is mainly determined according to the size of cracks of the original concrete to be painted, the new and old concrete members and the degree of cement neutralization. If the concrete is used as old concrete construction, the dosage of the sealing impervious waterproof agent can be properly increased when the sealing impervious waterproof agent is mixed with cement concrete, and proper Ca (OH) can be added 2 For replenishing the reactive alkaline substances in old cement concrete; if the concrete structure is a concrete structure with leakage and water-gushing points, when the impervious waterproof agent is mixed with cement concrete, the leakage points are chiseled in advance, and the water-gushing is blocked by quick-drying cement. Or the proportion of the sealing impervious waterproof agent is properly increased when the plugging waterproof mortar is prepared, and the plastering repair is carried out by using the sealing impervious waterproof agent. And after curing, coating construction and curing by using a conventional sealing impervious waterproof agent. If it is aimed at a new concrete structure, it canThe proportion of the sealing impervious waterproof agent to the cement is properly reduced, but the sealing impervious waterproof agent cannot be lower than 1 at least: 50.
in summary, the present invention provides a new silicon-containing anionic surfactant and its use for preparing an organosilicon modified penetration enhancer, which mainly has the following beneficial effects:
1. Provides a novel silicon-containing anionic surfactant and a preparation method thereof;
2. the novel silicon-containing anionic surfactant is used for preparing an organosilicon modified penetration enhancer, and the organosilicon modified penetration enhancer can promote inorganic silicate, water glass and other components to penetrate into a cement concrete structure, so that the cement concrete has high strength and high compactness, has a very good permanent waterproof and impervious effect, and can be used for reinforcing low-grade concrete structures or repairing and reinforcing concrete damaged by formed fine cracks. A large number of practices prove that the water-proof anti-permeability agent is obviously superior to the existing water-proof anti-permeability agent, and has great market competitiveness.
2. The novel silicon-containing anionic surfactant and the application thereof in preparing the sealing impervious waterproof agent are provided, and the sealing impervious waterproof agent prepared by mixing a permeation promoter prepared by the silicon-containing anionic surfactant with inorganic silicate, water glass and other components can permeate into a building base material to form a compact waterproof layer, resist water pressure permeation, improve the compactness of a concrete test piece and generate a reinforcing effect. The method is suitable for concrete culvert pipe leakage repair, airport runway concrete reinforcement, old building waterproof and antiseep, high-rise building basement waterproof and antiseep, waterproof and antiseep of wall surface which is corroded by wind and rain for a long time, large-area terrace of industrial factory building preventing from being damped, concrete damage caused by acid, alkali, salt and the like, leakage and corrosion repair and the like, can be used for anticorrosion engineering concrete base layer treatment, can inhibit neutralization and salt injury, protects chemical force from being deteriorated, and has lasting protection effect.
3. The novel silicon-containing anionic surfactant and the application thereof in preparing compact cement mortar are provided, the sealing impervious waterproof agent can be mixed with cement concrete to prepare cement mortar, and the cement mortar has excellent performances of reinforcement, corrosion resistance, water resistance, frost crack resistance and the like due to the mixing of an organosilicon additive, and can form permanent compact cement.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are intended to facilitate the understanding of the present invention without any limitation thereto. The reagents used in this example are all known products and are obtained by purchasing commercially available products.
Example 1 preparation of silicon-containing anionic surfactant
Taking 472g (maleic anhydride) of maleic anhydride, dissolving in 1040g ethanol (95% concentration), dripping 960g of coupling agent KH-550 (amino active alkoxy silane) at 40-50 ℃ for 2.5hr, maintaining for 1 hour after dripping, adding 1096g ethanol and 432g sodium methoxide solution dissolved in advance, measuring pH while adding, and observing transparency until no turbidity or opalescence appears clear, thus obtaining the required qualified product.
Example 2 preparation of polyether modified Silicone penetrant (formula II)
1g of hexamethyldisiloxane (MM), 93g of vinyl double head (ViVi) and octamethyl cyclotetrasiloxane (D) 4 ) 740g, by equilibrium telomerization. Taking 366g of prepared polysiloxane A, 200g of unsaturated polyether (AA 600) and 100g of MQH with H content of 0.8%, and carrying out addition reaction under the action of a platinum (Pt) -containing catalyst to obtain the polyether modified organosilicon penetrant (formula II).
Example 3 preparation of polyether modified Silicone penetrant (formula III)
162g of hexamethyldisiloxane (MM) and octamethyl cyclotetrasiloxane (D) 4 ) 110g, and 86g of vinyl ring (tetramethyl tetravinyl cyclotetrasiloxane) to give polysiloxane A' having vinyl groups in its side chains. And (3) adding 540g of prepared polysiloxane A', 200g of unsaturated polyether (AA 600) and 100g of MQH with H content of 0.8% under the action of a platinum (Pt) -containing catalyst to obtain the polyether modified organosilicon penetrant (formula III).
EXAMPLE 4 preparation of organosilicon modified penetration enhancers (A: B: C=30:10:50)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 5 preparation of organosilicon modified penetration enhancer (A: B: C=20:10:50)
20 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 6 preparation of organosilicon modified penetration enhancer (A: B: C=10:10:50)
10 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 7 preparation of organosilicon modified penetration enhancer (A: B: C=40:10:50)
40 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 8 preparation of organosilicon modified penetration enhancer (A: B: C=80:10:50)
80 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 9 preparation of organosilicon modified penetration enhancer (A: B: C=30:1:50)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 1 part of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 10 preparation of organosilicon modified penetration enhancer (A: B: C=30:0.5:50)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 0.5 part of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate salt) are respectively mixed according to mass fractions to prepare the organic silicon modified penetrating agent.
EXAMPLE 11 preparation of organosilicon modified penetration enhancer (A: B: C=30:15:50)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 15 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 12 preparation of organosilicon modified penetration enhancer (A: B: C=30:20:50)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 20 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 13 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:45)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 45 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 14 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:35)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 35 parts of the C component (sodium sulfonate salt) are respectively mixed according to mass fractions to prepare the organic silicon modified penetrating agent.
EXAMPLE 15 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:75)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 75 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 16 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:85)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 85 parts of the C component (sodium sulfonate) are mixed according to mass fractions respectively to prepare the organic silicon modified penetrating agent.
EXAMPLE 17 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:50)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) provided in example 2 and 50 parts of the C component (fatty alcohol polyoxyethylene ether sodium sulfate) are respectively mixed according to mass fractions to prepare the organic silicon modified penetration enhancer.
EXAMPLE 18 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:50)
30 parts of the A component (silicon-containing anionic surfactant) provided in example 1, 10 parts of the B component (polyether modified organic silicon penetrating agent) (formula III) provided in example 3 and 50 parts of the C component (sodium sulfonate salt) are mixed according to mass fractions, respectively, to prepare the organic silicon modified penetration enhancer.
EXAMPLE 19 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:50)
The component A is prepared by a method disclosed in synthesis of an organosilicon anionic surfactant containing amido (Wang Chao, university of zihaar, university of filling treatises) according to mass fraction, 30 parts of a component B (polyether modified silicone penetrating agent) 10 parts and a component C (sodium sulfonate salt) 50 parts provided in example 2 were mixed to prepare a silicone modified penetration enhancer.
EXAMPLE 20 preparation of organosilicon modified penetration enhancer (A: B: C=30:10:50)
30 parts of a component A (silicon-containing anionic surfactant) provided in example 1 and 50 parts of a component C (sodium sulfonate salt) are mixed according to mass fractions, wherein the component B is a polyether modified organosilicon penetrant prepared by a method disclosed in a document (Li Jiao and the like, printing and dyeing auxiliary, 35 rolls and 10 times) for synthesizing the polyether modified organosilicon anionic surfactant, and the organosilicon modified penetrant is prepared.
Example 21 comparative test of permeation resistance enhancing Effect of sealing permeation resistance waterproofing agent
The reagent provided in examples 1-20, or the pure C component, and inorganic silicate (purchased from Qingdao sodium silicate factory, name: liquid sodium silicate) were used to prepare the anti-permeability waterproof agent according to a mass ratio of 1.5:100, and the anti-permeability enhancing effect of the anti-permeability waterproof agent on the test piece was examined. The test piece mixing ratio is as follows: cement: water: sand: stone = 1:0.85:2.50:4.20, test piece dimensions: 10cm. Times.10 cm. The curing conditions are as follows: demoulding after 24h molding, taking out after 28 days of standard curing, carrying out compressive strength test, immediately unloading after loading to the limit, then coating impervious waterproofing agent on the reagent for 3 times, curing for 7 days in outdoor natural environment, carrying out loading test again, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the penetration depth, the water pressure resistance and the chemical corrosion resistance after coating. The detection method of the penetration depth comprises the following steps: breaking the test piece, and measuring the transverse depth of the hard shell; the detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the results are shown in Table 1.
TABLE 1 comparison of the permeation resistance enhancement effect of the sealing permeation resistance waterproofing agent
As can be seen from table 1, when a single component is mixed with an inorganic silicate, the permeability thereof is poor, and it may be difficult to reduce the surface tension of the inorganic silicate, thereby making it difficult to achieve the permeation promoting effect. When the three components are matched in a synergistic way, the penetration promoting effect is obviously enhanced, which means that when the A, B, C three components are matched in use, the surface tension of the inorganic silicate can be obviously reduced, the inorganic silicate can be kept stable in strong alkali, the inorganic silicate is promoted to gradually penetrate into a test piece and slowly solidify to form gel, the strength is greatly improved, and the permanent cement stone is formed.
Meanwhile, when the inorganic silicate is used for preparing the impervious waterproof agent, the proportion relation of the A, B, C three components has great influence on the prepared penetration enhancer, and the content of A or B is too high or too low, so that the final waterproof and impervious effects and the strength of the cement structure are influenced. Therefore, when the mass ratio of the A, B, C three components is 20-40 percent to 1-15 percent to 45-75 percent, the waterproof and impervious effects are better, and the most preferable ratio is 30:10:50 (example 4).
As can be seen from comparative examples 4 and 17, the component C adopts sodium sulfonate or sodium fatty alcohol-polyoxyethylene ether sulfate, and has little difference in the anti-permeability enhancement performance of cement structures, wherein the effect is slightly better than that of the sodium fatty alcohol-polyoxyethylene ether sulfate when the component C adopts sodium sulfonate.
As can be seen from a comparison of examples 4 and 18, the component B has little difference in the permeation resistance enhancing performance of the cement structure by adopting the formula II or the formula III, wherein the effect is slightly better than that of the sodium fatty alcohol polyoxyethylene ether sulfate when the component B adopts the formula II.
As can be seen from a comparison of example 4 with examples 19 and 20, the use of other silicon-containing anionic surfactants or polyether modified silicone penetrants does not allow for the formation of a stable system with inorganic silicate and promotes its penetration into cement concrete with a significant difference in effect.
EXAMPLE 22 organosilicon modified penetration enhancer and inorganic silicate formulation of Water and Water repellent Agents
The permeation resistant waterproofing agent was prepared by mixing 1 part of the silicone modified permeation promoter provided in example 4 with 100 parts of an inorganic silicate (commercially available from Qingdao sodium silicate works, brand name: liquid sodium silicate) according to mass fractions.
EXAMPLE 23 organosilicon modified penetration enhancer and inorganic silicate formulation of Water and Water repellent Agents
1.2 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of an inorganic silicate (purchased from Qingdao sodium silicate factory, name: liquid sodium silicate) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 24 organosilicon modified penetration enhancer and inorganic silicate formulation as a Water and permeation resistant Agents
1.3 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of inorganic silicate (purchased from Qingdao sodium silicate factory, name: liquid sodium silicate) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 25 organosilicon modified penetration enhancer and inorganic silicate formulation of Water and Water repellent Agents
1.5 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of an inorganic silicate (purchased from Qingdao sodium silicate factory, name: liquid sodium silicate) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 26 organosilicon modified penetration enhancer and inorganic silicate formulation as a Water and permeation resistant Agents
1.7 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of inorganic silicate (purchased from Qingdao sodium silicate factory, name: liquid sodium silicate) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 27 organosilicon modified penetration enhancer and inorganic silicate formulation as a Water and permeation resistant Agents
1.9 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of inorganic silicate (purchased from Qingdao sodium silicate factory, name: liquid sodium silicate) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 28 Effect of organosilicon modified penetration enhancers on the ratio relationship with inorganic silicate
In this example, the permeation-resistant enhancing effects of the permeation-resistant waterproofing agents provided in examples 22 to 27 were examined, respectively, so that the permeation-resistant enhancing effects of the permeation-resistant waterproofing agent were exhibited by the ratio of the permeation accelerator to the inorganic silicate in the permeation-resistant waterproofing agent. The test piece mixing ratio is as follows: cement: water: sand: stone = 1:0.85:2.50:4.20, test piece dimensions: 10cm. Times.10 cm. The curing conditions are as follows: demoulding after 24h molding, taking out after 28 days of standard curing, carrying out compressive strength test, immediately unloading after loading to the limit, then coating impervious waterproofing agent on the reagent for 3 times, curing for 7 days in outdoor natural environment, carrying out loading test again, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the penetration depth, the water pressure resistance and the chemical corrosion resistance after coating. The detection method of the penetration depth comprises the following steps: breaking the test piece, and measuring the transverse depth of the hard shell; the detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the test results are shown in Table 2.
TABLE 2 comparison of permeation resistance enhancement effect of sealing permeation resistance waterproofing agent
As can be seen from Table 2, when the mass ratio of the permeation enhancer to the inorganic silicate is 1.2:100-1.5:100, the prepared sealing permeation-resistant waterproof agent has better permeation-resistant enhancement effect, deeper permeation depth and higher water-resistant pressure; wherein, when the optimal mass ratio of the penetration enhancer to the inorganic silicate is 1.3:100, the prepared sealing impervious waterproof agent has optimal impervious reinforcing effect, and the penetration depth, the water pressure resistance and the chemical corrosion resistance are ideal.
EXAMPLE 29 organosilicon modified penetration enhancer and Water glass formulation as a Water-repellent
The permeation-resistant waterproofing agent was prepared by mixing 1 part of the silicone-modified permeation accelerator provided in example 4 with 100 parts of water glass (purchased from the Qingdao-blue alkali factory) according to mass fractions.
EXAMPLE 30 organosilicon modified penetration enhancer and Water glass formulation as anti-permeation Water repellent
1.3 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of water glass (purchased from Qingdao sodium silicate factory) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 31 organosilicon modified penetration enhancer and Water glass formulation as a Water and permeation resistant agent
1.5 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of water glass (purchased from Qingdao sodium silicate factory) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 32 organosilicon modified penetration enhancer and Water glass formulation as a Water-repellent
1.7 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of water glass (purchased from Qingdao sodium silicate factory) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 33 organosilicon modified penetration enhancer and Water glass formulation as anti-permeation Water repellent
1.9 parts of the organosilicon modified penetration enhancer provided in example 4 are mixed with 100 parts of water glass (purchased from Qingdao sodium silicate factory) according to mass fractions, respectively, to prepare the impervious waterproof agent.
EXAMPLE 34 Effect of organosilicon modified penetration enhancer on Water glass ratio
In this example, the permeation-resistant enhancing effects of the permeation-resistant waterproofing agents provided in examples 29 to 33 were examined, respectively, so that the permeation-resistant enhancing effects of the permeation-resistant waterproofing agent were exhibited by the proportional relationship between the permeation accelerator and the water glass in the permeation-resistant waterproofing agent. The test piece mixing ratio is as follows: cement: water: sand: stone = 1:0.85:2.50:4.20, test piece dimensions: 10cm. Times.10 cm. The curing conditions are as follows: demoulding after 24h molding, taking out after 28 days of standard curing, carrying out compressive strength test, immediately unloading after loading to the limit, then coating impervious waterproofing agent on the reagent for 3 times, curing for 7 days in outdoor natural environment, carrying out loading test again, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the penetration depth, the water pressure resistance and the chemical corrosion resistance after coating. The detection method of the penetration depth comprises the following steps: breaking the test piece, and measuring the transverse depth of the hard shell; the detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the test results are shown in Table 3.
TABLE 3 comparison of permeation resistance enhancement effect of sealing permeation resistance waterproofing agent
As shown in Table 3, when the mass ratio of the permeation enhancer to the water glass is 1.3:100-1.7:100, the prepared sealing permeation-resistant waterproof agent has better permeation-resistant enhancement effect, deeper permeation depth and higher water-resistant pressure; wherein, when the optimal mass ratio of the penetration enhancer to the water glass is 1.5:100, the prepared sealing anti-permeability waterproof agent has optimal anti-permeability enhancement effect, and the penetration depth, the water pressure resistance and the chemical corrosion resistance are ideal.
EXAMPLE 35 organosilicon modified penetration enhancer and waterproofing agent formulated with silica sol
1 part of the organic silicon modified permeation promoter provided in example 4 was mixed with 100 parts of silica sol (purchased from Qingdao Kang Yexin medical silica gel Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 36 organosilicon modified penetration enhancer and method for preparing impervious Water-proofing agent from silica sol
1.5 parts of the organic silicon modified permeation enhancer provided in example 4 were mixed with 100 parts of silica sol (purchased from Qingdao Kang Yexin medical silica gel Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 37 organosilicon modified penetration enhancer and method for preparing impervious Water-proofing agent from silica sol
2.0 parts of the organic silicon modified permeation enhancer provided in example 4 were mixed with 100 parts of silica sol (purchased from Qingdao Kang Yexin medical silica gel Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 38 organosilicon modified penetration enhancer and method for preparing impervious Water repellent from silica sol
2.5 parts of the organic silicon modified permeation enhancer provided in example 4 were mixed with 100 parts of silica sol (purchased from Qingdao Kang Yexin medical silica gel Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 39 organosilicon modified penetration enhancer and method for preparing impervious Water repellent from silica sol
3.0 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of silica sol (purchased from Qingdao Kang Yexin medical silica gel Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 40 organosilicon modified penetration enhancer and waterproofing agent formulated with silica sol
3.5 parts of the organic silicon modified permeation enhancer provided in example 4 were mixed with 100 parts of silica sol (purchased from Qingdao Kang Yexin medical silica gel Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 41 Effect of organosilicon modified penetration enhancer on silica sol ratio
In this example, the permeation-resistant enhancing effects of the permeation-resistant waterproofing agents provided in examples 35 to 40 were examined, respectively, so that the permeation-resistant enhancing effects of the permeation-resistant waterproofing agent were reflected by the proportional relationship between the permeation accelerator and the silica sol in the permeation-resistant waterproofing agent. The test piece mixing ratio is as follows: cement: water: sand: stone = 1:0.85:2.50:4.20, test piece dimensions: 10cm. Times.10 cm. The curing conditions are as follows: demoulding after 24h molding, taking out after 28 days of standard curing, carrying out compressive strength test, immediately unloading after loading to the limit, then coating impervious waterproofing agent on the reagent for 3 times, curing for 7 days in outdoor natural environment, carrying out loading test again, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the penetration depth, the water pressure resistance and the chemical corrosion resistance after coating. The detection method of the penetration depth comprises the following steps: breaking the test piece, and measuring the transverse depth of the hard shell; the detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the test results are shown in Table 4.
TABLE 4 comparison of the permeation resistance enhancement effect of the sealing permeation resistance waterproofing agent
As can be seen from Table 4, when the mass ratio of the penetration enhancer to the silica sol is 1.5:100-3.0:100, the prepared sealing anti-permeability waterproof agent has better anti-permeability enhancement effect, deeper penetration depth and higher water-resistant pressure; wherein, when the optimal mass ratio of the penetration enhancer to the silica sol is 2.0:100, the prepared sealing anti-permeability waterproof agent has optimal anti-permeability enhancement effect, and the penetration depth, the water pressure resistance and the chemical corrosion resistance are ideal.
EXAMPLE 42 organosilicon modified penetration enhancer and waterproofing agent formulated with orthosilicate
1 part of the silicone modified permeation enhancer provided in example 4 was mixed with 100 parts of orthosilicate (available from Zhongjie new materials, inc. in Guangzhou) according to mass fractions, respectively, to prepare a permeation-resistant waterproof agent.
EXAMPLE 43 organosilicon modified penetration enhancer and waterproofing and impervious agent formulated from orthosilicate
1.3 parts of the silicone modified permeation enhancer provided in example 4 was mixed with 100 parts of orthosilicate (available from Zhongjie new materials, inc. in Guangzhou) according to mass fractions, respectively, to prepare a permeation-resistant waterproof agent.
EXAMPLE 44 organosilicon modified penetration enhancer and waterproofing and impervious agent formulated from orthosilicate
1.5 parts of the silicone modified permeation enhancer provided in example 4 was mixed with 100 parts of orthosilicate (available from Zhongjie new materials, inc. in Guangzhou) according to mass fractions, respectively, to prepare a permeation-resistant waterproof agent.
EXAMPLE 45 organosilicon modified penetration enhancer and Water repellent formulated with orthosilicate
1.7 parts of the silicone modified permeation enhancer provided in example 4 was mixed with 100 parts of orthosilicate (available from Zhongjie new materials, inc. in Guangzhou) according to mass fractions, respectively, to prepare a permeation-resistant waterproof agent.
EXAMPLE 46 organosilicon modified penetration enhancer and waterproofing and impervious agent formulated from orthosilicate
1.9 parts of the silicone modified permeation enhancer provided in example 4 was mixed with 100 parts of orthosilicate (available from Zhongjie new materials, inc. in Guangzhou) according to mass fractions, respectively, to prepare a permeation-resistant waterproof agent.
EXAMPLE 47 organosilicon modified penetration enhancer and waterproofing agent formulated with orthosilicate
The permeation resistant waterproofing agent was prepared by mixing 2.1 parts by mass of the silicone modified permeation promoter provided in example 4 with 100 parts by mass of orthosilicate (available from new materials, inc. of Zhongjie, guangzhou).
EXAMPLE 48 Effect of organosilicon modified penetration enhancer on the ratio relationship to orthosilicate
In this example, the permeation-resistant enhancing effects of the permeation-resistant waterproofing agents provided in examples 42 to 47 were examined, respectively, so that the permeation-resistant enhancing effects of the permeation-resistant waterproofing agent were exhibited by the proportional relationship between the permeation accelerator and the orthosilicate. The test piece mixing ratio is as follows: cement: water: sand: stone = 1:0.85:2.50:4.20, test piece dimensions: 10cm. Times.10 cm. The curing conditions are as follows: demoulding after 24h molding, taking out after 28 days of standard curing, carrying out compressive strength test, immediately unloading after loading to the limit, then coating impervious waterproofing agent on the reagent for 3 times, curing for 7 days in outdoor natural environment, carrying out loading test again, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the penetration depth, the water pressure resistance and the chemical corrosion resistance after coating. The detection method of the penetration depth comprises the following steps: breaking the test piece, and measuring the transverse depth of the hard shell; the detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the test results are shown in Table 5.
TABLE 5 comparison of permeation resistance enhancement effect of sealing permeation resistance waterproofing agent
As can be seen from Table 5, when the mass ratio of the permeation enhancer to the orthosilicate is 1.3:100-1.9:100, the prepared sealing permeation-resistant waterproof agent has better permeation-resistant enhancement effect, deeper permeation depth and higher water-resistant pressure; wherein, when the optimal mass ratio of the penetration enhancer to the orthosilicate is 1.7:100, the prepared sealing impervious waterproof agent has optimal impervious reinforcing effect, and the penetration depth, the water pressure resistance and the chemical corrosion resistance are ideal.
EXAMPLE 49 organosilicon modified penetration enhancer and method for preparing impervious waterproofing agent from calcium hydroxide
1 part of the silicone modified permeation enhancer provided in example 4 was mixed with 100 parts of calcium hydroxide (available from upper Rao Furui industrial Co., ltd.) according to mass fractions, respectively, to prepare a water-repellent agent.
EXAMPLE 50 organosilicon modified penetration enhancer and calcium hydroxide formulated into a Water and permeation resistant agent
1.3 parts of the silicone modified permeation enhancer provided in example 4 was mixed with 100 parts of calcium hydroxide (available from upper Rao Furui industrial Co., ltd.) according to mass fractions, respectively, to prepare a permeation-resistant waterproof agent.
EXAMPLE 51 organosilicon modified penetration enhancer and calcium hydroxide to prepare impervious waterproofing agent
1.5 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of calcium hydroxide (available from upper Rao Furui Utility Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 52 organosilicon modified penetration enhancer and method for preparing impervious waterproofing agent from calcium hydroxide
1.7 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of calcium hydroxide (available from upper Rao Furui Utility Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 53 organosilicon modified penetration enhancer and method for preparing impervious waterproofing agent from calcium hydroxide
1.9 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of calcium hydroxide (available from upper Rao Furui Utility Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 54 organosilicon modified penetration enhancer and anti-permeation waterproof agent prepared from calcium hydroxide
2.1 parts of the organosilicon modified penetration enhancer provided in example 4 were mixed with 100 parts of calcium hydroxide (available from upper Rao Furui Utility Co., ltd.) according to mass fractions, respectively, to prepare an anti-permeability waterproof agent.
EXAMPLE 55 Effect of organosilicon modified penetration enhancer on calcium hydroxide ratio
In this example, the permeation-resistant enhancing effects of the permeation-resistant waterproofing agents provided in examples 49 to 54 were examined, respectively, so that the permeation-resistant enhancing effects of the permeation-resistant waterproofing agent were reflected in the relation between the permeation accelerator and calcium hydroxide in the permeation-resistant waterproofing agent. The test piece mixing ratio is as follows: cement: water: sand: stone = 1:0.85:2.50:4.20, test piece dimensions: 10cm. Times.10 cm. The curing conditions are as follows: demoulding after 24h molding, taking out after 28 days of standard curing, carrying out compressive strength test, immediately unloading after loading to the limit, then coating impervious waterproofing agent on the reagent for 3 times, curing for 7 days in outdoor natural environment, carrying out loading test again, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the penetration depth, the water pressure resistance and the chemical corrosion resistance after coating. The detection method of the penetration depth comprises the following steps: breaking the test piece, and measuring the transverse depth of the hard shell; the detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the test results are shown in Table 6.
TABLE 6 comparison of permeation resistance enhancement effect of sealing permeation resistance waterproofing agent
As can be seen from Table 6, when the mass ratio of the penetration enhancer to the calcium hydroxide is 1.5:100-3.0:100, the prepared sealing anti-permeability waterproof agent has better anti-permeability enhancing effect, deeper penetration depth and higher water-resistant pressure; wherein, when the optimal mass ratio of the penetration enhancer to the calcium hydroxide is 2.0:100, the prepared sealing anti-permeability waterproof agent has optimal anti-permeability enhancing effect, and the penetration depth, the water pressure resistance and the chemical corrosion resistance are ideal.
EXAMPLE 56 organosilicon modified penetration enhancer and method for preparing impervious Water-proofing agent from Cement leachate
And (3) taking 1 part of the organosilicon modified penetration enhancer provided in the example 4 and 100 parts of the cement leaching solution according to mass fractions, and mixing to prepare the impervious waterproof agent. The preparation method of the cement leaching solution comprises the following steps: immersing the cement concrete sample block into pure water with neutral pH value after curing, wherein the mass ratio of the cement concrete sample block to the pure water is 1:1, detecting the pH value of the reaction system every time a period of time, and taking out the cement concrete sample block after the pH value is stable to obtain the leaching solution.
EXAMPLE 57 organosilicon modified penetration enhancer and method for preparing impervious Water repellent from Cement leachate
And (3) taking 1.2 parts of the organosilicon modified penetration enhancer provided in the example 4 and 100 parts of cement leaching solution according to mass fractions, and mixing to prepare the impervious waterproof agent. The preparation method of the cement leaching solution comprises the following steps: immersing the cement concrete sample block into pure water with neutral pH value after curing, wherein the mass ratio of the cement concrete sample block to the pure water is 1:1, detecting the pH value of the reaction system every time a period of time, and taking out the cement concrete sample block after the pH value is stable to obtain the leaching solution.
EXAMPLE 58 organosilicon modified penetration enhancer and method for preparing impervious Water-proofing agent from Cement leachate
And (3) taking 1.5 parts of the organosilicon modified penetration enhancer provided in the example 4 and 100 parts of cement leaching solution according to mass fractions, and mixing to prepare the impervious waterproof agent. The preparation method of the cement leaching solution comprises the following steps: immersing the cement concrete sample block into pure water with neutral pH value after curing, wherein the mass ratio of the cement concrete sample block to the pure water is 1:1, detecting the pH value of the reaction system every time a period of time, and taking out the cement concrete sample block after the pH value is stable to obtain the leaching solution.
EXAMPLE 59 organosilicon modified penetration enhancer and method for preparing impervious Water-proofing agent from Cement leachate
And (3) taking 1.7 parts of the organosilicon modified penetration enhancer provided in the example 4 and 100 parts of cement leaching solution according to mass fractions, and mixing to prepare the impervious waterproof agent. The preparation method of the cement leaching solution comprises the following steps: immersing the cement concrete sample block into pure water with neutral pH value after curing, wherein the mass ratio of the cement concrete sample block to the pure water is 1:1, detecting the pH value of the reaction system every time a period of time, and taking out the cement concrete sample block after the pH value is stable to obtain the leaching solution.
EXAMPLE 60 organosilicon modified penetration enhancer and method for preparing impervious waterproofing agent from Cement leachate
1.9 parts of the organosilicon modified penetration enhancer provided in the example 4 are taken and mixed with 100 parts of cement leaching solution according to mass fractions, so as to prepare the impervious waterproof agent. The preparation method of the cement leaching solution comprises the following steps: immersing the cement concrete sample block into pure water with neutral pH value after curing, wherein the mass ratio of the cement concrete sample block to the pure water is 1:1, detecting the pH value of the reaction system every time a period of time, and taking out the cement concrete sample block after the pH value is stable to obtain the leaching solution.
EXAMPLE 61 organosilicon modified penetration enhancer and method for preparing impervious waterproofing agent from Cement leachate
2.1 parts of the organosilicon modified penetration enhancer provided in the example 4 are taken and mixed with 100 parts of cement leaching solution according to mass fractions respectively to prepare the impervious waterproof agent. The preparation method of the cement leaching solution comprises the following steps: immersing the cement concrete sample block into pure water with neutral pH value after curing, wherein the mass ratio of the cement concrete sample block to the pure water is 1:1, detecting the pH value of the reaction system every time a period of time, and taking out the cement concrete sample block after the pH value is stable to obtain the leaching solution.
EXAMPLE 62 Effect of organosilicon modified penetration enhancer on the ratio relationship with Cement leachate
In this example, the permeation-resistant enhancing effects of the permeation-resistant waterproofing agents provided in examples 56 to 61 were examined, respectively, so that the permeation-resistant enhancing effects of the permeation-resistant waterproofing agent were exhibited by the relation between the permeation accelerator and the cement leachate in the permeation-resistant waterproofing agent. The test piece mixing ratio is as follows: cement: water: sand: stone = 1:0.85:2.50:4.20, test piece dimensions: 10cm. Times.10 cm. The curing conditions are as follows: demoulding after 24h molding, taking out after 28 days of standard curing, carrying out compressive strength test, immediately unloading after loading to the limit, then coating impervious waterproofing agent on the reagent for 3 times, curing for 7 days in outdoor natural environment, carrying out loading test again, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the penetration depth, the water pressure resistance and the chemical corrosion resistance after coating. The detection method of the penetration depth comprises the following steps: breaking the test piece, and measuring the transverse depth of the hard shell; the detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the test results are shown in Table 7.
TABLE 7 comparison of permeation resistance enhancement effect of sealing permeation resistance waterproofing agent
As can be seen from Table 7, when the mass ratio of the penetration enhancer to the cement leaching solution is 1.5:100-2.1:100, the prepared sealing anti-permeability waterproof agent has better anti-permeability enhancing effect, deeper penetration depth and higher water-resistant pressure; wherein, when the optimal mass ratio of the penetration enhancer to the cement leaching solution is 1.9:100, the prepared sealing impervious waterproof agent has optimal impervious reinforcing effect, and the penetration depth, the water pressure resistance and the chemical corrosion resistance are ideal.
EXAMPLE 63 Effect of sealing impervious waterproofing Agents on the proportional relationship of Cement mortar
The embodiment adopts the sealing impervious waterproof agent provided in the embodiment 24, wherein the mass ratio of the penetration enhancer to the inorganic silicate is 1.3:100, cement mortar is prepared respectively according to different mass ratios with cement mortar, and the prepared cement impervious test piece comprises the following components in percentage by mass: cement, water, sand, stone=1:0.85:2.50:4.20, curing conditions are: and demolding after molding for 24 hours, taking out after standard curing for 28 days, performing compressive strength test, immediately unloading after loading to the limit, then coating the reagent with impervious waterproof agent for 3 times, curing for 7 days in an outdoor natural environment, then re-performing loading test, frequently watering during curing, recording the strength before and after the impervious test, and simultaneously detecting the water pressure resistance and chemical corrosion resistance after coating. The detection method of the water-resistant pressure is referred to GB50108-2001 (standard); the detection method of the chemical resistance comprises the following steps: respectively soaking a test piece in a 40% industrial sulfuric acid solution, a 20% industrial phosphoric acid solution, a 10% industrial hydrochloric acid solution and a 10% sodium hydroxide solution at room temperature for 28 days, and taking out; the test results are shown in Table 8.
Table 8 comparison of the permeation resistance enhancement effect of the cement stone permeation resistance test piece
As can be seen from Table 8, when the mass ratio of the sealing impervious waterproof agent to the cement mortar is 1:10-1:50, the prepared cement stone has better impervious reinforcing effect, deeper penetration depth and higher waterproof pressure; wherein, when the optimal mass ratio of the sealing impervious waterproof agent to the cement mortar is 1:30, the prepared cement stone has optimal impervious reinforcing effect, and the water pressure resistance and the chemical corrosion resistance are ideal.
EXAMPLE 64 stability investigation of the equilibrium reaction test of penetration enhancer with inorganic silicate
The inorganic silicate used in this example was purchased from Qingdao sodium silicate works (name: liquid sodium silicate).
In the example, the stability of the equilibrium reaction test of the A, B, C three components in the permeation enhancer and the inorganic silicate is examined, the stability of the component A, the component B or the component C and the inorganic silicate are uniformly mixed according to the mass ratio of 1.3:100, and the mixture is stood, and the result is shown in Table 9; the system stability in the equilibrium reaction test of the permeation enhancer and the inorganic silicate was examined, and the equilibrium reaction test was conducted by uniformly mixing the permeation enhancer provided in example 4 with the inorganic silicate in a mass ratio of 1.3:100, and the results are shown in Table 10.
Stability investigation of equilibrium reaction test of three components A, B, C in permeation enhancer and inorganic silicate, respectively
Table 10 stability investigation of equilibrium reaction test of permeation enhancer and inorganic silicate
R' Si (OR) in permeation enhancer 4–n-m x m It can be considered as an organosilicate which is soluble to some degree of hydrolysis. When the organic silicate and the inorganic alkali silicate are copolymerized in balance, a new modified product can be formed, and the reaction formula is shown in the formula IV:
in the growing polymeric silicate structure, the silicate solution is quite stable due to the effect of the stable ionic surface charge.
When the pH is changed or in the presence of a catalyst, the polymeric silicate forms a gel by silanol-based condensation, and eventually becomes insoluble solids. R' Si (OR) 4–n-m x m The modified silicate structure contains an alkoxy group (-OR) which is not completely retained by hydrolysis, and reacts with moisture attached to the surface of an inorganic substrate such as cement concrete to form a silanol group. The group forms a strong hydrogen bond with the surface of the hydroxylated cement concrete, and can further react with hydroxyl groups on the surface of the cement, so that a new gel is formed, and the compactness and the impermeability are improved.
EXAMPLE 62 investigation of the permeation resistance enhancing Effect of the sealing permeation-resistant waterproof agent
The embodiment adopts the organic silicon modified penetration enhancer provided in the embodiment 3, and is evenly mixed with inorganic silicate according to the mass ratio of 1.3:100 to prepare an anti-seepage waterproof agent, and the anti-seepage enhancement effect is examined, and the concrete anti-seepage test method in the test process refers to GBJ82-85 common concrete performance test, and the concrete process comprises the following steps: firstly, putting the well-maintained impervious test piece into a impervious instrument for impervious test until the top surface of the impervious test piece is permeated, recording impervious labels, then, naturally airing the test piece outdoors for 3 days, brushing the impervious waterproof agent of the organic silicon seal for 2 times according to the construction method of the waterproof agent of the organic silicon seal, and after curing for 2 days, brushing the waterproof agent of the cover face: BD-SII (i.e., HS-SII) track 1. After 3 days, the test piece was re-placed in a permeation resistance tester to conduct a permeation resistance test, and the result of the permeation resistance test was recorded, and the test was conducted by a first construction engineering company center laboratory in Zhejiang province, and the results are shown in Table 11.
Table 11 comparison of permeation resistance enhancing effect of sealing permeation resistance waterproofing agent
As can be seen from Table 11, the waterproof and impervious agent of the sealing and impervious agent provided by the invention can obviously improve the waterproof and impervious performance of concrete, can obviously strengthen low-grade concrete structures, has a reinforcing rate of more than 200%, can also improve cement grade, and has an impervious reinforcing effect far exceeding the standard impervious force of common elevation concrete.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.

Claims (1)

1. The use of a silicon-containing anionic surfactant for preparing a sealing, anti-seepage and waterproof agent for improving the strength of concrete is characterized in that the sealing, anti-seepage and waterproof agent consists of an organosilicon modified penetration enhancer and a penetration base material; the silicone modified permeation enhancer comprises a: a silicon-containing anionic surfactant; b: polyether modified organosilicon penetrant; c: sodium sulfonate; the permeable base material is inorganic silicate;
the preparation method of the A comprises the following steps: taking 472g of maleic anhydride, dissolving in 1040g of 95% ethanol, dripping KH-550960g of coupling agent at 40-50 ℃ for 2.5hr, maintaining for 1 hour after dripping, adding 1096g of ethanol and 432g of sodium methoxide solution which are dissolved in advance, measuring pH while adding, and observing transparency until no turbidity or opalescence appears clear, thus obtaining the required qualified product;
the preparation method of the B comprises the following steps: 81g of hexamethyldisiloxane, 93g of vinyl double-end socket and 740g of octamethyl cyclotetrasiloxane are subjected to equilibrium telomerization reaction to obtain monovinyl end-capped polysiloxane A; taking 366g of prepared polysiloxane A, 200g of unsaturated polyether and 100g of MQH with H content of 0.8%, and carrying out addition reaction under the action of a platinum-containing catalyst to obtain a polyether modified organosilicon penetrant;
The mass ratio of the A, B, C is 30:10:50;
the mass ratio of the organosilicon modified penetration enhancer to the inorganic silicate is 1.5:100;
the preparation process of the concrete comprises the following steps: cement is adopted: water: sand: stone=1:0.85:2.50:4.20, curing conditions are: demoulding after 24h molding, taking out after 28 days of standard curing, brushing impervious waterproof reagent for 3 times, curing for 7 days in outdoor natural environment, and then re-carrying out loading test, wherein watering is carried out frequently during curing.
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