CN1258540C - Macromolecule/A12O3 nano complex particle preparation method - Google Patents

Abstract

The present invention relates to a method for preparing high molecular/Al2O3 nanometer composite particles, which belongs to the technical field of macromolecular material. The present invention discloses a method for preparing high molecular/Al2O3 nanometer composite particles through microemulsion polymerization and a preparing method through microsuspension polymerization. The two methods comprise: alkene monomers, Al2O3 particles, coupling agents, emulsifying agents and initiating agents are used as raw materials, and the raw materials are treated to obtain spherical high molecular/Al2O3 nanometer composite particles which use needle-shaped inorganic nanometer Al2O3 particles as cores, organic olefin polymers as shells and chemical bonds for connecting the cores and the shells and have particle sizes smaller than 100 nm. The methods of the present invention are suitable for spherical or near spherical inorganic nanometer particles with high content of surface hydroxy groups as well as non spherical inorganic nanometer particles with low content of surface hydroxy groups. The methods solve the problem that the original needle-shaped particles or non spherical particles with low content of surface hydroxy groups are different to coat and simultaneously solve the problem that the coating layers of the original coating type nanometer particles are easy to fall off.

Description

Preparation method of polymer/Al2O3 nanocomposite particles

technical field

The preparation method of polymer/Al ₂ O ₃ nano composite particles involved in the invention belongs to the technical field of polymer materials.

Background technique

In recent years, more and more researchers have paid attention to the preparation and application of nanoparticles, and more and more nanocomposite technologies have been introduced in the fields of polymer materials, chemical engineering, biology, medicine, and microelectronics. In the field of polymer materials, inorganic nano-powders commonly used to fill the matrix of materials include SiO ₂ , Al ₂ O ₃ , ZnO, TiO ₂ and so on. However, when these inorganic powders are filled in the polymer matrix, since the powder itself is inorganic and the filled phase is an organic polymer, the compatibility between the two is very poor, which leads to the formation of inorganic powder particles in the matrix. The dispersibility is very poor, so the filling effect is also very limited. The preparation technology of polymer/inorganic powder nanocomposites makes the product have the characteristics of both inorganic nanoparticles and organic polymers, and greatly improves the compatibility between the particles and the matrix, so its development and preparation are increasingly becoming high-tech. A hot direction in the research of new molecular materials.

The inventor has successfully carried out the grafting and coating of the surface macromolecule layer on the nano- _SiO2 particle (patent application number 02155458.7), and this composite particle has the characteristics of the above-mentioned macromolecule/inorganic powder nanocomposite material, It has good interfacial compatibility with the matrix so that the properties of the matrix can be qualitatively improved. In addition, in the Chinese patent (publication number CN1369511A), SiO ₂ /macromolecule or polymer/inorganic powder nano-hybrid body with SiO ₂ as the main body was obtained by using different methods. However, the common limitation of the above methods is that the inorganic particles are required to be spherical or quasi-spherical, which is not suitable for many non-spherical particles such as needles, because the latter have higher surface energy than spherical particles and thus are more unstable. At the same time, the above methods are not applicable to the surface grafting and coating of other inorganic powders except _SiO2 , because compared with other inorganic nanoparticles, the surface of _SiO2 has more hydroxyl groups, which makes it more effective in the preparation of The process is relatively stable, and the preparation difficulty is relatively low. On the other hand, a large number of hydroxyl groups make it easy for SiO ₂ to chemically react with the polymer layer through an appropriate method to form a chemical bond on the interface. Although it is mentioned in the Chinese patent CN 1369511 A that the core of the particles in its polymer/inorganic particle hybrid can be obtained by coating other inorganic substances on the surface of _SiO (such as coating aluminum oxide), the formulation and process of the It can be seen that the alumina coated on the surface of _SiO2 is at the molecular level rather than at the nanometer level, which is completely different from the coating of nanoscale alumina; and the content of these non- _SiO2 inorganic substances is very small, so its technical essence is still Polymer coating is performed on _SiO2 . It can be seen from the above that the coating problems of inorganic nanoparticles other than SiO ₂ or non-spherical particles such as needles still need to be solved.

The present invention intends to use polymers or monomers that can react with the surface of the inorganic particles, or can react with the functional groups introduced on the surface of the inorganic particles, to form a polymer coating layer through functional group reactions or polymerization reactions. Grafted on the surface of inorganic nanoparticles, finally forming nanocomposite particles with the inorganic particles as the core and the polymer layer as the shell. The present invention can ensure the formation of strong chemical bonds between the polymer layer and the surface of the inorganic particles; meanwhile, the present invention is applicable to non-spherical inorganic nanoparticles, which can solve the problem that non-spherical particles such as needles are difficult to coat in the past, and can also Solving the dispersion problem of Al ₂ O ₃ will create the necessary prerequisites for the application of nano-Al ₂ O ₃ in the filling modification of polymer materials.

Contents of the invention

The purpose of the present invention is to provide a method for preparing polymer/Al ₂ O ₃ nanocomposite particles. This method solves the problem that non-spherical particles such as needles are difficult to coat in the past by changing the process conditions, and at the same time solves the problem of Al ₂ O ₃ dispersibility problem, and by grafting a polymer coating layer on the surface of Al ₂ O ₃ inorganic particles, the problem that the coating layer of coated nanoparticles in the past is easy to fall off during use is solved, which greatly improves Its application value is confirmed, and it has far-reaching application prospects in the development of nanotechnology.

The purpose of the present invention is achieved through the following technical solutions:

The invention discloses a microemulsion polymerization preparation method of macromolecule/Al ₂ O ₃ nanocomposite particles, which is characterized in that: the method uses the following materials as raw materials:

Olefin monomer: 100 parts by weight,

Al ₂ O ₃ particles: 0.1 to 30 parts,

Coupling agent: accounts for 1-30wt% of Al ₂ O ₃ particles,

Emulsifier: 15-65 parts,

Water-soluble initiator: 0.1 to 3 parts,

The specific process steps are as follows:

1) After the Al ₂ O ₃ particles are treated with the coupling agent, they are added to the olefin monomer according to the above ratio, so that they are mixed and dispersed uniformly;

2) The mixture obtained in step 1) is added to a reactor containing deionized water and an emulsifier and heated to 40°C to 50°C in advance, and then 20-70% of all water-soluble initiators are added to the reactor, And make it warm up to the temperature range of 60 ℃ ~ 70 ℃ to react for 2 ~ 8 hours;

3) Add the remaining water-soluble initiator, and continue the reaction at 80°C to 90°C for 0.5 to 1 hour;

4) After cooling and discharging, after demulsification, washing and drying steps, a needle-shaped inorganic nano- _Al2O3 particle is used as the core, an organic olefin polymer is used as _the shell, and the core-shell is connected by a chemical bond. The particle size is less than 100nm spherical polymer/Al ₂ O ₃ nanocomposite particles.

The olefin monomers mentioned in the present invention refer to monoolefin or polyolefin substances containing carbon-carbon unsaturated double bonds in the molecular structure.

The monoolefins described in the present invention adopt alpha-olefins, including one or more of styrene, vinyl chloride, acrylonitrile, acrylate, and methacrylate; the multiolefin substances adopt diolefins or multiolefins , including one or more of butadiene, isoprene, and trimethylolpropane trimethacrylate.

The coupling agent in the present invention refers to a substance that should contain at least one carbon-carbon unsaturated double bond in the _molecular structure and can form a chemical bond with the surface of _Al2O3 particles, including silane type, aluminate type, borate type , titanate type, boroaluminate type, borotitanate type or titanate type or one or more of them.

The emulsifier of the present invention adopts one or more of the following materials:

a. Cationic type: including tri-C _1-18 alkyl methyl ammonium chloride, tri-C _1-18 alkyl methyl ammonium bromide, tri-C _1-18 alkyl benzyl ammonium chloride, tri-C _1-18 Alkyl benzyl ammonium bromide, or tri-C _1-18 alkyl methyl benzyl ammonium chloride, tri-C _1-18 alkyl ethyl benzyl ammonium chloride, tri-C _1-18 alkyl methyl benzyl ammonium Ammonium bromide, three C _1~18 alkyl ethyl benzyl ammonium bromide;

b. Anionic type: including C12~18 alkyl sodium sulfate, C12~18 alkyl potassium sulfate, C12~18 alkyl sulfonate sodium, C12~18 alkyl sulfonate potassium, C12~18 alkylbenzene sulfonate sodium, Potassium C12-18 alkylbenzene sulfonate;

c. Non-ionic type: including C3~10 alkylphenol polyoxyethylene (4~50) ether, C2~18 fatty alcohol polyoxyethylene (4~50) ether, polyoxyethylene (4~50) sorbitol single C11 ～18 fatty acid esters, polyoxyethylene (4～50) sorbitol three C11～18 fatty acid esters.

The water-soluble initiator described in the present invention refers to a water-soluble substance that can have a dissociation energy of 30-35 kcal/mol and can generate free radicals to cause the polymerization of olefin monomers under the condition of 40-95 ° C, including water-soluble persulfates Hydrogen peroxide, hydrogen peroxide, or a redox system composed of hydrogen peroxide, ferrous salt, sulfite, and thiosulfate.

The present invention also discloses a microsuspension polymerization preparation method of macromolecule/Al ₂ O ₃ composite nanoparticles, which is characterized in that: the method uses the following materials as raw materials:

Olefin monomer: 100 parts by weight,

Al ₂ O ₃ particles: 0.1 to 30 parts,

Coupling agent: accounts for 1-30wt% of Al ₂ O ₃ particles,

Emulsifier: 15-65 parts,

Oil-soluble initiator: 0.1 to 3 parts,

The specific process steps are as follows:

1) After the Al ₂ O ₃ particles are treated with the above-mentioned coupling agent, mix it with 20-70% of all oil-soluble initiators, add it to the above-mentioned olefin monomer, make it mix and disperse evenly;

2) Add the mixture obtained in step 1) into a reactor containing deionized water and an emulsifier that is pre-heated to 40°C to 50°C, and heat it up to a temperature range of 60°C to 70°C for 2 to 8 minutes. Hour;

3) Add the remaining oil-soluble initiator, and continue the reaction at 80°C to 90°C for 0.5 to 1 hour;

4) After cooling and discharging, and through demulsification, washing and drying steps to obtain a needle-shaped inorganic nano-Al ₂ O ₃ particle as the core, an organic olefin polymer as the shell, and a particle size smaller than that connected by a chemical bond between the core and the shell. 100nm spherical polymer/Al ₂ O ₃ nanocomposite particles.

The oil-soluble initiator in the present invention refers to an oil-soluble substance that has a dissociation energy of 30-35 kcal/mol and can generate free radicals to cause the polymerization of olefin monomers under the condition of 40-95°C, including oil-soluble azobisiso Butyronitrile, dibenzoyl peroxide, or a redox system composed of dibenzoyl peroxide, ferrous salt, sulfite, and thiosulfate respectively.

Under the background of the existing technology, the present invention adopts a brand-new process to better solve a series of difficult problems existing in this field such as needle-shaped non-spherical particles and particles with low surface hydroxyl content are difficult to coat. There are two main reasons for the above-mentioned problems in the past: one is that non-spherical particles have higher surface energy than spherical particles, and are extremely unstable, so they are easy to separate from the system during the preparation process and cause precipitation, which leads to coating failure; When the particle surface hydroxyl content is very small, its stability in the preparation system is correspondingly reduced, which is not conducive to the reaction with polymers, and it is also easy to cause separation from the system. However, in the various polymerization preparation methods in the past, the exothermic heat of the polymerization reaction will seriously damage the stability of the system, especially when the stability of the particle itself is relatively poor, and this phenomenon is more obvious. Therefore, the present invention adopts a microemulsion or a microsuspension system, which first improves the stability of the system thermodynamically; secondly, through a large number of studies, it is found that the exothermic phenomenon in the early stage of polymerization is obvious, and at this time, the particles are in the molding stage, and the stability of the system is easily affected. to destruction. Therefore, the present invention divides the polymerization process into two steps. In the first step, by controlling the addition amount and reaction temperature of the initiator in the early stage, the polymerization rate in this period is maintained in a very low range, avoiding the reaction caused by the reaction in the previous one-step method. The high rate and obvious exothermic effect caused the problem of particles leaving the system and causing precipitation; after the nucleation and growth of the particles were stable, the reaction temperature was raised to the usual reaction temperature to speed up the preparation process, and finally the polymer/Al ₂ O ₃ nanocomposite was prepared. Particles, the nano-scale Al ₂ O ₃ in the particle is needle-shaped, and the product after coating is spherical with a particle size of less than 100 nanometers, which is in the nanoscale category, so it has many special properties of nanoparticles, and has great significance in the development of nanotechnology. Far-reaching application prospects. The preparation method of macromolecule/ _Al2O3 nanocomposite particle of the present invention _, its total reaction yield is all more than 90% generally, grafting rate can be between tens to tens of thousands of percentages according to monomer and The proportion of Al ₂ O ₃ is adjusted, and the grafting efficiency is generally above 90%. In addition, the preparation of the polymer/Al ₂ O ₃ nanometer composite particles is simple and easy to realize industrial production, and the prepared product can be stably maintained in an emulsion state or dried into a powder state, which is easy to store and use. These characteristics will make the polymer/Al ₂ O ₃ nanocomposite particles of the present invention widely used in the future development of nanomaterial science and technology.

Description of drawings

Figure 1 is the infrared spectra of PS/Al ₂ O ₃ nanocomposite particles (a) and original Al ₂ O ₃ (b).

Figure 2a is _an electron micrograph of pristine _Al2O3 .

Figure 2b is an electron micrograph of PS/Al ₂ O ₃ nanocomposite particles.

Fig. 3 is the particle size distribution curve of PS/Al ₂ O ₃ nanocomposite particles.

The present invention will be further described below in conjunction with the examples.

Example 1: After the short rod-shaped nano _-Al2O3 with an average particle size of 30±5nm, an aspect ratio of 5, and a specific _surface area of 180m2 ^/ g is dry-treated with 10wt% KH-570 silane coupling agent, Weigh 4 parts and add to 100 parts of styrene monomer, stir and ultrasonically disperse evenly. Add 370 parts of deionized water, 50 parts of sodium dodecylsulfonate (SDS) and 6 parts of nonylphenol polyoxyethylene ether (10 parts) in a four-necked bottle equipped with mechanical stirring, reflux condenser, nitrogen protection and thermometer. ), heated to 40°C and stirred to dissolve, then added the mixture of monomer and Al ₂ O ₃ at 50°C. Then, add 20% of the initiator aqueous solution made up of 0.5 parts of ammonium persulfate (APS) and 75 parts of deionized water, heat up to 60°C and react for 3 hours, add the remaining initiator solution, heat up to 80°C to continue the reaction for 1 Cool and discharge after 1 hour. Part of the emulsion after discharge was demulsified, washed, and dried to obtain a white powder product, and the other part of the emulsion was placed in a test tube, and it was found that no precipitation occurred after 12 months of storage. The total reaction yield was calculated to be 98.1%, and after the dried composite nanoparticles were extracted with xylene for 12 hours, the grafting rate was measured to be 2328%, and the grafting efficiency was 93.1%. Its infrared spectrum is shown in Figure 1 (infrared spectrum of Al ₂ O ₃ nanoparticles and PS/Al ₂ O ₃ nanocomposite particles after extraction), and the spectrum (b) shows obvious PS and Al ₂ O ₃ , indicating that PS is grafted on the surface of Al ₂ O ₃ through chemical bonds. It can be seen from Fig. 2 (a: Al ₂ O ₃ nanoparticles; b: PS/Al ₂ O ₃ nanocomposite particles) and Fig. 3 (test results of particle size distribution of PS/Al ₂ O ₃ nanocomposite particles). The particle size distribution is in the range of 40-50nm, and the particles have a spherical core-shell structure.

Embodiment 2: The emulsifier SDS among the embodiment 1 is changed into hexadecyltrimethylammonium bromide, and the consumption is increased to 65 parts, and all the other formulas are the same as the example 1. The yield, grafting rate and grafting efficiency of the obtained product are 92.5%, 2290% and 90.6% respectively, and the particle size distribution is 40-50nm.

Embodiment 3: The emulsifier SDS is changed into octylphenol polyoxyethylene ether (20), and the consumption is reduced to 15 parts, and the remaining formulas and steps are the same as in Example 1. The yield, grafting rate and grafting efficiency of the obtained product are 87.3%, 2262% and 91.5% respectively, and the particle size distribution is 70-80nm.

Embodiment 4: On the basis of Embodiment 1, 70% of the initiator was added after the temperature was raised to 60° C., and all the other formulation steps were unchanged. The yield, grafting rate and grafting efficiency of the obtained product are 85.2%, 2270% and 87.9% respectively, and the particle size distribution is 50-60nm.

Example 5: Reduce the amount _{of Al2O3} added from 4 parts to 0.1 part, the amount of KH-570 _is 1wt% of _Al2O3 , after the reaction starts, the temperature is raised to 70 ° C for 2 hours, after adding the remaining initiator Raise the temperature to 90° C. and react for 0.5 hour, and the rest of the formula and steps are the same as in Example 1. The yield, grafting rate and grafting efficiency of the obtained product are 99.4%, 89700% and 89.7% respectively, and the particle size distribution is 30-40nm.

Example 6: Increase the amount of _Al2O3 added to ₃₀ parts, reduce the amount of APS to 0.1 part, and the amount of KH-570 is 30wt% of _Al2O3 , then react for ₈ hours and then heat up to 80 ° C, the rest of the formula and The steps are the same as Example 1. The yield, grafting rate and grafting efficiency of the obtained product are 90.2%, 2297% and 90.9% respectively, and the particle size distribution is 50-60nm.

Example 7: Increase the amount of APS to 3 parts, react at 60° C. for 8 hours and then increase the temperature and add the remaining initiator. The rest of the formula and steps are the same as in Example 1. The yield, grafting rate and grafting efficiency of the obtained product are 85.8%, 2247% and 90.5% respectively, and the particle size distribution is 70-80nm.

Embodiment 8: Sodium dodecyl sulfonate is changed into the same amount of sodium dodecylbenzene sulfonate, and styrene is changed into the mixture of equal amounts of methyl methacrylate and ethyl acrylate (half and half) simultaneously , other formulas and steps are the same as in Example 1. The yield, grafting rate and grafting efficiency of the obtained product are 92.2%, 2516% and 91.5% respectively, and the particle size distribution is 40-50nm.

Example 9: After the short rod-shaped nano Al ₂ O ₃ with an average particle size of 30±5nm, an aspect ratio of 5, and a specific surface area of 180m ² /g was dry-treated with 10wt% KH-570 silane coupling agent, Weigh 4 parts and add to 100 parts of styrene monomer, stir and ultrasonically disperse evenly. Add 0.1 part of azobisisobutyronitrile to the above mixture and mix well. Add 370 parts of deionized water, 60 parts of sodium dodecylsulfonate (SDS) and 5 parts of nonylphenol polyoxyethylene ether (10 parts) in a four-necked bottle equipped with mechanical stirring, reflux condenser, nitrogen protection and thermometer. ), heated up to 40°C and stirred to dissolve, then added the mixture of monomer, Al ₂ O ₃ and partially oil-soluble initiator at 50°C. After raising the temperature to 60°C and reacting for 3 hours, add the remaining azobisisobutyronitrile into the system, raise the temperature to 80°C and continue the reaction for 1 hour, then cool and discharge. The total reaction yield is 93.6%, the grafting rate is 2494%, the grafting efficiency is 91.7%, and the particle size distribution is 40-50nm.

Example 10: The coupling agent was changed to an equivalent amount of oleic acid aluminate coupling agent, the initiator was changed to 3 parts of dibenzoyl peroxide, and the rest of the formulation steps were the same as in Embodiment 9. The yield, grafting rate and grafting efficiency of the obtained product are 90.8%, 2461% and 93.8% respectively, and the particle size distribution is 40-50nm.

Example 11: Change the coupling agent to an equivalent amount of boroaluminate coupling agent, change the initiator to a redox initiation system consisting of 2 parts of dibenzoyl peroxide and 1 part of sodium sulfite, and the remaining formulas and steps are the same as Example 9 is the same. The yield, grafting rate and grafting efficiency of the obtained product are 91.2%, 2239% and 91.6% respectively, and the particle size distribution is 40-50nm.

In the above examples, examples 1, 2, 3, 4, 5, 6, 7, and 8 belong to the method of microemulsion polymerization, and examples 9, 10, and 11 belong to the method of microsuspension polymerization.

Comparative Example 1: The preparation method is the same as that of Example 1, but Al ₂ O ₃ is not treated with a coupling agent, and it is found that the system precipitates during the reaction. This shows that Al ₂ O ₃ particles can be well dispersed in olefin monomers only in the presence of coupling agent to make the reaction go smoothly.

Comparative Example 2: The preparation method is the same as that of Example 1, but the amount of sodium dodecylsulfonate added is changed to 10 parts, and the system undergoes demulsification and precipitation during the reaction process. It can be seen that, in the microemulsion polymerization method of the present invention, the amount of emulsifier must be large enough, and within the given range of the present invention, the system can be relatively stable.

Comparative Example 3: The preparation method is the same as that of Example 9, but the amount of sodium dodecylsulfonate added is changed to 10 parts, and the system undergoes demulsification and precipitation during the reaction process. , it can be seen that in the microsuspension polymerization method of the present invention, the amount of emulsifier (or dispersant) must be large enough, and within the given range of the present invention, the system can be relatively stable.

Comparative example 4: preparation method is the same as example 1, but the amount of sodium dodecylsulfonate added is changed into 70 parts, and the productive rate, grafting rate and grafting efficiency of final product are respectively: 85.5%, 671% and 27.5% %, the grafting efficiency dropped significantly. The particle size distribution is 30 to 60 nm, which is significantly broadened. This shows that the consumption of emulsifying agent should not be too large, must strictly follow the given dosage range of the present invention to obtain ideal results.

Comparative Example 5: The preparation formula is the same as that of Example 1, but the temperature of the system rises to 80° C. after the initiator is added for the first time, and a large amount of precipitation appears in the system after the reaction starts. This shows that the one-step process in the prior art is not suitable for the preparation of the system of the present invention because the initial reaction speed is too fast and exothermic is obvious, which causes the system stability to be destroyed. Therefore, the two-step method of the present invention must be used to make the system stable. The reaction proceeded stably.

Comparative Example 6: The preparation formula was the same as that of Example 1, but all the initiators were added at one time at 60°C. After the reaction started, a large amount of hard lumpy precipitates appeared in the system, and the reaction could not proceed. This shows that in the existing emulsion polymerization process, the method of adding the initiator at one time cannot obtain a stable system due to the inability to effectively control the reaction speed, and the step of adding the initiator in batches according to the present invention can be used to obtain the particles.

Comparative Example 7: The preparation formula is the same as that of Example 9, but all the oil-soluble initiators are directly mixed with the monomers at the beginning, and then the phenomenon of demulsification and precipitation occurs soon after the reaction starts. This shows that in the existing suspension polymerization process, the method of adding the initiator at one time cannot obtain a stable system due to the inability to effectively control the reaction speed, and the step of adding the initiator in batches according to the present invention can only be obtained. said particles.

Although the present invention has been described in various preferred embodiments, those skilled in the art can easily understand that the present invention is not limited to the above description, and it can be changed or improved in various other ways without departing from the claims of the present invention. The spirit and scope set forth in.

Claims (8)

1. polymer/Al ₂O ₃The micro-emulsion polymerization preparation method of nano-complex particle is characterized in that: this method is a raw material with following material:

Olefinic monomer: 100 parts by weight,

Al ₂O ₃Particle: 0.1～30 part,

Coupling agent: account for Al ₂O ₃1～30wt% of particle,

Emulsifying agent: 15～65 parts,

Water soluble starter: 0.1～3 part,

Concrete processing step is as follows:

1) with Al ₂O ₃Particle with described coupling agent treatment after, join according to the above ratio in the described olefinic monomer, make it to mix and be uniformly dispersed;

2) mixture that step 1) is obtained joins and contains deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor, in this reactor, add the 20-70% of whole water soluble starters again, and make it to be warming up to 60 ℃～70 ℃ temperature range internal reaction 2～8 hours;

3) add the residue water soluble starter, 80 ℃～90 ℃ are continued reaction 0.5～1 hour down;

4) behind the cooling discharging, obtain having with needle inorganic nano Al through breakdown of emulsion, washing and drying step processing ₂O ₃Particle is the particle diameter that connects with chemical bond between shell, the nucleocapsid spherical polymer/Al less than 100nm for nuclear, with the olefinic organic hydrocarbon polymer ₂O ₃Nano-complex particle.

2. according to the described preparation method of claim 1, it is characterized in that: described olefinic monomer is meant monoolefine or the Polyene Hydrocarbons material that contains carbon carbon unsaturated double-bond in molecular structure.

3. according to the described preparation method of claim 2, it is characterized in that: described monoolefine adopts alpha-olefin, comprises in vinylbenzene, vinylchlorid, vinyl cyanide, acrylate, the methacrylic ester one or more; Described Polyene Hydrocarbons material adopts diolefine or polyene hydrocarbon, comprises in suitable divinyl, isoprene, the trimethylolpropane trimethacrylate one or more.

4. according to the described preparation method of claim 1, it is characterized in that: described coupling agent be meant should contain at least in the molecular structure carbon carbon unsaturated double-bond and can with Al ₂O ₃Particle surface forms the material of chemical bonding, comprises in silane type, aluminic acid ester type, borate-type, titanic acid ester type, boron aluminic acid ester type, boron titanic acid ester type or the titanium aluminic acid ester type one or more.

5. according to the described preparation method of claim 1, it is characterized in that: described emulsifying agent adopts one or more in the following material:

A. cationic: as to comprise three C _1～18Alkyl methyl ammonium chloride, three C _1～18Alkyl methyl brometo de amonio, three C _1～18Alkyl benzyl ammonium chloride, three C _1～18Alkyl benzyl brometo de amonio or three C _1～18Alkyl methyl benzyl ammonium chloride, three C _1～18Alkyl ethylbenzylammonium chloride, three C _1～18Alkyl methyl benzyl brometo de amonio, three C _1～18Alkyl Ethylbenzyl brometo de amonio;

B. anionic: comprise C12～18 sodium alkyl sulfates, C12～18 alkylsurfuric acid potassium, C12～18 alkyl sodium sulfonates, C12～18 alkylsulphonic acid potassium, C12～18 sodium alkyl benzene sulfonates, C12～18 alkyl benzene sulphonate (ABS) potassium;

C. non-ionic type: comprise C3～10 alkyl phenol polyoxyethylenes (4～50) ether, C2～18 aliphatic alcohol polyethenoxies (4～50) ether, polyoxyethylene (4～50) sorbyl alcohol list C11～18 fatty acid esters, polyoxyethylene (4～50) sorbyl alcohol three C11～18 fatty acid esters.

6. according to the described preparation method of claim 1, it is characterized in that: described water soluble starter is meant can be under 40～95 ℃ of conditions, have 30～35kcal/mol ionic dissociation energy and can produce free radical and cause olefinic monomer polymeric water-soluble substances, comprise water miscible persulfuric acid salt, hydroperoxide kind material or the redox system of forming with ferrous salt, sulphite, thiosulphate respectively by hydrogen peroxide.

7. polymer/Al ₂O ₃The microsuspension preparation method of composite nano particle is characterized in that: it is raw material that this method adopts following material:

Olefinic monomer: 100 parts by weight,

Al ₂O ₃Particle: 0.1～30 part,

Coupling agent: account for Al ₂O ₃1～30wt% of particle,

Emulsifying agent: 15～65 parts,

Oil-soluble initiator: 0.1～3 part,

Concrete processing step is as follows:

1) with Al ₂O ₃Particle with above-mentioned coupling agent treatment after, with itself and all 20-70% of oil-soluble initiators mix, join in the above-mentioned olefinic monomer, make it to mix and be uniformly dispersed;

2) mixture that step 1) is obtained joins and contains deionized water and emulsifying agent and be warming up in advance in 40 ℃～50 ℃ the reactor, and makes it to be warming up to 60 ℃～70 ℃ temperature range internal reaction 2～8 hours;

O.5～1 hour 3) add the residue oil-soluble initiator, 80 ℃～90 ℃ are continued reaction down;

4) behind the cooling discharging, and handle through breakdown of emulsion, washing and drying step and to obtain having with needle inorganic nano Al ₂O ₃Particle is the particle diameter that connects with chemical bond between shell, the nucleocapsid spherical polymer/Al less than 100nm for nuclear, with the olefinic organic hydrocarbon polymer ₂O ₃Nano-complex particle.

8. microsuspension preparation method according to claim 7, it is characterized in that: described oil-soluble initiator is meant under 40～95 ℃ of conditions, have 30～35kcal/mol ionic dissociation energy and can produce free radical and cause olefinic monomer polymeric oil-soluble substance, comprise oil-soluble Diisopropyl azodicarboxylate, dibenzoyl peroxide, perhaps redox system for forming with ferrous salt, sulphite, thiosulphate respectively by dibenzoyl peroxide.

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