AMPHIPATHIC MULTIFUNCTIONAL HYBRID NANOPARTICLE, AND PREPARATION METHOD THEREFOR AND APPLICATION THEREOF

Abstract

Disclosed is an amphiphilic multifunctional hybrid nanoparticle. The nanoparticle of the present invention has a detachable hydrophilic organic polymer with both a water-soluble long chain and a hydrophobic long hydrocarbon functional group attached to the surface, wherein the body of the nanoparticle is a silica or an organofunctional group substituted silica or an organofunctional group substituted silicon-oxygen bond network, and the nanoparticle contains a free organosiloxane with hydrophobic long hydrocarbon functional groups and a fatty acid or fatty acid ester or aluminum complex of fatty acid with hydrophobic long hydrocarbon functional groups. The nanoparticle can reduce the water permeability of the cement-based material; the cement-based material has the internal hydration products and interfaces are hydrophobized, further reducing the possibility that the harmful particles erode the cement-based material through moisture penetration; furthermore, Si—Al oxides participate is beneficial to the improvement of its mechanical properties.

Claims

1. An amphiphilic multifunctional hybrid nanoparticle having a detachable hydrophilic organic polymer with both a water-soluble long chain and a hydrophobic long hydrocarbon functional group attached to the surface, wherein the body of the nanoparticle is a silica or an organofunctional group substituted silicon dioxide or an organofunctional group substituted silicon-oxygen bond network, and the nanoparticle contains a free organosiloxane with hydrophobic long hydrocarbon functional groups and a fatty acid or fatty acid ester or fatty acid aluminum complex with hydrophobic long hydrocarbon functional groups; the nanoparticle has an average diameter of not more than 1000 nm.

2. A preparation method of the amphiphilic multifunctional hybrid nanoparticle according to claim 1 comprises the following steps: (1) adding water, a first batch of a polymerizable monomer A, a first batch of a non-radical polymerizable siloxane C having hydrophobic hydrocarbon functional groups, and a first batch of a siloxane or organofunctional group substituted siloxane D to a reactor, stirring for fully mixing, adjusting the pH of the mixed solution to 2-10, introducing N.sub.2 to the mixed solution to remove O.sub.2, and adjusting the temperature of the reaction system to 0-70° C.; (2) immediately adding an aqueous solution of an initiator to the mixed solution prepared in step (1) or separately adding an initiator and water to initiate polymerization and also uniformly dropwise adding a polymerizable siloxane B, a second batch of the siloxane or organofunctional group substituted siloxane D, a second batch of the non-radical polymerizable siloxane C having hydrophobic hydrocarbon functional groups, and a second batch of the polymerizable monomer A, and reacting for 1-6 hours; and (3) adding a third batch of non-radical polymerizable siloxane C having a hydrophobic long chain and an organic component E to the mixed solution obtained after reaction in step (2), further stirring for 0.5-3 hours, returning the reaction system to room temperature, and adjusting the pH of the mixed solution to 7, thus obtaining a dispersion of the amphiphilic multifunctional hybrid nanoparticle; wherein the polymerizable monomer A has a double bond at one end to participate in a radical polymerization reaction, and also has a water-soluble long chain at the other end, and the polymerizable monomer A is one of or any combination of more than one of structures represented by the following formula (1) and formula (2), ##STR00008## where R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each independently represent H or CH.sub.3, X represents —OCH.sub.2CH.sub.2—, —OCH.sub.2CH.sub.2CH.sub.2CH.sub.2—, or saturated alkyl with 1 to 4 carbon atoms, and Y represents —NH— or —O—; a and b represent the average molar adduct numbers of ethoxy and isopropoxy in the side chain, respectively, the value of (a+b) ranges from 8 to 114 (8 and 114 are included), and the value of a/(a+b) is not more than ⅓; the polymerizable siloxane B is any one of or a mixture of more than one of methacryloxypropyltrimethoxysilane (MAPTMS), methacryloxypropyltriethoxysilane (MATTES), methacryloxymethyltriethoxysilane (AAPTMS), acryloyloxymethyltrimethoxysilane (AAMTMS), and acryloxypropyltrimethoxysilane (AAPTMS); the non-radical polymerizable siloxane C having hydrophobic hydrocarbon functional groups is one of or any combination of more than one of siloxanes having a structure of the following formula (3), ##STR00009## where R.sub.5 represents a hydrocarbon functional group with 4 to 22 carbon atoms, R.sub.6, R.sub.7 and R.sub.8 each independently represent saturated alkyl with 1 to 4 carbon atoms, and R.sub.5, as a source of hydrophobicity of the particle, needs to ensure a sufficient carbon chain length; the siloxane or organofunctional group substituted siloxane D is one of or any combination of more than one of siloxanes having a structure of the following general formula (4), ##STR00010## where R.sub.9 and R.sub.10 each independently represent saturated alkyl with 1 to 6 carbon atoms or saturated alkoxy with 1 to 4 carbon atoms, and R.sub.11 and R.sub.12 each independently represent saturated alkyl with 1 to 4 carbon atoms; the organic component E is one of or any combination of more than one of saturated or a unsaturated long-chain fatty acid or fatty acid ester F and an aluminum complex G of a saturated or unsaturated aliphatic long-chain fatty acid. the saturated or unsaturated long-chain fatty acid or fatty acid ester F is one or more than any one of saturated or unsaturated long-chain fatty acid or fatty acid esters having a structure of the following formula (5), ##STR00011## where the functional group R.sub.13 represents a hydrocarbon functional group with 5 to 21 carbon atoms, and R.sub.14 represents H or saturated alkyl with 1 to 22 carbon atoms; the aluminum complex G of the saturated or unsaturated aliphatic long-chain fatty acid is one of or any combination of more than one of aluminum complexes of formula Al(R.sub.15COO).sub.3 or Al(OH)(R.sub.16COO).sub.2, where R.sub.15 and R.sub.16 each independently represent a saturated or unsaturated hydrocarbon functional group with 8 to 18 carbon atoms; the total mass of effective reactants (A+B+C+D+E) in the reaction system accounts for no more than 30% of the total mass of the reaction system; the polymerizable monomer A accounts for 5-20% of the total mass of the effective reactants; the total mass of B and D accounts for 20-75% of the total mass of the effective reactants (A+B+C+D+E), and the mass of B accounts for 5-10% of the total mass of B and D; the total mass of C and E accounts for 20-75% of the total mass of the effective reactants (A+B+C+D+E), and the mass of C accounts for 20-80% of the total mass of C and E (C+E); the ratio of F to G in the organic component E is arbitrary; the use of water added in the step (1) accounts for 50-90% of the total water consumption of the reaction; if the polymerizable monomer A of formula (1) is adopted, all the polymerizable monomer A needs to be added at once in the preparation reaction step (1); if the polymerizable monomer A of formula (2) is used, the first batch of the polymerizable monomer A added in step (1) accounts for 0-10% of the total polymerizable monomer A by mass, and the remaining second batch of the polymerizable monomer A needs to be dropwise added uniformly in step (2). the non-radical polymerizable siloxane C having hydrophobic hydrocarbon functional groups is added to the reaction system in three batches, the first batch of the siloxane C added in the preparation reaction step (1) accounts for 5-25% of the total mass of the siloxane C, and the proportions of the remaining second batch added in the preparation reaction step (2) and the remaining third batch added in the preparation reaction step (3) are arbitrary; the siloxane or organofunctional group substituted siloxane D is added to the reaction system in two batches; the first batch of the siloxane or organofunctional group substituted siloxane D added in the preparation reaction step (1) accounts for 0-30% of the total mass of D, and the remaining second batch of D is dropwise added uniformly in the preparation reaction step (2).

3. The preparation method of the amphiphilic multifunctional hybrid nanoparticle according to claim 2, wherein the initiator is a thermal initiator or a redox initiator, and the dosage of the initiator is calculated based on the following method: if the initiator is a thermal initiator, the mass of the initiator is 0.4-4% of the total mass of the polymerizable monomer A and the polymerizable siloxane B; if the initiator is a redox initiator, the mass of an oxidizing agent and the mass of a reducing agent are each 0.1-4% of the total mass of the polymerizable monomer A and the polymerizable siloxane B.

4. The preparation method of the amphiphilic multifunctional hybrid nanoparticle according to claim 2, wherein the thermal initiator includes azobisisobutyrazoline hydrochloride (VA044), azobisisobutylphosphonium hydrochloride (V50), benzoyl peroxide, azobisisobutyronitrile (AIBN); and the redox initiator is composed of an oxidizing agent and a reducing agent, wherein the oxidizing agent includes hydrogen peroxide, ammonium persulfate and potassium persulfate, and the reducing agent includes ascorbic acid, sodium hydrogen sulfite and rongalite.

5. An application method of the amphiphilic multifunctional hybrid nanoparticle according to claim 1, wherein in a case of preparation of a cement-based material, the hybrid particle is directly added at a time and mixed in a mixing process, and the dosage of the hybrid nanoparticle is 0.1-0.5% of the total mass of the cementing material.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0054] FIG. 1 is a radial distribution of the hybrid particle prepared in Example 3 as measured by dynamic light scattering.

DETAILED DESCRIPTION OF THE INVENTION

[0055] In order to better understand the present invention, the contents of the present invention will be further clarified below with reference to embodiments, but the contents of the present invention are not limited to the following embodiments.

[0056] The units used below are all parts by mass, and all the compounds used are commercially available or synthetic products that have been reported.

[0057] The polymerizable monomer A of formula (2) is a commercially available reagent or a commercial product (Sigma-Aldrich, Meryer (Shanghai) Chemical Technology Co., Ltd., Huntsman, etc.) or synthesized according to the reference, and is prepared from methacrylic acid, acrylic acid and polyether by esterification or amidation (e.g., Polymer-Plastics Technology and Engineering, 2011, 50, 59), using a condensing agent for dehydration condensation reaction, for example, using a condensing agent N,N-dicyclohexylcarbodiimide (DCC) for condensation in the presence of a catalyst 4-dimethylaminopyridine (DMAP), or using a dehydrating agent such as toluene or cyclohexane for azeotropic dehydration in the presence of a strong acid functioning as a catalyst.

[0058] A2 is a reagent, and A4 and A5 are commonly used raw materials for domestic water reducing agent production, and are both commercially available.

[0059] Siloxanes B, C and D are all from commercially available reagents or industrial products (Meryer (Shanghai) Chemical Technology Co., Bailingwei Reagent and Sigma-Aldrich). The source of the aluminum complex G is synthesized according to the reference (J. Am. Chem. Soc., 1948, 70, 1053-1054) or a commercial reagent.

[0060] In addition, in general, under the condition of a high solid content, the preparation reaction of the hybrid particle is difficult, for example, aggregation occurs easily due to an excessive reaction rate, which results in loss of stability (particle agglomeration occurs); therefore, it can be controlled more easily than samples with a low solid content. The following embodiments which disclose the preparation of samples with a relatively high solid content (the total mass of A, B, C, D and E is 10-30% of the total mass of the reaction system) are described and compared.

TABLE-US-00001 TABLE 1 Names of compounds used in the embodiments A1 Polyethylene glycol monomethyl ether methacrylate, b = 8 A2 Polyethylene glycol monomethyl ether acrylate, b = 22 A3 N-poly(ethylene oxide-propylene oxide) monomethyl ether acrylamide, a + b = 42, a/(a + b) = 0.3 A4 Methyl allyl polyglycol ether, b = 114 A5 Allyl polyglycol ether, b = 8 A6 Polyethylene glycol monomethyl ether methacrylate, b = 114 B1 Methacryloxypropyltrimethoxysilane B2 Methacryloxypropyltriethoxysilane B3 Acryloyloxypropyltriethoxysilane B4 Acryloyloxymethyltrimethoxysilane B5 Acryloyloxypropyltrimethoxysilane C1 N-octyltrimethoxysilane C2 N-octadecyltrimethoxysilane C3 N-dodecyltriethoxysilane C4 N-docosyltrimethoxysilane C5 Isobutyl trimethoxysilane C6 5-hexenyltrimethoxysilane D1 Tetraethoxysilane D2 Tetramethoxysilane D3 Di-n-butyldimethoxysilane D4 Methyltriethoxysilane D5 Dimethyldiethoxysilane D6 Phenyltriethoxysilane F1 N-hexylic acid F2 Tetradecyl didodecanoate F3 Oleic acid F4 Methyl laurate F5 Benzoic acid G1 Aluminum hydroxylaurate G2 Aluminum stearate G3 Aluminum 2-ethylhexanoate

[0061] The structural formulas of the names of the compounds in Table 1 are as follows:

##STR00005## ##STR00006## ##STR00007##

(1) Preparation of Part of Polymerizable Monomers A

[0062] (1) A1 (Polyethylene Glycol Monomethyl Ether Methacrylate, b=8), Prepared from Methacrylic Acid and Polyethylene Glycol Monomethyl Ether (with a Number-Average Molecular Weight of 350, MPEG350, from Sigma-Aldrich):

[0063] Methacrylic acid (9.03 g, 0.105 mol) and polyethylene glycol monomethyl ether (with a number-average molecular weight of 350) (35 g, 0.1 mol) were dissolved in 500 mL of CHCl3, and DMAP (122 mg, 1 mmol) was then added thereto; a solution of DCC (22.67 g, 0.11 mol) dissolved in CHCl.sub.3 (200 mL) was dropwise added at room temperature, and 2 hours later, a white precipitate appeared in the system; the solution was further stirred for 2 hours, then filtered, and distilled under reduced pressure; the obtained liquid was dissolved with CHCl.sub.3, then precipitated with diethyl ether, and then centrifuged to take the lower liquid; the obtained liquid was repeatedly subjected to CHCl.sub.3/diethyl ether precipitation twice, and the final product was vacuum-dried to obtain a monomer A1 with a yield of 91%.

[0064] (2) A3 (N-Poly(Ethylene Oxide-Propylene Oxide) Monomethyl Ether Acrylamide, a+b=42, a/(a+b)=0.3), Prepared by the Reaction of Acrylic Acid and Amino Poly(Ethylene Oxide-Propylene Oxide) Monomethyl Ether (with a Number-Average Molecular Weight of 2000, m/n=7/3, m+n=42, from Huntsman):

[0065] Acrylic acid (7.56 g, 0.105 mol) and amino poly(ethylene oxide-propylene oxide) monomethyl ether (with a number-average molecular weight of 2000) (200 g, 0.1 mol) was dissolved in 1000 mL of CHCl3, and DMAP (0.122 g, 1 mmol) was then added thereto; a solution of DCC (22.67 g, 0.11 mol) dissolved in CHCl.sub.3 (200 mL) was dropwise added at room temperature, and 4 hours later, a white precipitate appeared in the system; the solution was further stirred for 6 hours, then filtered, and distilled under reduced pressure; the obtained solid was dissolved with CHCl.sub.3, then precipitated with diethyl ether, and then filtered; the obtained solid was then repeatedly subjected to CHCl.sub.3/diethyl ether precipitation twice, and the final product was vacuum-dried to obtain a monomer A3 with a yield of 80%.

[0066] (3) A6 (Polyethylene Glycol Monomethyl Ether Methacrylate, b=114), Prepared by the Reaction of Methacrylic Acid and Polyethylene Glycol Monomethyl Ether (with a Number-Average Molecular Weight of 5000, from Sigma-Aldrich):

[0067] Methacrylic acid (9.03 g, 0.105 mol) and polyethylene glycol monomethyl ether (with a number-average molecular weight of 5000) (500 g, 0.1 mol) were dissolved in 2000 mL of CHCl3, and DMAP (122 mg, 1 mmol) was then added thereto; a solution of DCC (22.67 g, 0.11 mol) dissolved in CHCl3 (200 mL) was dropwise added at room temperature, and 12 hours later, a white precipitate appeared in the system; the solution was further stirred for 12 hours, then filtered, and distilled under reduced pressure; the obtained liquid was dissolved with CHCl.sub.3, and then precipitated with diethyl ether; the obtained solid was repeatedly subjected to CHCl.sub.3/diethyl ether precipitation twice, and the final product was vacuum-dried to obtain a monomer A6 with a yield of 73%.

(2) Preparation of a Hybrid Nanoparticle Dispersion

Example 1

[0068] (1) 0.75 part of A1, 0.375 part of C1 and 200 parts of water were added to a reactor. Stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 2 with dilute sulfuric acid, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was adjusted to 5° C.

[0069] (2) 0.56 part of 30% H.sub.2O.sub.2 was added to the solution immediately, and after stirring for 5 minutes, an aqueous solution of ascorbic acid (prepared by dissolving 0.437 part of the ascorbic acid in 49 parts of water) was dropwise added thereto, and a mixed solution comprising 11.25 parts of the polymerizable siloxane B1, 101.25 parts of the organosiloxane D1 and 7.125 parts of C1 and an aqueous solution of the polymerizable monomer A1 (prepared by dissolving 6.75 parts of the polymerizable monomer A1 in 100 parts of water) was also dropwise added uniformly to react for 2 hours.

[0070] (3) 22.5 parts of F1 was added, the reaction system was stirred for 1 hour, the reaction system was then returned to room temperature, and the pH of the dispersion was adjusted to 7 with a sodium hydroxide solution to obtain a dispersion P1 of the hybrid nanoparticle.

Example 2

[0071] (1) 0.5 part of A2, 2.25 parts of C1 and 300 parts of water were added to a reactor. Stirring was carried out to thoroughly mix the solution, N.sub.2 was introduced in the mixed solution to remove O.sub.2, the pH of the mixed solution was adjusted to 4 with dilute sulfuric acid, and the temperature of the reaction system was adjusted to 5° C.

[0072] (2) 0.22 part of 30% H.sub.2O.sub.2 was added to the solution immediately, and after stirring for 5 minutes, an aqueous solution of rongalite (prepared by dissolving 0.1 part of the rongalite in 49.695 parts of water) was added dropwise thereto, and a mixed solution comprising 0.5 parts of the polymerizable siloxane B2, 9.5 parts of the organosiloxane D6 and 6 parts of C1 and an aqueous solution of the polymerizable monomer A2 (prepared by dissolving 4.5 parts of the polymerizable monomer A2 in 100 parts of water) were also dropwise added uniformly to react for 4 hours.

[0073] (3) 6.75 parts of C1, 10 parts of F1 and 10 parts of G1 were added, the reaction system was stirred for 1 hour and then returned to room temperature, and the pH of the dispersion was adjusted to 7 with a sodium hydroxide solution to obtain a dispersion P2 of the hybrid nanoparticle.

Example 3

[0074] (1) 30 parts of A3, 3.75 parts of C2 and 250 parts of water were added to a reactor. Stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 10 with a sodium hydroxide solution, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was increased to 60° C.

[0075] (2) An aqueous solution of ammonium persulfate (prepared by dissolving 0.72 part of the ammonium persulfate in 49.28 parts of water) and an aqueous solution of sodium hydrogen sulfite (prepared by dissolving 0.72 part of the sodium hydrogen sulfite in 49.28 parts of water) were dropwise added simultaneously and immediately, and a mixed solution comprising 6 parts of the polymerizable siloxane B3, 69 parts of the organosiloxane D2 and 6 parts of C2 was also dropwise added uniformly to react for 3 hours.

[0076] (3) 5.25 parts of C2, 6 parts of F3 and 24 parts of G2 were added, the reaction system was stirred for 1 hour and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P3 of the hybrid nanoparticle.

[0077] Reference can be made to FIG. 1 for the particle size test results of this batch of samples, the corresponding average radius is (159±116) nm, and PDI is 0.527; the test instrument used is ALV/CGS-3, the incident angle is 90°, the laser wavelength is 620 nm, and the corresponding average radius is (159±116) nm and PDI is 0.527.

Example 4

[0078] (1) 0.5 part of A4, 1.6 parts of C3 and 250 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 9 with a sodium hydroxide solution, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was increased to 40° C.

[0079] (2) an aqueous solution of VA044 (prepared by dissolving 0.25 part of VA044 in 49.75 parts of water) was added to the mixed solution at a time immediately, and a mixed solution comprising 7.5 parts of B4, 67.5 parts of D5 and 8 parts of C3 and an aqueous solution of A4 (prepared by dissolving 4.5 parts of A4 in 100 parts of water) are also uniformly added dropwise to react for 6 hours.

[0080] (3) 6.4 parts of C3 and 4 parts of G1 were added, the reaction system was stirred for 3 hours and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P4 of the hybrid nanoparticle.

Example 5

[0081] (1) 15 part of A4, 1.12 parts of C3, 15.98 parts of D3 and 300 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 9 with a sodium hydroxide solution, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was increased to 60° C.

[0082] (2) An aqueous solution of V50 (prepared by dissolving 0.21 part of V50 in 49.79 parts of water) was added to the mixed solution at a time immediately, and a mixed solution comprising 6 parts of B4, 90.52 parts of D5 and 10.13 parts of C3 was also dropwise added uniformly to react for 4 hours.

[0083] (3) 7.5 parts of F4 and 3.75 parts of G3 were added at a time, the reaction system was stirred for 2 hours and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P5 of the hybrid nanoparticle.

Example 6

[0084] (1) 1.5 parts of A6, 1.5 parts of C5, 15.19 parts of D4 and 200 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 4 with sulfuric acid, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was adjusted to 10° C.

[0085] (2) 0.2 part of 30% H.sub.2O.sub.2 was added to the solution immediately, and after stirring for 5 minutes, an aqueous solution of ascorbic acid (prepared by dissolving 0.156 part of the ascorbic acid in 49.644 parts of water) was dropwise added thereto, and a mixed solution comprising 11.25 parts of B1, 86.06 parts of D4 and 4.5 parts of C5 and an aqueous solution of A6 (prepared by dissolving 28.5 parts of A6 in 100 parts of water) were also dropwise added uniformly to react for 2 hours.

[0086] (3) 1.5 parts of F2 was added at a time, the reaction system was stirred for 0.5 hour and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P6 of the hybrid nanoparticle.

Example 7

[0087] (1) 0.75 part of A1, 11.25 parts of C4, 4.28 parts of D4 and 200 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 9 with a sodium hydroxide solution, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was adjusted to 70° C.

[0088] (2) An aqueous solution of ammonium persulfate (prepared by dissolving 0.18 part of the ammonium persulfate in 49.82 parts of water) was added to the mixed solution at a time, and a mixed solution comprising 1.5 parts of B3 and 24.22 parts of D4 and an aqueous solution of A1 (prepared by dissolving 6.75 parts of A1 in 100 parts of water) were also dropwise added uniformly to react for 6 hours.

[0089] (3) 33.75 parts of C4, 30 parts of F4 and 37.5 parts of G1 were added at a time, the reaction system was stirred for 2 hours and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P7 of the hybrid nanoparticle.

Example 8

[0090] (1) 1.5 part of A2, 0.9 part of C3, 15.19 parts of D3 and 200 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 9 with a sodium hydroxide solution, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was adjusted to 45° C.

[0091] (2) An aqueous solution of VA044 (prepared by dissolving 0.525 part of VA044 in 49.475 parts of water) was added to the mixed solution at a time immediately, and a mixed solution comprising 11.25 parts of B4, 86.06 parts of D3 and 5.4 parts of C3 and an aqueous solution of A2 (prepared by dissolving 13.5 parts of A2 in 100 parts of water) were also dropwise added uniformly to react for 6 hours.

[0092] (3) 11.7 parts of C3 and 4.5 parts of F2 were added at a time, the reaction system was stirred for 1 hour and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P8 of the hybrid nanoparticle.

Example 9

[0093] (1) 30 parts of A3, 1.8 parts of C5, 8.55 parts of D5 and 300 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 2 with sulfuric acid, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was adjusted to 25° C.

[0094] (2) 0.31 part of 30% H.sub.2O.sub.2 was immediately added to the solution, and after stirring for 5 minutes, an aqueous solution of ascorbic acid (prepared by dissolving 0.24 part of the ascorbic acid in 49.45 parts of water) was dropwise added thereto, and a mixed solution comprising 1.5 parts of B2, 19.95 parts of D5 and 16.2 parts of C5 was also dropwise added uniformly to react for 1 hour.

[0095] (3) 60 parts of F2 and 12 parts of G2 were added at a time, the reaction system was stirred for 3 hours and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P9 of the hybrid nanoparticle.

Example 10

[0096] (1) 2.25 parts of C1, 3.6 parts of D1, and 325 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 4 with sulfuric acid, N2 was introduced in the mixed solution to remove O2, and the temperature of the reaction system was adjusted to 70° C.

[0097] (2) 0.136 part of AIBN was dropwise added immediately, and a mixed solution comprising 3 parts of B2, 8.4 parts of D1 and 4.5 parts of C1 and an aqueous solution of A4 (prepared by dissolving 3.75 parts of A4 in 99.864 parts of water) were also dropwise added uniformly to react for 4 hours.

[0098] (3) 38.25 parts of C1 and 11.25 parts of G3 were added at a time, the reaction system was stirred for 3 hours and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P10 of the hybrid nanoparticle.

Example 11

[0099] (1) 15 parts of A5, 9.38 parts of C6, 17.1 parts of D6 and 250 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 2 with sulfuric acid, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was adjusted to 55° C.

[0100] (2) An aqueous solution of ammonium persulfate (prepared by dissolving 0.18 part of the ammonium persulfate in 49.82 parts of water) and an aqueous solution of sodium hydrogen sulfite (prepared by dissolving 0.36 part of the sodium hydrogen sulfite in 49.64 parts of water) were dropwise added uniformly and separately, and a mixed solution comprising 3 parts of B5, 39.9 parts of D6 and 18.75 parts of C6 was also dropwise added uniformly to react for 3 hours.

[0101] (3) 9.37 parts of C6, 7.5 parts of F5 and 30 parts of G2 were added at a time, the reaction system was stirred for 2 hours and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P11 of the hybrid nanoparticle.

Example 12

[0102] (1) 2 parts of A6, 0.5 parts of C2, 16.8 parts of D2 and 200 parts of water were added to a reactor, stirring was carried out to thoroughly mix the solution, the pH of the mixed solution was adjusted to 2 with sulfuric acid, N.sub.2 was introduced in the mixed solution to remove O.sub.2, and the temperature of the reaction system was adjusted to 10° C.

[0103] (2) 0.24 part of 30% H.sub.2O.sub.2 was added to the solution immediately, and after stirring for 5 minutes, an aqueous solution of ascorbic acid (prepared by dissolving 0.123 part of the ascorbic acid in 49.637 parts of water) was dropwise added thereto, and a mixed solution comprising 4 parts of B1, 39.2 parts of D2 and 8 parts of C2 and an aqueous solution of A6 (prepared by dissolving 18 parts of A6 in 100 parts of water) were also dropwise added uniformly to react for 3 hours.

[0104] (3) 1.5 parts of C2, 5 parts of F5 and 5 parts of G3 were added at a time, the reaction system was stirred for 2 hour and then returned to room temperature, and the pH of the dispersion was adjusted to 7 to obtain a dispersion P12 of the hybrid nanoparticle.

[0105] 3. Effect Comparison

[0106] Concrete application tests will be mainly described below to illustrate the use effect of the amphiphilic hybrid nanoparticle of the present patent. The mechanical property tests of concrete were carried out with reference to GB/T50080-2002 and GB/T50081-2002, the chloride ion permeability and electric flux tests were carried out with reference to GB/T50082-2009, and the water absorption of concrete was carried out with reference to BS1881-122-83. The slump of the concrete was adjusted to (20±1) cm by using a PCA-I® high-performance polycarboxylate water reducing agent produced by Jiangsu Subote New Material Co., Ltd., and its air content was adjusted to (2.5±0.3)%.

[0107] The materials used include: Jiangnan Xiaoyetian Cement (P⋅II⋅52.5), Grade II fly ash, river sand with a fineness modulus of 2.6, and 5-25 mm continuous graded gravel.

[0108] The mix proportion of the concrete is shown in Table 2. The test results of the concrete are shown in Table 3. Except for the age marked, all the test results are the test results of 28-day test blocks, and the water absorption is the weight increase of the test blocks soaked for 0.5 hour. The reference sample is concrete without the addition of the hybrid particle dispersions, and P1-P12 are concrete samples with an effective dosage of the hybrid particle being 0.4% relative to the total mass of cementing material. Zinc stearate is concrete with a dosage of calcium stearate being 1% relative to the total mass of cementing material; control sample 1 is concrete with zinc stearate and silica sol added separately, and the effective dosage of zinc stearate and silica sol is equivalent to 0.4% of the total mass of the cementing material; control sample 2 is a core-shell structured nanoparticle prepared according to the embodiment of the patent CN103922638B, and its dosage is 0.4% of the total mass of the cementing material.

[0109] All of the amphiphilic hybrid nanoparticle dispersions in the embodiments of the present invention can maintain good stability without coagulation when mixed with a saturated Ca(OH).sub.2 solution.

TABLE-US-00002 TABLE 2 Mix proportion of concrete Cement Fly ash Fine ore Sand Stone Water 193 83 147 750 1067 147

TABLE-US-00003 TABLE 3 Properties of fresh concrete and macro-properties at different ages Compressive Electric Cl.sup.− diffusion Water absorption (%) strength flux coefficient at different ages (MPa) (C) (10.sup.−12 m.sup.2/s) 7 days 28 days Reference 58.6 925.3 7.0 2.01 1.65 P1 64.8 478.5 2.0 0.96 0.80 P2 62.0 305.0 2.4 0.57 0.43 P3 64.5 462.1 2.3 0.85 0.69 P4 68.0 370.6 1.2 0.81 0.69 P5 65.2 241.6 1.5 0.56 0.43 P6 66.1 498.3 2.1 1.04 0.86 P7 61.6 295.7 2.2 0.48 0.43 P8 65.5 334.6 1.3 0.62 0.51 P9 61.8 452.9 2.8 0.78 0.64 P10 64.1 335.2 2.0 0.71 0.59 P11 63.1 350.2 1.9 0.66 0.53 P12 65.7 453.7 2.0 0.97 0.80 Zinc 44.5 666.2 6.0 0.96 0.73 stearate Control 54.8 518.2 2.9 1.11 0.94 sample 1 Control 59.3 592.2 3.2 1.19 0.99 sample 2

[0110] The following conclusion may be reached from the data in the table:

[0111] (1) Compared with the concrete reference sample, the 28-day compressive strength of the concrete samples doped with the amphiphilic hybrid nanoparticles of the present invention is increased slightly to varying degrees from 58.6 MPa to 61.6-68.0 MPa, with a strength increase of 5-16.2%; the 28-day electrical flux of the concrete samples is decreased from 925.3C to 241.6-478.5C, with a reduction of 46-74%; in addition, the 28-day Cl-diffusion coefficient of the concrete samples is decreased significantly from 7.0×10.sup.−12 m.sup.2/s to 1.2-2.8×10.sup.−12 m.sup.2/s, with a reduction of 59-83%; the 7-day water absorption and 28-day water absorption of the concrete samples are also reduced by 51-76% and 50-78% to varying degrees, respectively.

[0112] (2) In a case of a high dosage (1.0% of the total mass of the cementing material) of a stearate (here compared to zinc stearate), its effect of reducing water absorption is slightly weaker than that of the hybrid particle, but it also can significantly reduce water absorption by 52-56%, however, the compressive strength of the concrete is reduced by 24%, and it does not show significant effect in improving the Cl-diffusion coefficient; therefore, its performance is obviously inferior to that of the amphiphilic hybrid particle.

[0113] (3) The control sample 1 shows the application performance in a case where a stearate and silica sol are added into concrete separately. When the dosages of the stearate and silica sol are both 0.4% of the total mass of the cementing material, although the 28-day compressive strength of the concrete is weakened slightly, the electric flux, the Cl-diffusion coefficient, and the 7-day and 28-day water absorption of concrete can be reduced, but not as good as the amphiphilic hybrid nanoparticle.

[0114] More importantly, it is difficult to mix the stearate and silica sol and they must be added separately, which obviously increases the difficulty of application; in addition, silica sol will coagulate in a saturated Ca(OH).sub.2 solution and loses its stability. In contrast, all the amphiphilic hybrid particle dispersions maintain good stability when mixed with a saturated Ca(OH).sub.2 solution, without coagulation, and thus have superior application performance.

[0115] (4) The control sample 2 solves the problem of particle stability by using a core-shell structured particle, but its performance in improving the 28-day electric flux, the Cl-diffusion coefficient and the water absorption of concrete are obviously inferior to that of the amphiphilic hybrid particle.