CN105924612A - Regulating and controlling preparation method for nano-silicon dioxide sol and nano-silicon dioxide sol enhanced hydrophilic polyurethane grouting material - Google Patents
Regulating and controlling preparation method for nano-silicon dioxide sol and nano-silicon dioxide sol enhanced hydrophilic polyurethane grouting material Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention discloses a regulating and controlling preparation method for nano-silicon dioxide sol and a nano-silicon dioxide sol enhanced hydrophilic polyurethane grouting material. The hydrophilic polyurethane grouting material is characterized by being formed by mixing a component A and a component B; the component A is formed by mixing a prepolymer which is generated by isocyanate and polymer polyol through a polymerization reaction and a diluting agent; the component B is the nano-silicon dioxide sol prepared by regulating and controlling, and is formed by mixing a silica sol and a polyol, wherein the silica sol is generated from a silicon-containing compound by performing in-situ regulating and controlling on a hydrolysis reaction and a condensation polymerization. The hydrophilic polyurethane grouting material is simple in preparation process, wide in raw material source and easy to popularize, and can be used for anti-seepage water plugging of a coal mine, a tunnel, a subway and other underground engineering.
Description
Technical field
The present invention relates to the regulation and control preparation method of a kind of nano silicon dioxide sol and strengthen hydrophilic polyurethane injecting paste material, special
Do not relate to a kind of high intensity for underground engineering antiseepage draining, high size, high stability, the nano silicon of low cost
Modified hydrophilic polyurethane injecting paste material and preparation method thereof.
Background technology
Polyurethane injecting paste material is the chemical sizwe synthesized by polyreaction with polymer polyatomic alcohol by polyisocyanates, because it coagulates
The glue time is adjustable, viscosity is low, impervious leakage-stopping ability is relatively strong, the more high reason of consolidation strength, has been widely used in civil engineering
In waterproofing and leakage-stopping, dam foundation grouting and the anti-of dam concrete crack blend retention of excessive fluid in reinforcement, tunnel piercing and mine construction
The sealing in area and the consolidation of crushed zone, soft foundation reinforcing etc..Traditional polyurethane injecting paste material is by the polymerization of low-molecular-weight
Thing polyhydric alcohol and polyisocyanates are base material, are equipped with the one pack system of the auxiliary agent synthesis such as catalyst or the oil soluble polyurethane note of bi-component
Pulp material.Its gel time is adjustable, viscosity is low, expansion rate is high, anti-permeability is good.Oil soluble polyurethane chemical grouting material simultaneously
Material is elastic little, strong with the adhesion strength of base material, is relatively suitable for impervious leakage-stopping and the reinforcing of concrete in static seam.But run into a large amount of dynamic water
In the case of, owing to it is the most hydrophilic, easily it is unable to reach the effect of anticipation by broken off by water flush.
In order to solve this problem, currently mainly use hydrophilic polyurethane injecting paste material.Conventional hydrophilic polyurethane slip casting material
The material Hydrophilicrto polyether polyhydric alcohol selecting high molecular more, and block with isocyanates.Meet after water can self emulsifying rapidly,
And there is chain extension, branched and cross-linking reaction formation gel induration, to reach the purpose of antiseepage water blockoff.Owing to its bag water yield is big,
Penetration radius is big, is suitable for the leak stopping retention of excessive fluid on dynamic water stratum.Hydrophilic polyurethane injecting paste material owing to can react rapidly with water, institute
High with water blockoff efficiency.But it is relatively costly, low strength, stability deviation make its application be restricted.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the regulation and control preparation method of a kind of nano silicon dioxide sol and strengthens hydrophilic
Property polyurethane injecting paste material, it is intended to retaining on the basis of original hydrophilic polyurethane grouting for water blocking material high combination property, carrying
Its strength and stability high.
The present invention solves technical problem, adopts the following technical scheme that
The present invention first disclose a kind of regulate and control preparation nano silicon dioxide sol, its each raw material by the composition of mass fraction is:
Described silicon-containing compound is waterglass or hydrophilic Ludox；Described waterglass is sodium silicate or KP1, and modulus is
2～4；The mean diameter of described hydrophilic Ludox is 10～20nm, and density is 1.15～1.30g/cm3, dioxide-containing silica is
30%～40%.
Described catalyst is triethanolamine, triethylene diamine, dimethyl cyclohexyl amine, dibutyltin diacetate and tin dilaurate two fourth
The synergistic catalyst of one or more compositions of base stannum；
Described pH adjusting agent is sodium hydroxide, potassium hydroxide, ammonia, hydrochloric acid, sodium carbonate, potassium carbonate, citric acid, Pyrusussuriensis
One or more in acid, malic acid, tartaric acid, acetic acid or lactic acid；
Described polyhydric alcohol is Polyethylene Glycol, polypropylene glycol, ethylene glycol, glycerol, diethylene glycol, trimethylolpropane or Ji Wusi
One or more in alcohol.
The invention also discloses the regulation and control preparation method of above-mentioned nano silicon dioxide sol, it is characterised in that: by silicon-containing compound,
Catalyst, pH adjusting agent, polyhydric alcohol and water pH value be 3～7, temperature be 15～40 DEG C under conditions of mixing and stirring,
I.e. obtain the nano silicon dioxide sol of regulation and control preparation.
The present invention further discloses nano silicon dioxide sol and strengthen hydrophilic polyurethane injecting paste material, it is by component A and group
Obtain after dividing B 1:1 in mass ratio～5 mixing；
Described component A is the performed polymer generated by polyreaction by isocyanates and polymer polyatomic alcohol, mixes with inert diluent
Close；In described component A, each raw material is configured to by mass fraction:
Polymer polyatomic alcohol 100 parts,
Isocyanates 15～50 parts,
Inert diluent 40～100 parts；
Described component B is the nano silicon dioxide sol of above-mentioned regulation and control preparation.
Described polymer polyatomic alcohol is hydrophilic polyether polyhydric alcohol, EO >=80%, degree of functionality 3～6, molecular weight 5000～15000, hydroxyl
Value is 18～60mgKOH/g.
Described isocyanates is methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate, naphthalene two
One or more in isocyanates, polymethylene multi-phenenyl isocyanate or isophorone diisocyanate.
Described inert diluent is diethylene glycol ether acetate, dibutyl phthalate, citric acid tri butyl ester, Oleum Ricini first
One or more in acid fat, alkyl phosphate, propylene carbonate or 2-Butoxyethyl acetate.
The preparation method of above-mentioned hydrophilic polyurethane injecting paste material, comprises the steps:
(1) component A is prepared: adding polymer polyatomic alcohol in equipped with the reactor of agitator, decompression is de-at 110～130 DEG C
Water 1.5～3.5 hours, be cooled to 25～40 DEG C, adds isocyanates 5～15 parts, reacts 2-5 hour at 60～90 DEG C, then add
Enter residual isocyanate, react 0.5-3 hour at 60～90 DEG C；It is cooled to 25～40 DEG C, adds inert diluent, stir,
Obtain component A；
(2) prepare component B: by silicon-containing compound, catalyst, pH adjusting agent, polyhydric alcohol and water pH value be 3～7, temperature
Degree is mixing and stirring under conditions of 15～40 DEG C, it is thus achieved that the nano silicon dioxide sol of regulation and control preparation, is component B；
(3) component A is mixed homogeneously with component B 1:1～1:5 in mass ratio, obtain hydrophilic polyurethane injecting paste material.
During use, component A is mixed homogeneously with component B 1:1 in mass ratio～5, it is thus achieved that hydrophilic polyurethane grouting for water blocking material
Material, injects it rapidly and needs the position of impervious leakage-stopping, can gel solidification rapidly, play the effect of impervious leakage-stopping.
The present invention, with cheap silicon-containing compound for silicon source, is hydrolyzed into the mistake of nano silicon by regulation and control silicon-containing compound in situ
Journey, prepares that particle diameter is less, narrow distribution, finely dispersed nano silicon dioxide sol, is subsequently adding polyhydric alcohol and passes through electrostatic
Adsorption makes polyhydric alcohol be coated on the surface of nano silicon, significantly improves nano-silicon dioxide particle and hydrophilic
The compatibility of polyurethane matrix；Finally by the chemical reaction of isocyanates Yu water, it is prepared for based on original position controlling type nano-silica
The hydrophilic polyurethane injecting paste material of the increased response of SiClx colloidal sol.Due in nano silicon molecular structure containing a lot of not
Saturated residual bond and different key and the hydroxyl of state, serve the effect of a crosslinking points in polyurethane matrix, improve polyurethane
The interior crosslink density of material, makes the polyurethane material of the present invention have the advantages that concretion body strength is high, dimensional stability is high.Introduce
Cheap silicon-containing compound, low cost.Further, the existence of silicon-containing compound intermediate ion makes induration osmotic pressure uprise, and is difficult to
Dehydration；Gel time is adjustable, nonflammable, weatherability is good.
Compared with the prior art, beneficial effects of the present invention is embodied in:
The hydrophilic polyurethane injecting paste material of the present invention has higher concretion body strength and dimensional stability, have de-luxe compartment aqueous,
Gel time is adjustable, repeat the advantage that water shut-off is good.
The hydrophilic polyurethane injecting paste material preparation of the present invention is simple, easy construction.With cheap silicon-containing compound for silicon source, logical
Cross in situ regulation and control silicon-containing compound and be hydrolyzed into the process of nano silicon, prepare that particle diameter is less, narrow distribution, be uniformly dispersed
Nano silicon dioxide sol, add polyhydric alcohol and drastically increase the compatibility of nano silicon and polyurethane matrix so that
Nano silicon in polyurethane matrix homogeneous grain diameter, be uniformly dispersed.The hydrophilic injecting paste material obtained can be according to actual feelings
The gel time that condition regulation is different.With the silicone hydroxyl in silicon-containing compound as internal crosslinker, the degree of cross linking is high.Introduce hydrophilic silicon molten
Glue, good hydrophilic property, interior crosslinking degree are high.Introduce waterglass, with low cost, and remain sodium ion therein or potassium ion,
Improve the osmotic pressure of induration.Induration is made on the one hand to be not easy dehydration, the most permissible in the case of complete dehydration
Imbibition faster, can the most perfectly realize the effect of secondary water blockoff.Introduce pH adjusting agent, by regulation pH value
Control hydrolysis and the polycondensation speed of silicon-containing compound, prepare the nano-silica of the nano-scale distribution that particle diameter is less, distribution is the narrowest
SiClx, particle diameter its specific surface area the least of nano silicon is equivalent to the most greatly improve crosslink density.Introduce water, pass through water
Form polyurethane induration with the isocyanato generation chemical reaction in base polyurethane prepolymer for use as, heat can be released in this process
Amount generates carbon dioxide simultaneously.The generation of heat promotes the carrying out of reaction the most to a certain extent, and the carbon dioxide energy generated
Substantial amounts of volumetric expansion is provided, thus blocks crack and play the effect of antiseepage water blockoff, and the carbon dioxide of part can be dissolved in aquatic
Becoming carbonic acid, the hydrion that carbonic acid provides can promote again the generation of nano silicon further.Introduce polyhydric alcohol, due to silicate
Isoelectric point, IP be pH=2, it is meant that at pH > 2 time silicate be electronegative.And the oxygen atom on hydroxyl contains in polyhydric alcohol
Lone pair electrons, can be combined with proton hydrogen and form positively charged oxonium ion.Therefore, when pH=3～7, electrostatic interaction is passed through
Polyhydric alcohol can be adsorbed onto the surface of nano silicon, and polyhydric alcohol can form hydrogen bond action and chemistry with the main chain of polyurethane matrix again
In conjunction with, thus solve when traditional method is directly added into inorganic particulate the problem of the compatibility, nanometer between organic facies and inorganic phase
Silicon dioxide also acts as the effect of inorganic fill while playing crosslinking points effect, and therefore concretion body strength is big.It is particularly well-suited to
The antiseepage water blockoff of colliery, tunnel, subway and other underground engineerings.
Detailed description of the invention
Below by the mode of embodiment, the present invention is further described, but the most therefore limits the present invention to described reality
Execute among example scope.
In following embodiment, the method for testing of volume stability is: stir rapidly after component A being mixed with component B, makes
A diameter of 5cm, the induration of a height of 5cm, be placed in induration in 70 DEG C of baking ovens and be dried 24h, be then placed in water leaching
Bubble 168h.Volume stability is the volume after soaking and the ratio drying front volume.
Embodiment 1
(1) (hydroxyl value is 20mgKOH/g, sense to add hydrophilic polyether polyhydric alcohol 100 parts in equipped with the reactor of agitator
Degree is 4, molecular weight is about 11000, EO content accounts for 85%), at 110 DEG C, decompression dehydration 2.5 hours, are cooled to 30
DEG C, it is subsequently adding toluene di-isocyanate(TDI) 10 parts, reacts 4 hours at 60 DEG C, add methyl diphenylene diisocyanate 20
Part, 90 DEG C are reacted 1 hour, are cooled to 25 DEG C, add diethylene glycol ether acetate 40 parts and stir, it is thus achieved that component A；
(2) by 150 parts of water, waterglass (sodium silicate, modulus is 3.3) 30 parts, triethanolamine 1 part, tetramethylolmethane 15
Part, pH adjusting agent (sodium hydroxide and hydrochloric acid) 50 parts is in pH=4, mixing and stirring at 20 DEG C, it is thus achieved that receiving of regulation and control preparation
Rice silicon dioxide gel, is component B；
(3) when using, component A is mixed homogeneously with the weight ratio of 1:1 with B component, obtain what nano silicon strengthened
Hydrophilic polyurethane injecting paste material.
The technical specification of the present embodiment products obtained therefrom is shown in Table 1:
Table 1
| Component A viscosity | 340mPa·s |
| Gel time | 15s |
| Bag aqueous | 20 times of water |
| Volume stability | 0.85 |
| Compressive strength | 0.67MPa |
| Vertical combustion experimental grade | FV-1 |
Embodiment 2
(1) (hydroxyl value is 28mgKOH/g, sense to add hydrophilic polyether polyhydric alcohol 100 parts in equipped with the reactor of agitator
Degree is 3, molecular weight is about 6000, EO content accounts for 80%), decompression dehydration 1.5 hours at 130 DEG C, it is cooled to 40 DEG C,
It is subsequently adding toluene di-isocyanate(TDI) 12 parts, reacts 3.5 hours at 70 DEG C, add methyl diphenylene diisocyanate 30 parts,
80 DEG C are reacted 2 hours, are cooled to 30 DEG C, add citric acid tri butyl ester 50 parts and stir, it is thus achieved that component A；
(2) by 200 parts of water, waterglass (sodium silicate, modulus is 3.0) 10 parts, dimethyl cyclohexyl amine 1.5 parts, the third three
Alcohol 10 parts, pH adjusting agent (sodium hydroxide and citric acid) 30 parts are in pH=3, mixing and stirring at 25 DEG C, it is thus achieved that regulation and control
The nano silicon dioxide sol of preparation, is component B；
(3) when using, component A is mixed homogeneously with the weight ratio of 1:1 with B component, obtain what nano silicon strengthened
Hydrophilic polyurethane injecting paste material.
The technical specification of the present embodiment products obtained therefrom is shown in Table 2:
Table 2
| Component A viscosity | 360mPa·s |
| Gel time | 19s |
| Bag aqueous | 20 times of water |
| Volume stability | 0.82 |
| Compressive strength | 0.56MPa |
| Vertical combustion experimental grade | FV-1 |
Embodiment 3
(1) (hydroxyl value is 30mgKOH/g, sense to add hydrophilic polyether polyhydric alcohol 100 parts in equipped with the reactor of agitator
Degree is 4, molecular weight is about 10000, EO content accounts for 85%), decompression dehydration 2 hours at 115 DEG C, it is cooled to 30 DEG C,
It is subsequently adding isophorone diisocyanate 10 parts, reacts 4.5 hours at 60 DEG C, add polymethylene multi-phenenyl isocyanate
25 parts, 70 DEG C are reacted 2 hours, are cooled to 25 DEG C, add 2-Butoxyethyl acetate 60 parts and stir, it is thus achieved that component A；
(2) by 250 parts of water, Ludox (density 1.20g/cm3, particle diameter 15nm, dioxide-containing silica is 33%) 40 parts,
Catalyst (triethanolamine and triethylene diamine mass ratio 1:1) 1 part, polypropylene glycol 20 parts, pH adjusting agent (ammonia and Fructus Mali pumilae
Acid) 70 parts in pH=6, mixing and stirring at 30 DEG C, it is thus achieved that the nano silicon dioxide sol of regulation and control preparation, it is component B；
(3) when using, component A is mixed homogeneously with the weight ratio of 1:3 with B component, obtain what nano silicon strengthened
Hydrophilic polyurethane injecting paste material.
Above example obtains technical target of the product and is shown in Table 3:
Table 3
Embodiment 4
(1) in equipped with the reactor of agitator add hydroxyl value be hydrophilic polyether polyhydric alcohol 100 parts (hydroxyl value be 35mgKOH/g,
Degree of functionality is 4, molecular weight is about 13000, EO content accounts for 90%), at 125 DEG C, decompression dehydration 2 hours, are cooled to
35 DEG C, it is subsequently adding isophorone diisocyanate 5 parts, reacts 3.5 hours at 70 DEG C, add toluene di-isocyanate(TDI) 30
Part, 90 DEG C are reacted 0.5 hour, are cooled to 40 DEG C, add 30 parts of Oleum Ricini formic acid fat and stir, it is thus achieved that component A；
(2) by 180 parts of water, waterglass (KP1, modulus is 3.0) 25 parts, triethylene diamine 1.5 parts, diethylene glycol
18 parts, pH adjusting agent (ammonia and hydrochloric acid) 80 parts is in pH=4, mixing and stirring at 25 DEG C, it is thus achieved that the nanometer of regulation and control preparation
Silicon dioxide gel, is component B；
(3) when using, component A is mixed homogeneously with the weight ratio of 1:4 with B component, obtain what nano silicon strengthened
Hydrophilic polyurethane grouting for water blocking material.
The technical specification of the present embodiment products obtained therefrom is shown in Table 4:
Table 4
| Component A viscosity | 330mPa·s |
| Gel time | 33s |
| Bag aqueous | 13 times of water |
| Volume stability | 0.88 |
| Compressive strength | 0.51MPa |
| Vertical combustion experimental grade | FV-1 |
Embodiment 5
(1) (hydroxyl value is 26mgKOH/g, sense to add hydrophilic polyether polyhydric alcohol 100 parts in equipped with the reactor of agitator
Degree is 3, molecular weight is about 8000, EO content accounts for 80%), decompression dehydration 1.5 hours at 130 DEG C, it is cooled to 30 DEG C,
It is subsequently adding hexamethylene diisocyanate 10 parts, reacts 5 hours at 60 DEG C, add polymethylene multi-phenenyl isocyanate
35 parts, 70 DEG C are reacted 2.5 hours, are cooled to 20 DEG C, add propylene carbonate 70 parts and stir, it is thus achieved that component A；
(2) by 150 parts of water, Ludox (density 1.15g/cm3, particle diameter 15nm, dioxide-containing silica is 35%) 25 parts,
Dibutyltin diacetate 2 parts, tetramethylolmethane 15 parts, pH adjusting agent (potassium hydroxide and acetic acid) 60 parts pH=5,40 DEG C
Lower mixing and stirring, it is thus achieved that the nano silicon dioxide sol of regulation and control preparation, is component B；
(3) when using, component A is mixed homogeneously with the weight ratio of 1:2 with B component, obtain what nano silicon strengthened
Hydrophilic polyurethane grouting for water blocking material.
The technical specification of the present embodiment products obtained therefrom is shown in Table 5:
Table 5
| Component A viscosity | 350mPa·s |
| Gel time | 28s |
| Bag aqueous | 15 times of water |
| Volume stability | 0.84 |
| Compressive strength | 0.54MPa |
| Vertical combustion experimental grade | FV-1 |
Claims (9)
1. the nano silicon dioxide sol regulating and controlling preparation, it is characterised in that: each raw material by the composition of mass fraction is:
The nano silicon dioxide sol of regulation and control preparation the most according to claim 1, it is characterised in that: described silicon-containing compound
For waterglass or hydrophilic Ludox；Described waterglass is sodium silicate or KP1, and modulus is 2～4；Described hydrophilic silicon
The mean diameter of colloidal sol is 10～20nm, and density is 1.15～1.30g/cm3, dioxide-containing silica is 30%～40%.
The nano silicon dioxide sol of regulation and control preparation the most according to claim 1, it is characterised in that: described catalyst is three
Ethanolamine, triethylene diamine, dimethyl cyclohexyl amine, dibutyltin diacetate and one or more groups of dibutyl tin laurate
The synergistic catalyst become；
Described pH adjusting agent is sodium hydroxide, potassium hydroxide, ammonia, hydrochloric acid, sodium carbonate, potassium carbonate, citric acid, Pyrusussuriensis
One or more in acid, malic acid, tartaric acid, acetic acid or lactic acid；
Described polyhydric alcohol is Polyethylene Glycol, polypropylene glycol, ethylene glycol, glycerol, diethylene glycol, trimethylolpropane or Ji Wusi
One or more in alcohol.
4. the regulation and control preparation method of nano silicon dioxide sol described in any one in a claims 1 to 3, it is characterised in that:
By silicon-containing compound, catalyst, pH adjusting agent, polyhydric alcohol and water pH value be 3～7, under conditions of temperature is 15～40 DEG C
Mixing and stirring, i.e. obtains the nano silicon dioxide sol of regulation and control preparation.
5. a nano silicon dioxide sol strengthens hydrophilic polyurethane injecting paste material, it is characterised in that: described hydrophilic polyurethane
Injecting paste material is to be obtained by after component A and component B 1:1 in mass ratio～5 mixing；
Described component A is the performed polymer generated by polyreaction by isocyanates and polymer polyatomic alcohol, mixes with inert diluent
Close；In described component A, each raw material is configured to by mass fraction:
Polymer polyatomic alcohol 100 parts,
Isocyanates 15～50 parts,
Inert diluent 40～100 parts；
Described component B is the nano silicon dioxide sol of the regulation and control preparation in claims 1 to 3 described in any one.
Hydrophilic polyurethane injecting paste material the most according to claim 5, it is characterised in that: described polymer polyatomic alcohol is parent
Water polyether polyol, EO >=80%, degree of functionality 3～6, molecular weight 5000～15000, hydroxyl value is 18～60mgKOH/g.
Hydrophilic polyurethane injecting paste material the most according to claim 5, it is characterised in that: described isocyanates is diphenyl
Methane diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl
One or more in isocyanates or isophorone diisocyanate.
Hydrophilic polyurethane injecting paste material the most according to claim 5, it is characterised in that: described inert diluent is diethyl
Glycol ether acetate, dibutyl phthalate, citric acid tri butyl ester, Oleum Ricini formic acid fat, alkyl phosphate, propylene glycol
One or more in carbonic ester or 2-Butoxyethyl acetate.
9. the preparation method of hydrophilic polyurethane injecting paste material described in any one in a claim 5～8, it is characterised in that bag
Include following steps:
(1) component A is prepared: adding polymer polyatomic alcohol in equipped with the reactor of agitator, decompression is de-at 110～130 DEG C
Water 1.5～3.5 hours, be cooled to 25～40 DEG C, adds isocyanates 5～15 parts, reacts 2-5 hour at 60～90 DEG C, then add
Enter residual isocyanate, react 0.5-3 hour at 60～90 DEG C；It is cooled to 25～40 DEG C, adds inert diluent, stir,
Obtain component A；
(2) prepare component B: by silicon-containing compound, catalyst, pH adjusting agent, polyhydric alcohol and water pH value be 3～7, temperature
Degree is mixing and stirring under conditions of 15～40 DEG C, it is thus achieved that the nano silicon dioxide sol of regulation and control preparation, is component B；
(3) component A is mixed homogeneously with component B 1:1～1:5 in mass ratio, obtain hydrophilic polyurethane injecting paste material.
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