CN108658491B

CN108658491B - Amphiphilic multifunctional hybrid particle based on aluminum oxide and preparation method thereof

Info

Publication number: CN108658491B
Application number: CN201810529769.0A
Authority: CN
Inventors: 舒鑫; 冉千平; 杨勇; 严涵; 翟树英; 黄振; 张志勇; 毛永琳
Original assignee: Jiangsu Bote New Materials Co Ltd; Bote Building Materials Tianjin Co Ltd; Bote New Materials Taizhou Co Ltd
Current assignee: Jiangsu Bote New Materials Co Ltd; Bote Building Materials Tianjin Co Ltd; Bote New Materials Taizhou Co Ltd
Priority date: 2018-05-29
Filing date: 2018-05-29
Publication date: 2020-11-17
Anticipated expiration: 2038-05-29
Also published as: CN108658491A

Abstract

The invention discloses amphiphilic multifunctional hybrid particles based on aluminum oxide, wherein a detachable water-soluble long side chain and a hydrophobic long chain are attached to the surface layer of the particles, the components in the particles are aluminum oxide or hydroxide networks with hydrophobic long carbon chains for complexing or covalent substitution, and free fatty acid or fatty acid ester or fatty acid aluminum complex with hydrophobic long carbon chains is also contained in the particles. The hybrid particles have good storage stability, and the water permeability of the cement-based material is greatly reduced; the hydration products and interfaces in the cement-based material using the hybrid particles are hydrophobized, so that the possibility that harmful particles erode the cement-based material through water penetration is further reduced, and the anti-permeability performance is improved more obviously; the particles of the invention have excellent improvement on the impermeability of the cement-based material, and the interaction of the aluminum oxide and the aluminum hydroxide with the hydration product compacts the cement-based material matrix, thus slightly improving the mechanical properties of the cement-based material.

Description

Amphiphilic multifunctional hybrid particle based on aluminum oxide and preparation method thereof

Technical Field

The invention belongs to the field of cement-based material additives, and particularly relates to a hybrid particle capable of improving the impermeability and mechanical properties of a cement-based material and a preparation method thereof.

Background

The term "concrete" as used herein generally refers indiscriminately to concrete, such as concrete, mortar or grout, which is also applicable elsewhere herein.

Concrete is a porous material with pore sizes in the nanometer to millimeter range. These pores, and in particular the interconnected pores, are key factors in the invasion of harmful substances leading to the erosion (freeze-thawing, carbonization, chemical attack, alkali-aggregate reaction, corrosion of reinforcing steel bars, etc.) of concrete structures. Various harmful substances (such as chloride ions, sulfate ions and the like) are adsorbed to the surface layer of the concrete through the capillary action of the aqueous solution and further permeate into the concrete, so that serious corrosion damage is brought to the reinforced concrete structure. The important way for improving the durability of concrete is to perform waterproofing treatment on the concrete or add various waterproofing agents and the like in the preparation of the concrete to weaken the moisture permeability and compact the pore structure of the concrete.

The permeability of the concrete can be improved by treating the surface of the concrete. Currently common organic surface treatments and hydrophobic impregnation coatings include silanes and siloxanes, epoxy resins, polyurethanes, acrylates, polystyrene resins, neoprene, etc. The organic surface treating agent has strong hydrophobicity, and can permeate into concrete to block pores and form a hydrophobic film on the pore walls of the concrete. However, the organic coating affects the air permeability of concrete, the protection life is short, meanwhile, the organic surface treatment agent has poor fire resistance and is easy to age, the effect is obviously reduced under the irradiation of high temperature and ultraviolet rays, cracks or peeling are generated, and the organic surface treatment agent is difficult to clean from a building after failure. Although the acrylic acid treatment agent can significantly reduce the water permeability of concrete, it is poor in the resistance to chloride ion permeation, and therefore, it is not suitable for use in marine engineering. Compared with the inorganic surface treatment agent, the inorganic surface treatment agent (prepared by adding various pigments, fillers, auxiliaries and curing agents into water glass series, phosphate series and cement-based series) has better ageing resistance. The inorganic surface treating agent can permeate into the concrete and perform complex physical and chemical reaction with cement hydration products to generate new substances to block capillary pores, so that corrosive media in the external environment can be prevented from entering the concrete for a long time, the concrete and steel bars are protected from being corroded, and the durability of a reinforced concrete structure is improved. But they do not fundamentally change the hydrophilic characteristic of concrete, so that the waterproof effect is limited, and the performance is inferior to that of organic hydrophobic coatings. In addition, the surface treatment of sodium silicate and the like can improve the alkalinity of concrete, and possibly increase the probability of alkali-aggregate reaction. The penetration depth of the permeable waterproofing agent is very limited, and the waterproofing effect is not ideal in some special cases. When the concrete cracks, the protective layer is ineffective, and harmful substances can still permeate into the concrete along the cracks to corrode.

In order to improve the water content and the permeability of harmful substances of the concrete fundamentally, the micro interface property of the concrete must be changed by adopting an internal doping material. The reaction between the nanometer material and the alkaline component in concrete to densify the matrix is effective method of refining pore distribution and improving permeability, and the use of silica fume, flyash, nanometer alumina, ferric oxide, etc. can improve chlorine ion permeability and lower electric flux. The use of hydrophobic silanes or fatty acids to render their microscopic interfaces, particularly pore interfaces, completely hydrophobic is an important means of reducing water permeability of concrete.

Hydrophobic silane is insoluble in water, an organic solvent or an emulsifier system is needed to prepare an emulsion, the organic solvent has VOC pollution, and the emulsifier system is stable in a certain period of time, but the performance is poor due to particle agglomeration caused by the Ostwald Ripening process after long-term storage. Particularly, when the concrete is added into a strong-alkali high-salt solution environment, the structure of the emulsion is easy to damage, so that the waterproof component wrapped in the emulsion is easy to seep out, the waterproof component is agglomerated and floats upwards, siloxane is quickly hydrolyzed and attached to a hydration product in an alkali environment and is possibly buried by an early hydration product, and the application performance of the siloxane is weakened. If an alkoxysilane is used as the hydrophobic component, it reacts with water itself and releases small alcohols, which cause the emulsion to polymerize and lose stability (see patent CN 1183060C). Meanwhile, the use of an emulsifier (surfactant) has a great influence on the workability of concrete, and components such as air entraining, defoaming and thickening are additionally adopted to adjust the workability during the application of the concrete, so that troubles are caused to the use (CN103864340B and CN 103922638B). Although the organosilicon waterproof emulsion prepared by the overseas giant heads such as wacker, degussa and the like has good performance, the price is high, and the popularization is not facilitated. The preparation of hydrophobic silane into polymer emulsion is an effective solution for improving stability (CN103864340B, CN103922638B), but compared with free-migrating small organic molecules, the surface area of polymer particles is limited, and the occupied area is limited when the polymer particles are adsorbed on the interface of concrete pores, and meanwhile, the surface of nanoparticles is rendered hydrophilic by using a reactive emulsifier (containing sulfonic acid groups), which is obviously unfavorable for improving the water resistance by increasing the hydrophobicity of the interface.

The fatty acid waterproof agent can be divided into a soluble metal soap waterproof agent and an asphaltene metal soap waterproof agent. The soluble metal soap waterproof agent is prepared by mixing stearic acid, palmitic acid, abietic acid, sodium hydroxide solution, potassium hydroxide (or potassium carbonate), water and the like according to a certain proportion, heating and saponifying. Aqueous solutions of higher saturated and unsaturated organic acids (RCOOH) and their alkali metals are among the hydrophobic surfactants. The water-proofing agent is a colored slurry, which is mixed in cement mortar or concrete, the carboxylic acid groups of the colored slurry and calcium hydroxide in the cement mortar act to form an adsorption layer of insoluble calcium soap, and long-chain alkyl forms a hydrophobic adsorption layer between the cement surface and aggregate to generate insoluble substances, so that the water-proofing agent plays a role in filling tiny pores and blocking capillary passages. According to the research of the inventor, when the fatty acid waterproof agent is added into a cement-based material, the solubility of the fatty acid waterproof agent is also limited due to the rapid generation of insoluble species such as fatty acid calcium and the like, and the fatty acid salt is agglomerated, so that defects can be generated in concrete on one hand, the surface area of the fatty acid waterproof agent is limited, and the performance is limited at a low mixing amount on the other hand.

In conclusion, the two main classes of organic waterproof agents cannot gradually act on a micro interface of a cement hydration product in a hydration reaction in a monomolecular dispersion state in a cement-based material, and meanwhile, the two main classes of organic waterproof agents have low density and can be freely migrated and enriched in a few millimeters of an upper layer of the cement-based material (research on the waterproof and chloride ion corrosion resistance effect of the internally-doped waterproof agent on concrete, 2010, the Master thesis of Qingdao university of science and technology), and the content of hydrophobic components in the concrete is limited below the depth, so that the improvement on the impermeability of the concrete is very limited. The effective amount of the water repellent is not less than 1% of the mass of the glue, however, the strength of the concrete is significantly affected by the water repellent, for example, the strength of the water repellent is reduced by at least 26% by the conventional fatty acid salt water repellent in Tangming et al (Liaoning building material, 2002 (1)).

The traditional impervious material not only influences the air permeability of concrete, but also has short protection life, and meanwhile, the organic surface treatment agent has poor fire resistance and easy aging, the effect is obviously reduced under the irradiation of high temperature and ultraviolet rays, cracks or peeling are generated, the building is difficult to clean after the organic surface treatment agent loses efficacy, and the waterproof effect is not ideal. When the concrete cracks, the protective layer is ineffective, and harmful substances can still permeate into the concrete along the cracks to corrode. But the nano materials are easy to agglomerate, which greatly influences the working performance of the cement-based materials and limits the exertion of the performance, and in addition, the improvement of the waterproof performance of the materials is not better than that of the hydrophobic waterproof agent. Although the emulsifier system is stable within a certain period of time, the performance of the emulsifier system is poor due to particle agglomeration caused by the Ostwald Ripening process after long-term storage, and the emulsifier system is high in price and not beneficial to popularization. When the fatty acid waterproof agent is added into a cement-based material, the solubility of the water-based material is limited due to the fact that insoluble species such as fatty acid calcium are rapidly generated, and the fatty acid salt is agglomerated, so that defects can be generated in concrete on one hand, the surface area of the water-based material is limited, and the performance is limited when the mixing amount is low. The free migration is enriched on the upper layer of the cement-based material.

Disclosure of Invention

In order to overcome the defects that the traditional impervious material is difficult to use, limited in impervious effect, easy to lose efficacy, high in cost or unfavorable for the mechanical property of the cement-based material, the invention provides aluminum oxide-based hybrid particles for the cement-based material and a preparation method thereof.

The invention combines the advantages of nano-micron materials in improving pore structures, improving mechanical properties of cement-based materials and hydrophobic materials in reducing water permeability, designs amphiphilic multifunctional hybrid particles based on aluminum oxide, and attaches hydrophilic long chains and hydrophobic molecules to the surface layers of the particles, wherein the hydrophilic long chains enable the particles to be stable in storage and application through steric hindrance, and in a strong alkaline environment, the hydrophilic long chains gradually fall off, the surfaces of the particles are occupied by the hydrophobic components, so that the surfaces of the particles are subjected to hydrophobic modification, and the water permeability of particle interfaces is reduced.

The surface layer of the particles plays the role of a soft skeleton or a capsule, contains a mixed component formed by aluminum oxide and organic molecules through hybridization modes such as blending, covalent bond, coordination complex and the like, and is mixed with Ca (OH) in the strong alkaline environment of the cement-based material₂The reaction becomes thin, the mixed components contained in the concrete continuously interact with the alkaline environment to gradually release hydrophobic small molecules which can be attached to the surface of a hydration product, so that the pores of the concrete are fully covered to be completely hydrophobic interfaces, and harmful species are prevented from being corroded in a mode of dissolving and permeating aqueous phase solution. The aluminum oxide component is also active in hydration, as can Ca (OH)₂Reacting or directly filling the internal pores of the cement-based material to improve the mechanical property, and in addition, because the outer hydrophilic long chains of the aluminum oxide particles fall off, the rest hydrophobic structureThe anti-seepage performance is obviously improved.

The invention provides amphiphilic multifunctional hybrid particles based on aluminum oxide, wherein a detachable water-soluble long side chain and a hydrophobic long chain are attached to the surface layer of the particles, the components in the particles are aluminum oxide or hydroxide networks with hydrophobic long chain hydrocarbon functional groups for complexing or covalent substitution, and the particles also contain free fatty acid or fatty acid ester or fatty acid aluminum complex with hydrophobic long chain hydrocarbon functional groups; the average diameter of the amphiphilic multifunctional hybrid particles is not more than 1000 nm.

The invention provides a preparation method of amphiphilic multifunctional hybrid particles based on aluminum oxide, which comprises the following specific steps:

(1) adding water, a first batch of polymerizable monomer A, all polymerizable monomers B and a first batch of cross-linking agent C into a reactor, adjusting the temperature of a reaction system to 0-80 ℃, stirring for fully mixing, adjusting the pH of the mixed solution to 7-11, and introducing N into the mixed solution₂Removing O₂；

(2) Immediately adding an aqueous solution of an initiator into the mixed solution prepared in the step (1) or respectively adding the initiator and water to initiate polymerization, simultaneously adding a second batch of polymerizable monomer A, a second batch of cross-linking agent C and a first batch of organic component D into the mixed solution at a constant speed, and reacting for 2-12 hours;

(3) and (3) regulating the pH of the mixed solution after the reaction in the step (2) to 2-4 again, regulating the temperature to 60-90 ℃, adding a second batch of organic component D and organic matter E into the mixed solution at a constant speed, reacting for 6-24h, recovering the reaction system to room temperature, and regulating the pH of the mixed solution to 7 to obtain the dispersion liquid of the amphiphilic multifunctional hybrid particles.

In order to satisfy the stability requirement in the preparation process of the polymer particles, the amounts of the polymerizable monomer A, the crosslinking agent C and the organic component D as components added in portions in each preparation step are also defined as follows:

the polymerizable monomer A is added in the steps (1) and (2) in batches, and the mass fraction of the first polymerizable monomer A in the total polymerizable monomer A is not less than 20%;

the cross-linking agent C is added in the step (1) and the step (2) in batches, and the proportion of the two batches is arbitrary;

the organic component D is a main source of hydrophobic components in the hybrid particles, is contained in the hybrid particles, and is added in steps (2) and (3) in batches, wherein the mass of the organic component D in the first batch accounts for 0-30% of the total mass of all the organic components D;

since the organic substance E is the main source of aluminum oxide and aluminum hydroxide in the hybrid particles, and must be added in step (3), the organic component D is added in batches to make the distribution of the organic component in the hybrid particles more uniform.

The water added in the step (1) accounts for 30-75% of the total water used in the reaction.

The polymerizable monomer A is selected from one or a mixture of two of polyethylene glycol monounsaturated fatty acid ester and methoxy polyethylene glycol monounsaturated fatty acid ester, and is any one or any combination of more than one of the structures shown in the following general formula (1):

wherein the functional group R₁Is unsaturated long-chain hydrocarbon functional group containing 5-11 carbon atoms, the end of the unsaturated long-chain hydrocarbon functional group is unsaturated double bond, the end refers to the end far away from ester bond in the general formula (1), R₂Represents H or methyl, a is polyethylene glycol chain ethylene glycol unit (-CH)₂CH₂O-) and the average molar addition number is in the range of 4-22.

The polymerizable monomer A has free radical polymerization activity and can be prepared by esterification reaction of corresponding unsaturated fatty acid and polyethylene glycol or methoxy polyethylene glycol.

The polymerizable monomer B is unsaturated fatty acid or a mixture thereof;

the polymerizable monomer B is any one or any combination of more than one of linoleic acid, palmitoleic acid or a structure shown in the following general formula (2):

in the general formula (2), b represents-CH₂-the number of repeating units, which ranges from an integer of 3 to 9.

The cross-linking agent C is any one of the structures shown in the general formula (3),

R₃represents H or CH₃X represents a saturated alkyl group having 2 to 12 carbon atoms or (CH)₂CH₂O)_cCH₂CH₂Wherein c is an ethylene oxide structure (-CH)₂CH₂O-) average molar addition number, and the value range of c is 1-11;

the addition of the crosslinking agent C is beneficial to improving the stability of particles, so that the surface layer is relatively compact, and in addition, crosslinking functional groups are damaged in an alkaline solution, so that the surface layer is cracked, and the accelerated release of aluminum oxide and hydrophobic components is promoted. Too large a value of C will make the monomer lower in molar weight and become a monomer with stronger hydrophilicity, which is not favorable for the distribution of the cross-linking agent C in the oil phase during the polymerization process.

The organic component D is one or more than one of saturated or unsaturated long-chain fatty acid or fatty acid ester F and aluminum complex G of saturated or unsaturated fatty long-chain fatty acid.

The saturated or unsaturated long-chain fatty acid or fatty acid ester F is any one or any combination of more than one of structures shown in the following general formula (4);

functional group R in the general formula (4)₄Represents a saturated or unsaturated hydrocarbon function containing from 5 to 21 carbon atoms, R₅Represents a hydrogen atom or a saturated alkyl group of 1 to 22 carbon atoms.

The saturated or unsaturated esterThe aluminum complex G of the aliphatic long-chain fatty acid is represented by the general formula Al (R)₆COO)₃Or Al (OH) (R)₇COO)₂One or any combination of more than one of (1), wherein R₆And R₇Each independently represents a saturated or unsaturated hydrocarbon functional group containing from 8 to 18 carbon atoms.

The above functional group R₄、R₆And R₇The same is the source of hydrophobicity (control of the water permeability of the cement-based material, sufficient carbon chain length needs to be ensured); and R is₅It is introduced in order to modulate the rate of release of the hydrophobic component from the saturated or unsaturated long chain fatty acid or fatty acid ester F, the longer the length, the slower the release of the long chain fatty acid.

The organic component F is released in the strong alkaline environment of the cement-based material and gradually produces saturated or unsaturated long-chain fatty acid directly or through hydrolysis, and the saturated or unsaturated long-chain fatty acid is gradually produced through Ca²⁺The complex precipitates and the like are attached to the surface of the cement-based material in pores, so that the pore interfaces of the cement-based material become hydrophobic, thereby weakening water permeability. Meanwhile, the Al component is also beneficial to forming nano-level Al₂O₃The structure has the obvious effects of filling the pores of the cement-based material and compacting the matrix, and can effectively reduce the permeability of harmful components such as chloride ions and the like.

The organic matter E is an aluminum alkoxide organic matter and is any one or any mixture of more than one of structures shown by the following general formula (5):

wherein the functional group R in the general formula (5)₈Represents a saturated alkyl group having 2 to 6 carbon atoms.

The total mass of effective reactants (A + B + C + D + E) in the reaction system is not 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 polymerizable monomer B accounts for 0-10% of the total mass of the effective reactants, the cross-linking agent C accounts for 0-5% of the total mass of the effective reactants, the total mass of an organic component D and an organic matter E (D + E) accounts for 65-95% of the total mass of the effective reactants, the organic component D accounts for 20-80% of the total mass of D and E, and the proportion of F and G in the organic component D is arbitrary.

It is to be noted that the reaction pH in steps (1) to (2) is alkaline, which is to increase the ionization degree of the polymerizable monomer B (if the polymerizable monomer B is added to the particles), and the ionization of the carboxyl group of the surface layer B is suppressed in the reaction system under acidic pH conditions, and the coagulation is easy. Too high pH easily causes the polymerizable monomer A and the organic component D to react with water in the reaction process, so that the particles lose stability in the reaction process, and the later release performance of the particles is weakened, which is not beneficial to improving the impermeability of the cement-based material. The pH bias acidity of the step (3) can effectively inhibit the rapid hydrolysis flocculation precipitation of the organic matter E, and similarly, under the condition of higher temperature, if the pH is too low, the reacted polymerizable monomer A is hydrolyzed, the long chain falls off, and the particles are easy to lose stability in the strong alkali and high salt environment.

The initiator used in the preparation method disclosed by the invention is a conventional initiation system adopted by a person skilled in the art, the initiator can be a thermal initiation or redox initiator, and the initiator can be added at one time or continuously and uniformly added within a certain time, and only the following conditions are met: the initiator can successfully initiate polymerization at corresponding reaction pH and temperature, and the initiator is fully decomposed in the reaction process so as to prevent the storage stability of the particle aqueous dispersion liquid from being influenced by the change after the reaction is finished.

The redox initiator is combined by an oxidizing agent and a reducing agent, wherein the oxidizing agent comprises hydrogen peroxide, ammonium persulfate and potassium persulfate, and the reducing agent comprises ascorbic acid and sodium bisulfite; the thermal initiator comprises azobisisobutyramidine hydrochloride, benzoyl peroxide and azobisisobutyronitrile.

The amount 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, the polymerizable monomer B and the cross-linking agent C; if the initiator is a redox initiator, the mass of the oxidizing agent and the reducing agent is 0.4 to 4 percent of the total mass of the polymerizable monomer A, the polymerizable monomer B and the crosslinking agent C respectively.

The application method of the amphiphilic multifunctional hybrid particle based on aluminum oxide comprises the following steps: when the cement-based material is prepared, the hybrid particles are directly added into the cement-based material for one time in the mixing process to be stirred; the amount of the hybrid particles is 0.1-0.5% of the total glue mass, the anti-seepage performance is obviously improved at the amount of the hybrid particles, and in addition, the anti-seepage performance is improved by adding more particles, but the cost is increased more obviously, and the economical efficiency is slightly worse. The mixing amount of the invention refers to the ratio of the mass of the particles in the finally synthesized aqueous dispersion to the mass of the colloidal material in the cement-based material.

When the amphiphilic hybrid particles are used for modifying cement-based materials, the anti-permeability performance of the amphiphilic hybrid particles is improved along with the increase of the mixing amount; the particles only slightly improve the mechanical property, and the optimal mixing amount for improving the mechanical property is determined by systematic experiments according to different components and sizes of the prepared particles. The mixing amount (bwoc%) is calculated according to the proportion of the total mass of the cementing material, under the condition that the mixing amount is 0.4 bwoc%, the water absorption rate of the concrete in 7 days is reduced by 38-79%, the diffusion coefficient of chloride ions of the concrete in 28 days is reduced by 30-75%, the electric flux of the concrete in 28 days is reduced by 35-75%, and the compressive strength of the concrete in 28 days is slightly improved (improved by 4-11%).

Compared with the traditional technology or material, the amphiphilic hybrid particle provided by the invention can specifically solve the following problems, thereby fully improving the impermeability and mechanical property of the cement-based material:

(1) and (3) reducing the water permeability: the hybrid particles have good storage stability, when the cement-based material is added, the hydrophilic long chain enables the particles to be uniformly and stably dispersed in the cement-based material matrix, after the hydrophilic base on the surface layer is hydrolyzed and shed, the surface of the particles is hydrophobic, and the hydrophobic functional group can cover the surface of the cement-based material along with the hydration reaction; on the other hand, the particle surface layers are connected through a cross-linking agent, the surface layers are gradually hydrolyzed and cracked in an alkaline environment, hydrophobic components contained inside the particle surface layers are gradually released, fatty acid ester and fatty acid aluminum complex are gradually converted into the hydrophobic components in the alkaline environment or directly grow or are complexed and adsorbed on a pore interface, the adhesive force is strong, meanwhile, the failure or performance reduction caused by different modes that hydrophobic (fatty acid and hydrophobic silane) organic waterproof agents are singly used and are difficult to uniformly disperse (agglomerate) at the initial reaction stage, are quickly anchored to the surface of cement particles and are embedded by hydration products and difficult to dissolve and drift out and the like is avoided, and the hydrophobic components can fully act on the pores inside the cement-based material due to the factors, so that the water permeability of the cement-;

(2) reduction of permeability of other substances such as chloride ions: the aluminum oxide and hydroxide network can interact with the cement-based material to generate hydration products such as CSH and the like with finer sizes, so that the structure of the cement-based material is more compact, and meanwhile, the filling effect of stably dispersed particles can also reduce communicated gaps in the material, so that the pore structure of the material is fully refined, and the permeability of harmful substances is reduced; the aluminum phase is taken as high-valence metal and can complex chloride ions to weaken the diffusion performance of the chloride ions; compared with the traditional nano material, the hydration products and interfaces in the cement-based material of the hybrid particles prepared by the invention are hydrophobized, so that the possibility that the cement-based material is eroded by harmful particles through water penetration is further reduced, and the impermeability of the cement-based material is improved more obviously.

(3) No adverse effect or slight improvement on mechanical performance: the particles prepared according to the invention have excellent improvement on the impermeability of the cement-based material, so that the doping amount of the particles can be effectively reduced, and the adverse effect of hydrophobic components on hydration is weakened; due to gradual release of the hydrophobic effect components, the fatty acid compounds (which are complexed with covalent bonds of Al or Ca) can have stronger interaction with cement hydration products at a more uniform level, so that the fatty acid compounds and the cement hydration products form an integral chemical structure with the whole cement concrete, and the risk that the fatty acid compounds and the like are easy to migrate in mortar and concrete to damage interlayer structures or form saponified gel aggregates to become cement-based materials and reduce the strength of internal defects of the cement-based materials is avoided; meanwhile, the interaction of the aluminum oxide and the aluminum hydroxide with the hydration product compacts the cement-based material matrix, and the mechanical property of the cement-based material can be slightly improved.

Drawings

FIG. 1 is a graph of the radius distribution of the hybrid particles prepared in example 6, as determined by dynamic light scattering.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

All the following units are parts by mass, and all the compounds used are commercial products or synthetic products reported in the literature.

Polymerizable monomer A corresponding to general formula (1) is prepared by dehydrating and condensing a fatty acid with polyethylene glycol or methoxypolyethylene glycol according to literature synthesis (see any DCC dehydrating and condensing literature, such as Polymer-Plastics Technology and Engineering,2011,50,59), by dehydrating and condensing reaction with a condensing agent, such as condensing agent N, N-Dicyclohexylcarbodiimide (DCC) catalyzed by condensation in the presence of 4-Dimethylaminopyridine (DMAP), or by azeotropic dehydration with a dehydrating agent such as toluene, cyclohexane, etc., catalyzed by a strong acid.

The polymerizable monomer B, the crosslinking agent C and the organic substance F are commercially available reagents or industrial products (Meyer chemical technology Co., Ltd., Profenox reagent and Sigma-Aldrich). The source of organic G was either synthesized according to the literature (j.am. chem. soc.,1948,70, 1053-.

In addition, in general, the preparation reaction of the hybrid particles is difficult under the condition of high solid content, for example, the hybrid particles are easy to aggregate and lose stability (particle agglomeration occurs) due to the excessively fast reaction speed, and the sample with relatively low solid content is easier to control. The following examples illustrate and compare the preparation of relatively high solids samples (A, B, C, D, E having a total mass of 10-30% of the total mass of the reaction system).

Table 1 compound names used in the examples

The structural formula of each compound in table 1 is as follows:

preparation of (I) polymerizable monomer A

(1) A1 (polyethylene glycol monomethyl ether 5-hexenoate, a ═ 4), prepared from methacrylic acid and tetraethylene glycol monomethyl ether (from Sigma-Aldrich):

5-hexenoic acid (11.41g, 0.1mol) and tetraethylene glycol monomethyl ether (21.86g, 0.1mol) were each treated with 100mL CH₂Cl₂Dissolving to CH of tetraethylene glycol monomethyl ether₂Cl₂DMAP (122mg, 1mmol) was added to the solution, and DCC (22.67g, 0.11mol) dissolved in CH was added dropwise thereto at room temperature₂Cl₂(200mL) of the solution and CH of 5-hexenoic acid₂Cl₂Dropwise adding the solution for 2h to obtain white precipitate, stirring for 2h, filtering, distilling under reduced pressure to obtain liquid CH₂Cl₂Dissolving, washing with water for 3 times, and reacting with CH₂Cl₂The layer was concentrated and dried to obtain polymerizable monomer A1 in 83% yield.

(2) A2 (methoxy polyethylene glycol 10-undecenoate, a ═ 11), prepared from the reaction of 10-undecenoic acid and methoxy polyethylene glycol (number average molecular weight 500, Sigma-Aldrich):

10-undecylenic acid (18.25g, 0.10mol) and polyethylene glycol monomethyl ether (number average molecular weight 500) (52.5g, 0.105mol) were reacted with 500ml of HCl₃Dissolving, adding DMAP (0.122g, 1mmol), and adding DCC (22.67g, 0.11mol) dissolved in CHCl dropwise at room temperature₃(200mL) solution, dropwise adding for 2h to obtain white precipitate, stirring for 6h after dropwise adding, filtering, distilling under reduced pressure to obtain oily substance, dissolving with water, and adding CH₂Cl₂Repeatedly extracting, taking an organic phase, concentrating, precipitating by using normal hexane, and drying a final product in vacuum to obtain the monomer A2 with the yield of 64%.

(3) A3 (polyethylene glycol 7-octenoate), prepared by reacting 7-octenoate with tetraethylene glycol (carbofuran reagent):

7-octenoic acid (14.22g, 0.10mol) and tetraethyleneglycol (21.36g, 0.11mol) were dissolved in 300mL HCl₃DMAP (122mg, 1mmol) was added thereto, and DCC (24.73g, 0.12mol) was dissolved in CHCl dropwise at room temperature₃(200mL) solution, dropwise adding for 2h to obtain white precipitate, stirring for 4h after dropwise adding, filtering, distilling under reduced pressure, and separating and purifying the obtained oily liquid by column chromatography, wherein the eluent is CH₂Cl₂/CH₃OH 25/1 and the final product was dried in vacuo to afford monomer A3 in 56% yield.

(4) A4 (methoxypolyethylene glycol 11-dodecenoate, a ═ 22), prepared by reacting 11-dodecenoic acid with methoxypolyethylene glycol (number average molecular weight 950, carbofuran reagent):

11-dodecenoic acid (21.81g, 0.11mol) and polyethylene glycol monomethyl ether (number average molecular weight 950) (95g, 0.1mol) were reacted with 1000mL CH₂Cl₂DMAP (122mg, 1mmol) was added thereto, and DCC (24.73g, 0.12mol) was dissolved in CHCl dropwise at room temperature₃(200mL) solution, dropwise adding for 2h to obtain white precipitate, stirring for 6h after dropwise adding, filtering, distilling under reduced pressure to obtain viscous yellow liquid, and adding CHCl₃Dissolving, precipitating with diethyl ether, filtering, and repeating CHCl₃Ether precipitation 2 times, dissolved in water, with n-hexane washing 3 times, aqueous phase concentration and vacuum drying to obtain monomer A4, yield 72%.

(5) A5 (methoxy polyethylene glycol 11-dodecenoate, a ═ 22), prepared from the reaction of 11-dodecenoic acid and methoxy polyethylene glycol (number average molecular weight 500, Sigma-Aldrich):

mixing 11-dodecenoic acid (21.81g, 0.11mol) and polyethylene glycol monomethyl ether (number average molecular weight 500) (50g, 0.1mol) with 500mL CH₂Cl₂DMAP (122mg, 1mmol) was added thereto, and DCC (24.73g, 0.12mol) was dissolved in CHCl dropwise at room temperature₃(200mL) solution is dripped for 2h, white precipitate appears in the system, stirring is continued for 4h after the dripping is finished, filtering and reduced pressure distillation are carried out, thus obtainingDissolving the oily substance with water, and adding CH₂Cl₂Repeated extraction, organic phase concentration, n-hexane precipitation and final product vacuum drying to obtain monomer A2 in 68% yield.

Preparation of (II) hybrid particle Dispersion

Example 1

(1) 200 parts of water and a part (1.5 parts) of polymerizable monomer A1 were added to a reactor, and stirred to mix thoroughly, the temperature of the reaction system was adjusted to 5 ℃ and the pH of the mixture was adjusted to 11, and N was introduced into the mixture₂Removing O₂。

(2) A solution of 0.15 part of hydrogen peroxide dissolved in 100 parts of water was added thereto, and while stirring uniformly, a solution of 0.3 part of ascorbic acid dissolved in 49.55 parts of water, the remainder (6 parts) of polymerizable monomer A1 and a part (8.55 parts) of organic substance F1 were added uniformly thereto over a charge addition time of 3 hours, and the reaction was accumulated for 4 hours.

(3) And (3) adjusting the pH of the mixed solution to 2 again, adjusting the temperature to 60 ℃, uniformly adding an organic matter E1(114 parts) and a residual organic matter F1(19.95 parts), adding the materials for 12h, carrying out accumulative reaction for 24h, returning the reaction system to the room temperature, and adjusting the pH of the dispersion to 7 to obtain a dispersion PB01 of the hybrid particles.

Example 2

(1) Adding 200 parts of water, 5 parts of polymerizable monomer A2 and 2.5 parts of polymerizable monomer B2 into a reactor, stirring to fully mix, adjusting the temperature of a reaction system to 25 ℃, adjusting the pH of the mixed solution to 9, introducing N into the mixed solution₂Removing O₂。

(2) To this, 0.17 part of a solution of hydrogen peroxide dissolved in 200 parts of water was added, and while stirring uniformly, 0.34 part of a solution of ascorbic acid dissolved in 49.49 parts of water, a crosslinking agent C1(1 part), a part of organic substance F1 (3.11 parts), and a part of organic substance G1 (3.11 parts) were added uniformly, and the materials were added for 2 hours, followed by cumulative reaction for 2 hours.

(3) And (3) adjusting the pH of the mixed solution to 3 again, adjusting the temperature to 75 ℃, uniformly adding an organic matter E2(20.75 parts), an organic matter F1(7.26 parts) and the rest of an organic matter G1 (7.26 parts), adding the materials for 3 hours, carrying out accumulative reaction for 6 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion to 7 to obtain the dispersion PB02 of the hybrid particles.

Example 3

(1) 245 parts of water, a part (6 parts) of polymerizable monomer A3 and polymerizable monomer B3(15 parts) were added to a reactor, stirred to mix thoroughly, the temperature of the reaction system was adjusted to 60 ℃, the pH of the mixed solution was adjusted to 9, and N was introduced into the mixed solution₂Removing O₂。

(2) While uniformly adding thereto 52.5 parts of an aqueous solution in which 1.05 parts of ammonium persulfate was dissolved, 52.5 parts of an aqueous solution in which 1.05 parts of sodium hydrogensulfite was dissolved, the remainder (24 parts) of the polymerizable monomer A3 and the crosslinking agent C2(7.5 parts), the charge-addition time was 4 hours, and the cumulative reaction was carried out for 6 hours.

(3) And adjusting the pH of the mixed solution to 4 again, adjusting the temperature to 90 ℃, uniformly adding an organic matter E3(19.5 parts), an organic matter F3(52 parts) and an organic matter G2(26 parts), adding the materials for 3 hours, carrying out accumulative reaction for 12 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion to 7 to obtain the dispersion PB03 of the hybrid particles.

Example 4

(1) 199.82 parts of water, a part (2.5 parts) of polymerizable monomer A4, a part (5 parts) of polymerizable monomer B4 and a part (1 part) of crosslinking agent C2 are added to a reactor, stirred to be fully mixed, the temperature of a reaction system is adjusted to 40 ℃, the pH of a mixed solution is adjusted to 11, N is introduced into the mixed solution₂Removing O₂。

(2) To this was immediately added 0.36 part of azobisisobutyrimidazoline hydrochloride dissolved in 199.82 parts of water in one portion to initiate polymerization, while the remaining portion (2.5 parts) of polymerizable monomer A4 and the remaining portion (1 part) of crosslinking agent C2 were uniformly added, and the mass addition time was 2 hours, and the cumulative reaction time was 6 hours.

(3) And adjusting the pH of the mixed solution to 3 again, adjusting the temperature to 90 ℃, adding an organic substance E4(44 parts) and an organic substance G1(44 parts) into the mixed solution at one time, reacting for 12 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion to 7 to obtain the dispersion PB04 of the hybrid particles.

Example 5

(1) Adding 200 parts of water, a part (3 parts) of polymerizable monomer A5, polymerizable monomer B5(15 parts) and crosslinking agent C3(3 parts) into a reactor, stirring to mix thoroughly, adjusting the temperature of a reaction system to 60 ℃, adjusting the pH of the mixed solution to 9, introducing N into the mixed solution₂Removing O₂。

(2) To this, 0.33 part of azobisisobutyramidine hydrochloride dissolved in 149.67 parts of water was added at once to initiate polymerization, while the remaining part (12 parts) of polymerizable monomer A5, a part (2.92 parts) of organic F4 and a part (2.92 parts) of organic G3 were uniformly added, and the materials were charged for 4 hours to carry out cumulative reaction for 8 hours.

(3) The pH of the mixed solution was adjusted to 2 again, the temperature was adjusted to 90 ℃, the organic substance E3(58.5 parts), the remaining part of the organic substance F4 (26.33 parts), and the remaining part of the organic substance G3 (26.33 parts) were added thereto at a time, the reaction system was allowed to react for 24 hours, the reaction system was returned to room temperature, and the pH of the dispersion was adjusted to 7, to obtain a dispersion PB05 of the hybrid particles.

Example 6

(1) Adding 200 parts of water, polymerizable monomer A2(30 parts) and polymerizable monomer B1(3 parts) into a reactor, stirring to fully mix, adjusting the temperature of a reaction system to 75 ℃, adjusting the pH of the mixed solution to 9, introducing N into the mixed solution₂Removing O₂。

(2) 0.405 part of benzoyl peroxide and 149.6 parts of water were immediately added thereto in one portion, while the crosslinking agent C4(7.5 parts) was uniformly added thereto, and the contents were added for 6 hours, and the cumulative reaction was carried out for 12 hours.

(3) And adjusting the pH of the mixed solution to 2 again, adjusting the temperature to 75 ℃, adding an organic substance E2(54.75 parts) and an organic substance F2(54.75 parts) into the mixed solution at one time, reacting for 12 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion solution to 7 to obtain the dispersion solution PB06 of the hybrid particles.

Referring to FIG. 1, the particle size measurements of the batch samples correspond to an average radius (212. + -.149) nm and a PDI of 0.496, and the measurement apparatus used is ALV/CGS-3, an incident angle of 90 degrees, a laser wavelength of 620nm, and an average radius (212. + -.149) nm and a PDI of 0.496.

Example 7

(1) Adding 200 parts of water, polymerizable monomer A1(7.5 parts) and polymerizable monomer B2(15 parts) into a reactor, stirring to mix thoroughly, adjusting the temperature of a reaction system to 70 ℃, adjusting the pH of the mixed solution to 9, introducing N into the mixed solution₂Removing O₂。

(2) A solution of 0.51 part of ammonium persulfate dissolved in 149.49 parts of water was immediately added thereto in one portion, while the crosslinking agent C5(3 parts) was uniformly added thereto, and the contents were charged for 3 hours and the cumulative reaction was carried out for 8 hours.

(3) And (3) adjusting the pH of the mixed solution to 2 again, adjusting the temperature to 90 ℃, uniformly adding an organic matter E3(24.9 parts), an organic matter F4(49.8 parts) and an organic matter G1(49.8 parts), adding the materials for 2 hours, carrying out accumulative reaction for 12 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion liquid to 7 to obtain the dispersion liquid PB07 of the hybrid particles.

Example 8

(1) 200 parts of water, a polymerizable monomer A2(15 parts), a polymerizable monomer B3(3 parts) and a part (3.75 parts) of a crosslinking agent C1 were added to a reactor, stirred to mix thoroughly, the temperature of the reaction system was adjusted to 45 ℃, the pH of the mixed solution was adjusted to 7, and N was introduced into the mixed solution₂Removing O₂。

(2) Immediately, a solution of 0.51 part of azobisisobutyrimidazoline hydrochloride dissolved in 149.49 parts of water was uniformly added thereto, and at the same time, the remaining part (3.75 parts) of crosslinking agent C1 and a part (24.9 parts) of organic substance F2 were uniformly added thereto, and the mixture was charged for 4 hours and allowed to react cumulatively for 6 hours.

(3) And adjusting the pH of the mixed solution to 4 again, adjusting the temperature to 60 ℃, uniformly adding the organic matter E4(24.9 parts) and the rest of the organic matter F2 (74.7 parts), adding the materials for 6 hours, carrying out accumulative reaction for 24 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion to 7 to obtain the dispersion PB08 of the hybrid particles.

Example 9

(1) 200 parts of water, a part (15 parts) of polymerizable monomer A3, a part (7.5 parts) of polymerizable monomer B4 and a part (1.5 parts) of crosslinking agent C1 were added to a reactor, and stirred to mix thoroughly, the temperature of the reaction system was adjusted to 25 ℃, the pH of the mixed solution was adjusted to 10, and N was introduced into the mixed solution₂Removing O₂。

(2) A solution of 0.2 parts of hydrogen peroxide dissolved in 100 parts of water was immediately added thereto, a solution of 0.45 parts of ascorbic acid dissolved in 149.35 parts of water, the remaining part (15 parts) of polymerizable monomer A3, the remaining part (6 parts) of crosslinking agent C1, a part (16.8 parts) of organic matter F2 and a part (4.2 parts) of organic matter G2 were uniformly added thereto at the same time, and the materials were added for 2 hours to cumulatively react for 2 hours.

(3) And adjusting the pH of the mixed solution to 2 again, adjusting the temperature to 75 ℃, adding the organic matter E3(21 parts), the rest of the organic matter F2 (50.4 parts) and the rest of the organic matter G2 (12.6 parts) into the mixed solution at a time, reacting for 12 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion liquid to 7 to obtain the dispersion liquid PB09 of the hybrid particles.

Example 10

(1) Adding 200 parts of water, polymerizable monomer A2(3.75 parts) and polymerizable monomer B5(3.75 parts) into a reactor, stirring to mix thoroughly, adjusting the temperature of a reaction system to 70 ℃, adjusting the pH of the mixed solution to 7, introducing N into the mixed solution₂Removing O₂。

(2) To this, 0.3 part of azobisisobutyronitrile and 224.7 parts of water were immediately added in one portion, while a portion (2.7 parts) of the organic substance G3 was uniformly added thereto, and the mixture was added for 2 hours to carry out a cumulative reaction for 12 hours.

(3) And adjusting the pH of the mixed solution to 3 again, adjusting the temperature to 60 ℃, adding the organic matter E2(54 parts) and the rest of the organic matter G3 (10.8 parts) into the mixed solution at one time, reacting for 12 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion solution to 7 to obtain the dispersion solution PB10 of the hybrid particles.

Example 11

(1) Adding 200 parts of water and a part (12 parts) of polymerizable monomer A2 into a reactor, stirring to mix thoroughly, adjusting the temperature of the reaction system to 80 ℃, adjusting the pH of the mixed solution to 7, introducing N into the mixed solution₂Removing O₂。

(2) 0.45 part of benzoyl peroxide and 149.55 parts of water were immediately added thereto in one portion, while the remaining portion (3 parts) of the polymerizable monomer A2 and the crosslinking agent C3(3 parts) were uniformly added thereto, and the materials were added for 3 hours to cumulatively react for 8 hours.

(3) And (3) regulating the pH of the mixed solution to 2 again, regulating the temperature to 90 ℃, uniformly adding an organic matter E3(105.6 parts), an organic matter F5(8.8 parts), an organic matter G2(8.8 parts) and an organic matter G3(8.8 parts), adding the materials for 3 hours, carrying out accumulative reaction for 18 hours, returning the reaction system to the room temperature, regulating the pH of the dispersion to 7, and obtaining the dispersion PB11 of the hybrid particles.

Example 12

(1) Adding 120 parts of water, a part (10 parts) of polymerizable monomer A1 and polymerizable monomer B4(10 parts) into a reactor, stirring to mix thoroughly, adjusting the temperature of the reaction system to 75 ℃, adjusting the pH of the mixed solution to 9, introducing N into the mixed solution₂Removing O₂。

(2) Immediately, 0.32 part of potassium persulfate dissolved in 279.68 parts of water was uniformly added thereto, and at the same time, the remaining portion (10 parts) of the polymerizable monomer A1 and the crosslinking agent C3(2 parts) were uniformly added thereto, and the mass was charged for 8 hours and allowed to react cumulatively for 12 hours.

(3) And adjusting the pH of the mixed solution to 2 again, adjusting the temperature to 90 ℃, adding an organic substance E3(54.4 parts), an organic substance F5(6.8 parts) and an organic substance G3(6.8 parts) into the mixed solution at one time, reacting for 6 hours, returning the reaction system to the room temperature, and adjusting the pH of the dispersion to 7 to obtain the dispersion PB12 of the hybrid particles.

(III) comparison of use Effect

The concrete application experiment is mainly adopted to illustrate the use effect of the amphiphilic hybrid particles. The concrete mechanical property test is carried out according to GB/T50080-2002 and GB/T50081-2002, the chloride ion permeability and electric flux test is carried out according to GB/T50082-2009, and the concrete water absorption is tested according to the BS1881-122-83 standard. Concrete slump of New Material Ltd of Subot of Jiangsu

The high-performance polycarboxylic acid water reducing agent is adjusted to be (20 +/-1) cm, and the gas content is adjusted to be (2.5 +/-0.3)%.

The materials used included: the cement (P.II.52.5) for small open-field in south of Yangtze river, class II fly ash, river sand with fineness modulus of 2.6 and crushed stone with 5-25mm continuous gradation.

The concrete mixing proportion is shown in a table 2, the concrete test results are shown in a table 3, all test results are test results of the test block for 28 days except for the marked age, and the water absorption rate is the weight increase of the test block after being soaked for 0.5 h. The concrete was prepared without adding the dispersion of the hybrid particles, and PB01-PB12 was prepared as a concrete sample containing 0.4% of the effective amount of the hybrid particles relative to the total binder. The zinc stearate is concrete with 1 percent of total glue material mixed in the calcium stearate; the comparative sample 1 is concrete added with zinc stearate and nano-alumina respectively, and the effective mixing amount is 0.4 percent of the total glue material amount; comparative example 2 is core-shell structure particles prepared according to the example of patent CN103922638B, and the amount of the core-shell structure particles added is 0.4% of the total amount of the glue material.

The amphiphilic hybrid particle dispersion is mixed with saturated Ca (OH)₂The solution can keep good stability when mixed, and has no coagulation phenomenon.

TABLE 2 concrete mix ratio (kg/m)³)

Cement	Fly ash	Mineral powder	Sand	Stone (stone)	Water (W)
						193	83	147	750	1067	147

TABLE 3 fresh concrete mixing Properties and macroscopic Properties at different ages

As can be seen from the data in the table:

(1) compared with a concrete reference sample, the concrete doped with the amphiphilic hybrid particles has slightly improved compressive strength in 28 days, the compressive strength is increased to 61.6-65.0MPa from 58.6MPa, and the strength is slightly increased by 4-11%; the electric flux of the concrete test piece is reduced from 925.3C to 232-600C within 28 days, and the electric flux is reduced by 35-75 percent; in addition, the diffusion coefficient of chloride ions of the concrete is remarkably reduced from 7.0 multiplied by 10 in 28 days^-12m²The/s can be obviously reduced to 1.7-4.9 multiplied by 10^-12m²The/s is reduced by 30-75%; the water absorption of the concrete is reduced by 39-81% and 38-79% respectively in 7 days and 28 days.

(2) When the stearate (compared with zinc stearate) is added in a high amount (1.0% of the total glue material mass), the effect of reducing the water absorption is slightly weaker than that of hybrid particles, but the water absorption can be obviously reduced by 52-56%, however, the concrete compressive strength is reduced by 24%, the diffusion coefficient of chloride ions is not obviously improved, and the performance is obviously weaker than that of amphiphilic hybrid particles.

(3) Comparative example 1 is the application performance of adding stearate and silica sol into concrete separately, under the condition of adding 0.4% of glue material amount into the two, although the electric flux of concrete, the diffusion coefficient of chloride ions, and the water absorption rate in 7 days and 28 days can be reduced, the degree is equivalent to the lower limit of the performance improvement in the nano particles shown in the invention, but the strength of the concrete in 28 days is obviously weakened.

More importantly, the two are difficult to mix and must be added separately, which obviously increases the difficulty of application, and the nano-alumina is saturated with Ca (OH)₂The solution tends to aggregate and not disperse effectively, which is completely detrimental to the workability of the cement-based material. In contrast, all amphiphilic hybrid particle dispersions were mixed with saturated Ca (OH)₂The solution can keep good stability when mixed, and has no coagulation phenomenon, so the application performance is more excellent.

(4) The comparative sample 2 adopts the core-shell structure particles to solve the stability problem of the particles, but the improvement on the electric flux, the chloride ion diffusion coefficient and the concrete water absorption rate in 28 days is obviously weaker than that of the amphiphilic hybrid particles prepared by the invention.

Claims

1. A preparation method of amphiphilic multifunctional hybrid particles based on aluminum oxide is characterized by comprising the following specific steps:

(3) adjusting the pH of the mixed solution after the reaction in the step (2) to 2-4 again, adjusting the temperature to 60-90 ℃, adding a second batch of organic component D and organic matter E into the mixed solution at a constant speed, reacting for 6-24h, recovering the reaction system to room temperature, and adjusting the pH of the mixed solution to 7 to obtain the dispersion liquid of the amphiphilic multifunctional hybrid particles;

the surface layer of the amphiphilic multifunctional hybrid particle is attached with a detachable water-soluble long side chain and a hydrophobic long chain, the components in the particle are aluminum oxide or hydroxide network with a hydrophobic long chain hydrocarbon functional group for complexing or covalent substitution, and the particle also contains free fatty acid or fatty acid ester or fatty acid aluminum complex with a hydrophobic long chain hydrocarbon functional group;

the average diameter of the amphiphilic multifunctional hybrid particles is not more than 1000 nm;

the polymerizable monomer A is selected from one or a mixture of two of polyethylene glycol monounsaturated fatty acid ester and methoxy polyethylene glycol monounsaturated fatty acid ester;

the polymerizable monomer B is unsaturated fatty acid or a mixture thereof;

the organic component D is one or more than one of saturated or unsaturated long-chain fatty acid or fatty acid ester F and aluminum complex G of saturated or unsaturated fatty group long-chain fatty acid;

functional group R in the general formula (4)₄Represents a saturated or unsaturated hydrocarbon function containing from 5 to 21 carbon atoms, R₅Represents a hydrogen atom or a saturated alkyl group of 1 to 22 carbon atoms;

the aluminum complex G of the saturated or unsaturated fatty group long-chain fatty acid is Al (R)₆COO)₃Or Al (OH) (R)₇COO)₂One or any combination of more than one of (1), wherein R₆And R₇Each independently represents a saturated or unsaturated hydrocarbon functional group containing 8 to 18 carbon atoms;

the organic matter E is an aluminum alkoxide organic matter;

the polymerizable monomer A is added in the steps (1) and (2) in batches, and the mass fraction of the first polymerizable monomer A in the total polymerizable monomer A is not less than 20%; the cross-linking agent C is added in the step (1) and the step (2) in batches, and the proportion of the two batches is arbitrary; the organic component D is added in the steps (2) and (3) in batches, and the mass of the organic component D in the first batch accounts for 0-30% of the total mass of all the organic components D; the water added in the step (1) accounts for 30-75% of the total water used in the reaction;

2. The method for preparing amphiphilic multifunctional hybrid particles based on aluminum oxide according to claim 1, wherein the polymerizable monomer A is any one or any combination of more than one of the structures shown in the following general formula (1):

wherein the functional group R₁Is unsaturated long-chain hydrocarbon functional group containing 5-11 carbon atoms, the end of the unsaturated long-chain hydrocarbon functional group is unsaturated double bond, the end refers to the end far away from ester bond in the general formula (1), R₂Represents H or methyl, a is polyethylene glycol chain ethylene glycol unit (-CH)₂CH₂O-) average molar addition number, which takes the valueThe range is 4-22.

3. The method for preparing amphiphilic multifunctional hybrid particles based on aluminum oxide according to claim 2, wherein the polymerizable monomer B is any one or any combination of more than one of linoleic acid, palmitoleic acid or a structure represented by the following general formula (2):

4. The method for preparing amphiphilic multifunctional hybrid particles based on aluminum oxide according to claim 3, wherein the organic material E is any one or any mixture of more than one of the following structures represented by the following general formula (5):

5. The preparation method of the amphiphilic multifunctional hybrid particle based on aluminum oxide according to claim 4, wherein the initiator is a thermal initiator or a redox initiator; the amount 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, the polymerizable monomer B and the cross-linking agent C; if the initiator is a redox initiator, the mass of the oxidizing agent and the reducing agent is 0.4 to 4 percent of the total mass of the polymerizable monomer A, the polymerizable monomer B and the crosslinking agent C respectively.

6. The method of claim 5, wherein the redox initiator is composed of an oxidant and a reducing agent, the oxidant comprises hydrogen peroxide, ammonium persulfate and potassium persulfate, and the reducing agent comprises ascorbic acid and sodium bisulfite; the thermal initiator comprises azobisisobutyramidine hydrochloride, benzoyl peroxide and azobisisobutyronitrile.

7. The application method of the amphiphilic multifunctional hybrid particle based on aluminum oxide prepared by the preparation method of claim 1 is characterized in that when the cement-based material is prepared, the hybrid particle is added into the cement-based material directly in one step during the mixing process to participate in stirring, and the using amount of the hybrid particle is 0.1-0.5% of the total mass of the cement-based material.