CN104725778B

CN104725778B - A kind of polymer matrix composite and preparation method thereof

Info

Publication number: CN104725778B
Application number: CN201510040517.8A
Authority: CN
Inventors: 周兴平; 施雪军; 解孝林; 张平
Original assignee: Huazhong University of Science and Technology
Current assignee: Huazhong University of Science and Technology
Priority date: 2015-01-27
Filing date: 2015-01-27
Publication date: 2017-03-08
Anticipated expiration: 2035-01-27
Also published as: CN104725778A

Abstract

The invention discloses a kind of composite and preparation method thereof.Described composite, including silicon dioxide hollow nanosphere and polymeric matrix material, described silicon dioxide hollow nanosphere is scattered in polymeric matrix material, and its addition is the 0.1wt.%～10wt.% of polymeric matrix material.Described composite material and preparation method thereof comprises the following steps：(1) silicon dioxide hollow nanosphere is prepared using sol-gal process；(2) the silicon dioxide hollow nanosphere preparing step (1) is scattered in polymeric matrix material, forms polymeric matrix material-hollow silica ball dispersed system；(3) firming agent is added to solidify the polymeric matrix material obtaining in step (2).Polymeric matrix material-hollow silica ball composite that the present invention provides, has excellent mechanical property and acoustics damping capacity, and preparation method is simple, and reaction condition is gentle.

Description

A kind of polymer matrix composite and preparation method thereof

Technical field

The invention belongs to field of compound material, more particularly, to a kind of polymer matrix composite and preparation method thereof.

Background technology

Many excellent properties of polymer matrix composite itself make its range of application constantly expand, but polymer The shortcoming of matrix such as heat resistance itself, anti-wear performance, the aspect such as high mechanical strength also limit its development further, special It is not intensity and the toughness representing mechanical performance index.

Generally, inorganic particles packing modification can effectively improve the intensity of polymeric matrix, but often reduces its toughness.Often Toughening methods, such as elastic body toughening, but causes the decline by a relatively large margin of polymeric material intensity.Activeness and quietness becomes simultaneously The modified difficult point of polymeric material and research emphasis.Meanwhile, increase filler, generally result in composite materials density and increase Plus.

On the other hand, the control of vibration and noise is increasingly becoming the pressing issues in producing and living.Damping vibration attenuation is control The effective means of structure vibration and structure borne noise processed, it is vibrational energy to be transformed into thermal dissipation go out, thus reaching vibration and noise reducing Purpose.The low intensity of traditional polymer as damping material, should not be used as structural damping material, therefore can only be using interlayer knot Structure, but this sandwich during long use due to the fatigue damage of structural member, and progressively lose damping.

Therefore, developing a kind of structural material of high-intensity high-tenacity high-damping just has great science and economic implications.

Content of the invention

The invention provides a kind of polymer matrix composite and preparation method thereof, its object is to by being polymerized in matrix Add the hollow silica ball shape filler of surface modification in thing, thus solve existing collective polymeric material intensity, toughness not Good, acoustic damping effect is bad, its composite density replies increased technical problem.Can reach makes this composite simultaneously The effect that is kept approximately constant of density, and the thermal stability of composite, fire resistance all increases.

For achieving the above object, according to one aspect of the present invention, there is provided a kind of polymer matrix composite, including two Silicon oxide hollow nano-sphere and polymeric matrix material, described silicon dioxide hollow nanosphere, it is scattered in polymeric matrix material In, its addition is 0.1～10wt.% of epoxy resin.

Preferably, described composite, its its external diameter of silicon dioxide hollow nanosphere between 180nm～300nm, in it Footpath is between 80nm～160nm.

Preferably, described composite, its silicon dioxide hollow nanosphere specific surface area is about 61m²/ g, preferably in 58m²/ G to 63m²Between/g..

Preferably, described composite, its silicon dioxide hollow nanosphere is surface through coupling agent modified silicon dioxide Hollow nano-sphere.

Preferably, described composite, its polymeric matrix material is epoxy resin, silicone rubber or polyurethane.

Preferably, described epoxy resin-hollow silica ball composite, its epoxy resin is bisphenol A-type or double Phenol F type epoxy resin, preferably bisphenol f type epoxy resin；Silicone rubber is double component room temperature vulcanization silicon rubber, and polyurethane is dihydroxylic alcohols Polyurethane with PPDI component.

It is another aspect of this invention to provide that providing a kind of preparation method of described composite, comprise the following steps：

(1) prepare silicon dioxide hollow nanosphere：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds emulsifier for mixing so that it is mixed Uniformly, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.06 gram～0.16 gram；Condition in no oxygen Under, described system temperature is maintained at 50 DEG C～80 DEG C, adds potassium peroxydisulfate, the quality of every gram of deionized water potassium peroxydisulfate is 0.5 milligram～2 milligrams；After reaction 8 hours to 12 hours, it is added dropwise over the methylacryoyloxyethyl three of 0.01mL～0.05mL Ammonio methacrylate, continues reaction to complete, obtains the polystyrene emulsion of functionalization；This step reaction 24 general as a child, can Reach reaction complete state.

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.01 of preparation in step (1-1) Gram～0.1 gram and 0.01mL～0.02mL ammonia, stirring makes its mix homogeneously, under the conditions of 30 DEG C～60 DEG C, is added dropwise over Ethanol solution 0.08mL～the 0.2mL of 50wt% tetraethyl orthosilicate, reaction 3 hours or longer time, solid-liquid separation simultaneously retains Solid phase, obtains the compound particle of coated with silica polystyrene after washing, add organic solvent, washing to described compound particle Removing granules of polystyrene, vacuum drying, obtain hollow silica ball；

(2) according to silicon dioxide hollow nanosphere addition in described composite, by the titanium dioxide of preparation in step (1) Silicon hollow nano-sphere is scattered in polymeric matrix material, forms matrix-hollow silica ball dispersed system；

(3) add firming agent in the matrix-hollow silica ball dispersion prepared to step (2), carry out at solidification Reason, that is, be obtained described composite.

Preferably, described preparation method, its step (1) also includes following sub-step：

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2).

Preferably, described preparation method, the concrete operations of its step (1-3) are：

In every milliliter of ethanol water, 0.01 gram of silicon dioxide hollow nanosphere prepared by dispersed step (1-2) ～0.1 gram, obtain silicon dioxide hollow nanosphere/alcohol dispersion liquid A, in described ethanol water, ethanol and the mass ratio of water are 5:1～1:5；Add coupling agent in dispersion liquid A, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；By dispersion liquid B Filter, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

Preferably employ methanol, ethanol, the silicon dioxide hollow nanosphere of the acetone and other organic solvent described surface modification of washing； Drying condition is preferably：It is dried preferably 50 DEG C to be vacuum dried 24 hours.

Preferably, described preparation method, its step (2) adopts the method for ultrasonic disperse and high-speed stirred so that described two Silicon oxide hollow nano-sphere is dispersed in polymeric matrix material.

Preferably, described preparation method, the concrete operations of its step (2) are：According to interpolation surface modification in mass ratio Silicon dioxide hollow nanosphere, using high-speed stirred after ultrasonic disperse process for dispersing so that described silicon dioxide hollow Nanosphere is dispersed in epoxy resin.Described ultrasonic disperse power is preferably：200 watts, temperature is 50 DEG C～70 DEG C, ultrasonic Dispersion 0.5～2 hour；Described high-speed stirred is：40 DEG C～70 DEG C, 600～2000 revs/min, stir 1～2 hour.

Preferably, described preparation method, its polymeric matrix material is epoxy resin, silicone rubber or polyurethane.

In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show Beneficial effect：

(1) polymer matrix composite that the present invention provides, while improving polymeric material intensity, improves it Property, balance its mechanical property, have a good application prospect；

(2) polymer matrix composite that the present invention provides, because filler is nano-hollow ball, therefore has good sound Learn performance, acoustic damping is big, has the function of sound insulation and noise reduction；

(3) polymer matrix composite that the present invention provides, heat stability is good, has good fire resistance；

(4) polymer matrix composite that the present invention provides, comprehensive improve the mechanics of materials, acoustics, thermal property same When, maintain density and maintain an equal level before filler or reduction with adding, overcome the problem that filler leads to composite density to greatly increase；

(5) preparation method of the described polymer matrix composite that the present invention provides, reaction condition is gentle, suitably on a large scale Produce.

Brief description

Fig. 1 is the silicon dioxide hollow nanosphere transmission electron microscope photo that embodiment 1 is obtained；

Fig. 2 is that the ultrathin section transmission electron microscope of epoxy resin-hollow silica ball composite that embodiment 1 is obtained shines Piece；

Fig. 3 is that the ultrathin section transmission electron microscope of epoxy resin-hollow silica ball composite that embodiment 2 is obtained shines Piece；

Fig. 4 is that the ultrathin section transmission electron microscope of epoxy resin-hollow silica ball composite that embodiment 3 is obtained shines Piece.

Specific embodiment

In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and It is not used in the restriction present invention.As long as additionally, involved technical characteristic in each embodiment of invention described below The conflict of not constituting each other just can be mutually combined.

The composite that the present invention provides, including silicon dioxide hollow nanosphere and polymeric matrix material, described dioxy SiClx hollow nano-sphere, is scattered in polymeric matrix material, its addition be polymeric matrix material 0.1wt.%～ 10wt.%, preferably 0.5wt.%～8wt.%.Described its external diameter of silicon dioxide hollow nanosphere between 180nm～300nm, , between 80nm～160nm, specific surface area is in 61m for its internal diameter²/ g about, preferably 58m²/ g to 63m²/g.Preferably, described Silicon dioxide hollow nanosphere is surface through coupling agent modified silicon dioxide hollow nanosphere.Described polymeric matrix material is Epoxy resin, silicone rubber or polyurethane.Described epoxy resin, is commonly used for bisphenol A-type or bisphenol f type epoxy resin, preferably double Phenol F type epoxy resin；Described silicone rubber is double component room temperature vulcanization silicon rubber.

The preparation method of described composite, comprises the following steps：

(1) silicon dioxide hollow nanosphere is prepared using sol-gel process：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds emulsifying agent such as polyvinyl pyrrole Alkanone, stirring makes its mix homogeneously, obtains mixed system, and in every gram of deionized water, cinnamic quality is 0.06 gram～0.16 Gram；Under conditions of no oxygen, described system temperature is maintained at 50 DEG C～80 DEG C, adds the aqueous solution of potassium peroxydisulfate, often Gram deionized water corresponds to 0.5 milligram～2 milligrams of potassium peroxydisulfate；Reaction 8 hours to 12 hours after, be added dropwise over 0.01mL～ The MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.05mL, continues reaction to complete, obtains the polystyrene emulsion of functionalization； When preferably employing Polyvinylpyrrolidone as emulsifying agent, containing Polyvinylpyrrolidone quality in every gram of deionized water is 0.03 Gram～0.06 gram.This step reaction 24 general as a child, can reach reaction complete state.

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.01 of preparation in step (1-1) Gram～0.1 gram and 0.01mL～0.02mL ammonia, stirring makes its mix homogeneously, under the conditions of 30 DEG C～60 DEG C, is added dropwise over Ethanol solution 0.08mL～the 0.2mL of 50wt% tetraethyl orthosilicate, reaction 3 hours or longer time, solid-liquid separation simultaneously retains Solid phase, obtains the compound particle of coated with silica polystyrene after washing, add organic solvent, washing to described compound particle Removing granules of polystyrene, vacuum drying, obtain hollow silica ball；Ammonia typical concentrations 25wt% about；Organic molten The preferred oxolane of agent, toluene, acetone.

Preferably, surface modification is carried out using coupling agents for silica hollow nano-sphere, comprise the following steps that：

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.01 gram～0.1 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow Nanosphere/alcohol dispersion liquid A, wherein said ethanol water, ethanol is 5 with the mass ratio of water:1～1:5；To in dispersion liquid A Add coupling agent, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Dispersion liquid B is filtered, by residue washing and vacuum It is dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) the silicon dioxide hollow nanosphere that step (1) is obtained surface modification is dispersed in polymeric matrix material In, form dispersed system.

Preferably, according to the silicon dioxide hollow nanosphere adding surface modification in mass ratio, after ultrasonic disperse The process for dispersing of high-speed stirred is so that described silicon dioxide hollow nanosphere is dispersed in epoxy resin.Described ultrasonic point Scattered power is preferably：200 watts, temperature is 50 DEG C～70 DEG C, ultrasonic disperse 0.5～2 hour；Described high-speed stirred is：40 DEG C～ 70 DEG C, 600～2000 revs/min, stir 1～2 hour.

(3) add firming agent in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, then Carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Polymeric matrix material is epoxy resin, then preferred version, and described firming agent is imidazoles and/or anhydrides；Institute State curing reaction and include low temperature precuring and hot setting two step.

It is highly preferred that described firming agent is imidazole curing agent：2- ethyl imidazol(e), 2-ethyl-4-methylimidazole and anhydride Class firming agent：Methylhexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, therein a kind of or two kinds, wherein imidazoles Class firming agent and epoxy resin add ratio for 1g/100g～6g/100g, and acid anhydride type curing agent and epoxy resin interpolation ratio are 40g/ 100g～90g/100g.

Described curing reaction：Carry out low temperature precuring, 50 DEG C～80 DEG C of low temperature precuring temperature, pre-cure time first 0.5～3 hour；Then hot setting：140 DEG C～170 DEG C of hot setting temperature, 4～7 hours hardening times.

Epoxy resin-hollow silica ball composite that the present invention provides is a kind of strong mechanical performance, acoustic impedance The nano composite material of characteristic, can be used for mechanical structure material, and builds the fields such as deadener.

It is below embodiment：

Embodiment 1

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-51 bis-phenol A type epoxy resin-base, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 2wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-550 silane coupler Heart nanosphere, its outer diameter length is about 210nm, and in it, electrical path length is about 90nm, and specific surface area is about 61m²/g.

The preparation method of described epoxy resin-hollow silica ball composite, comprises the following steps：

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds emulsifier for mixing so that it is mixed Uniformly, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.05 gram；Under conditions of no oxygen, will be described System temperature is maintained at 70 DEG C, adds potassium peroxydisulfate, and in every gram of deionized water, the quality of potassium peroxydisulfate is 1.0 milligrams；Reaction 8 Hour, to after 12 hours, is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.03mL, continues reaction to complete, obtains Polystyrene emulsion to functionalization；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.055 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 50 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.15mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.01 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, is disperseed using ultrasound wave, obtains Silicon dioxide hollow nanosphere/alcohol dispersion liquid A.In ethanol water, ethanol is 1 with the mass ratio of water:1.To every milliliter point KH-550 silane coupler 0.03mL, continuously stirred 5 hours of room temperature is added, the silicon dioxide hollow obtaining modification is received in dispersion liquid A Rice ball dispersion liquid B.Dispersion liquid B is filtered, and filtering residue is adopted ethanol to wash after 3 times with distillation water mixed liquid, in 50 DEG C of vacuum It is dried 48 hours, obtain the silicon dioxide hollow nanosphere of surface modification.

(2) 3.5 grams of the silicon dioxide hollow nanosphere of the surface modification being obtained in step (1) is dispersed in asphalt mixtures modified by epoxy resin In 100 grams of fat, form dispersed system.

Dispersion condition is 50 DEG C, 200 watts of ultrasound wave disperse 1 hour；Then 60 DEG C, with 2000 revs/min of rotating speed high-speed stirring Mix 0.5 hour.

(3) 75 grams of (first of firming agent methylhexahydrophthalic anhydride are added in the dispersed system prepared to step (2) The ratio of base hexahydrophthalic anhydride and epoxy resin is 75g/100g), uniformly mixing vacuum outgass bubble；Then at 60 DEG C Low temperature precuring 3 hours, then at 170 DEG C of hot settings 5 hours, that is, obtains described epoxy resin-hollow silica ball and is combined Material.

The silicon dioxide hollow nanosphere that step (1) is obtained disperses in ethanol, using its pattern of transmission electron microscope observing, Result is shown in Fig. 1.

After the epoxy resin obtaining-hollow silica ball composite brittle failure, using scanning electron microscopic observation to dioxy SiClx hollow nano-sphere is dispersed in epoxy resin-base, and result is shown in Fig. 2.

The epoxy resin obtaining-hollow silica ball composite is adopted GB/T 1043-2008, GB/T 9341- 2008th, GB/T 50121-2005, GB/T 1033-2008 standard test impact strength, bending moduluses, sound insulation property and sample respectively Product density, the results are shown in Table 1.

Embodiment 2

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-54 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 3wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-550 silane coupler Heart nanosphere, its outer diameter length is about 210nm, and in it, electrical path length is about 90nm, and specific surface area is about 61m²/g.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.1 gram；Under conditions of no oxygen, Described system temperature is maintained at 70 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1 milligram； After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.03mL, continue reaction extremely complete Entirely, obtain the polystyrene emulsion of functionalization；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.06 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 40 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.15mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.06 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, is disperseed using ultrasound wave, obtains Silicon dioxide hollow nanosphere/alcohol dispersion liquid A.In ethanol water, ethanol is 5 with the mass ratio of water:1.To every milliliter point KH-550 silane coupler 0.05mL, continuously stirred 5 hours of room temperature is added, the silicon dioxide hollow obtaining modification is received in dispersion liquid A Rice ball dispersion liquid B.Dispersion liquid B is filtered, and filtering residue is adopted ethanol to wash after 3 times with distillation water mixed liquid, in 50 DEG C of vacuum It is dried 48 hours, obtain the silicon dioxide hollow nanosphere of surface modification.

(2) 5.1 grams of the silicon dioxide hollow nanosphere of the surface modification being obtained in step (1) is dispersed in asphalt mixtures modified by epoxy resin In 100 grams of fat, form dispersed system.

Dispersion condition is 50 DEG C, 200 watts of ultrasound wave disperse 1 hour；Then 60 DEG C, with 1900 revs/min of rotating speed high-speed stirring Mix 0.5 hour.

(3) 70 grams of (first of firming agent methylhexahydrophthalic anhydride are added in the dispersed system prepared to step (2) The ratio of base hexahydrophthalic anhydride and epoxy resin is 70g/100g), uniformly mixing vacuum outgass bubble；Then at 80 DEG C Low temperature precuring 1 hour, then at 160 DEG C of hot settings 6 hours, that is, obtains epoxy resin-hollow silica ball composite wood Material.

The epoxy resin obtaining-hollow silica ball composite is adopted GB/T 1043-2008, GB/T9341- 2008th, GB/T 50121-2005, GB/T 1033-2008 standard test impact strength, bending moduluses, sound insulation property and sample respectively Product density, the results are shown in Table 1.

After the epoxy resin obtaining-hollow silica ball composite brittle failure, using scanning electron microscopic observation to dioxy SiClx hollow nano-sphere is dispersed in epoxy resin-base, and result is shown in Fig. 3.

Embodiment 3

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and YDF-165 Bisphenol f type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 0.1wt.%.Described silicon dioxide hollow nanosphere, is to carry out the titanium dioxide after surface modification through NDZ-401 titanate coupling agent Silicon hollow nano-sphere, its outer diameter length is about 200nm, and in it, electrical path length is about 90nm, and specific surface area is about 61m²/g.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.09 gram；Condition in no oxygen Under, described system temperature is maintained at 70 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 0.8 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.04mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add 0.1 gram of the polystyrene emulsion of preparation in step (1-1) And 0.02mL ammonia, stirring makes its mix homogeneously, under the conditions of 40 DEG C, is added dropwise over the ethanol of 50wt% tetraethyl orthosilicate Solution 0.15mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica polyphenyl after washing The compound particle of ethylene, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains Hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.1 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, is disperseed using ultrasound wave, obtains Silicon dioxide hollow nanosphere/alcohol dispersion liquid A.In ethanol water, ethanol is 5 with the mass ratio of water:1.To every milliliter point Add NDZ-401 titanate coupling agent 0.08mL, continuously stirred 5 hours of room temperature in dispersion liquid A, obtain the silicon dioxide hollow of modification Nanosphere dispersion liquid B.Dispersion liquid B is filtered, and filtering residue is adopted ethanol to wash after 3 times with distillation water mixed liquid, true in 50 DEG C Empty dry 48 hours, obtain the silicon dioxide hollow nanosphere of surface modification.

(2) 0.14 gram of the silicon dioxide hollow nanosphere of the surface modification being obtained in step (1) is dispersed in epoxy In 100 grams of resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 60 DEG C, 1300 revs/min Clock stirs 0.5 hour.

(3) 40 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 40g/100g, the interpolation of 2-ethyl-4-methylimidazole and epoxy resin is than for 3g/ for the interpolation of anhydride and epoxy resin 100g.

Carry out low temperature precuring first：70 DEG C, solidify 2 hours；Then carry out hot setting：150 DEG C, hardening time 7 is little When.

After the epoxy resin obtaining-hollow silica ball composite brittle failure, using scanning electron microscopic observation to dioxy SiClx hollow nano-sphere is dispersed in epoxy resin-base, and result is shown in Fig. 4.

Embodiment 4

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and NPEF-170 Bisphenol f type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 4wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-540 silane coupler Heart nanosphere, its outer diameter length is about 230nm, and in it, electrical path length is about 100nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.07 gram；Condition in no oxygen Under, described system temperature is maintained at 70 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1.5 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.03mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.09 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 50 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.14mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds acetone, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains two Silicon oxide hollow ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.03 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 5 with the mass ratio of water:1；KH- is added in every milliliter of dispersion liquid A 540 silane coupler 0.09mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 7.6 grams of steps (1) In epoxy resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 60 DEG C, 1800 revs/min Clock stirs 0.5 hour.

(3) 90 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methyl tetrahydrophthalic anhydride and 2- ethyl imidazol(e) firming agent, wherein methyl tetrahydrophthalic acid Than for 90g/100g, the interpolation of 2- ethyl imidazol(e) and epoxy resin is than for 3g/100g for the interpolation of acid anhydride and epoxy resin.

Carry out low temperature precuring first：70 DEG C, solidify 3 hours；Then carry out hot setting：150 DEG C, hardening time 6 is little When.

Embodiment 5

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-45 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 5wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-550 silane coupler Heart nanosphere, its outer diameter length is about 300nm, and in it, electrical path length is about 150nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.14 gram；Condition in no oxygen Under, described system temperature is maintained at 70 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 0.5 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.05mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.05 of preparation in step (1-1) Gram and 0.02mL ammonia, stirring make its mix homogeneously, under the conditions of 30 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.18mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds toluene, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains two Silicon oxide hollow ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.07 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 5 with the mass ratio of water:2；KH- is added in every milliliter of dispersion liquid A 550 silane coupler 0.08mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 7.5 grams of steps (1) In epoxy resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 60 DEG C, 1200 revs/min Clock stirs 0.5 hour.

(3) add 70 grams of methylhexahydrophthalic anhydrides in the dispersed system prepared to step (2), uniformly mix And vacuum outgass bubble, then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 70g/100g, the interpolation of 2- ethyl 4-methylimidazole and epoxy resin is than for 5g/100g for the interpolation of anhydride and epoxy resin.

Carry out low temperature precuring first：60 DEG C, solidify 1 hour；Then carry out hot setting：160 DEG C, hardening time 7 is little When.

Embodiment 6

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-42 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 0.5wt.%.Described silicon dioxide hollow nanosphere, is to carry out the silicon dioxide after surface modification through KH-560 silane coupler Hollow nano-sphere, its outer diameter length is about 230nm, and in it, electrical path length is about 100nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.08 gram；Condition in no oxygen Under, described system temperature is maintained at 50 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 0.6 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.02mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.07 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 50 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.14mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds acetone, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains two Silicon oxide hollow ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.01 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 5 with the mass ratio of water:3；KH- is added in every milliliter of dispersion liquid A 560 silane coupler 0.06mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 0.9 gram of step (1) In epoxy resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 60 DEG C, 1600 revs/min Clock stirs 0.5 hour.

(3) 80 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methyl tetrahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl tetrahydrochysene O-phthalic Than for 80g/100g, the interpolation of 2-ethyl-4-methylimidazole and epoxy resin is than for 6g/ for the interpolation of anhydride and epoxy resin 100g.

Carry out low temperature precuring first：60 DEG C, solidify 3 hours；Then carry out hot setting：170 DEG C, hardening time 5 is little When.

Embodiment 7

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-51 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 3wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-560 silane coupler Heart nanosphere, its outer diameter length is about 280nm, and in it, electrical path length is about 100nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.06 gram；Condition in no oxygen Under, described system temperature is maintained at 80 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 2 millis Gram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.02mL, continue reaction To complete, obtain the polystyrene emulsion of functionalization；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.06 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 50 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.2mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica polyphenyl after washing The compound particle of ethylene, adds toluene, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains dioxy SiClx hollow ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.1 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 5 with the mass ratio of water:4；KH- is added in every milliliter of dispersion liquid A 560 silane coupler 0.12mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 3.18 grams of steps (1) In epoxy resin, form dispersed system.

(3) 6 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, so After carry out curing reaction, that is, be obtained described epoxy resin-hollow silica ball composite.

Firming agent is 2-ethyl-4-methylimidazole, and the ratio of the interpolation with epoxy resin is for 6g/100g.

Carry out low temperature precuring first：60 DEG C, solidify 2 hours；Then carry out hot setting：150 DEG C, hardening time 7 is little When.

Embodiment 8

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and YDF-165 Bisphenol f type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 7wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-540 silane coupler Heart nanosphere, its outer diameter length is about 230nm, and in it, electrical path length is about 160nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.13 gram；Condition in no oxygen Under, described system temperature is maintained at 50 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 0.8 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.05mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.095 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 60 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.15mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.1 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 1 with the mass ratio of water:5；KH- is added in every milliliter of dispersion liquid A 540 silane coupler 0.08mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 10.5 grams of steps (1) In epoxy resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 60 DEG C, 1500 revs/min Clock stirs 0.5 hour.

(3) 50 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 50g/100g, the interpolation of 2-ethyl-4-methylimidazole and epoxy resin is than for 5g/ for the interpolation of anhydride and epoxy resin 100g.

Carry out low temperature precuring first：60 DEG C, solidify 3 hours；Then carry out hot setting：150 DEG C, hardening time 7 is little When.

Embodiment 9

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-44 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 10wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-550 silane coupler Heart nanosphere, its outer diameter length is about 180nm, and in it, electrical path length is about 80nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.06 gram；Condition in no oxygen Under, described system temperature is maintained at 80 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 2 millis Gram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.04mL, continue reaction To complete, obtain the polystyrene emulsion of functionalization；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.05 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 40 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.10mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.03 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 2 with the mass ratio of water:5；KH- is added in every milliliter of dispersion liquid A 550 silane coupler 0.04mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 17.5 grams of steps (1) In epoxy resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 50 DEG C, 1000 revs/min Clock stirs 2 hours.

(3) 75 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 75g/100g, the interpolation of 2-ethyl-4-methylimidazole and epoxy resin is than for 3g/ for the interpolation of anhydride and epoxy resin 100g.

Carry out low temperature precuring first：70 DEG C, solidify 2 hours；Then carry out hot setting：150 DEG C, hardening time 6 is little When.

Embodiment 10

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-51 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 1wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-560 silane coupler Heart nanosphere, its outer diameter length is about 180nm, and in it, electrical path length is about 100nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.06 gram；Condition in no oxygen Under, described system temperature is maintained at 50 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1.9 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.01mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.06 of preparation in step (1-1) Gram and 0.02mL ammonia, stirring make its mix homogeneously, under the conditions of 40 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.08mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.01 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 3 with the mass ratio of water:5；KH- is added in every milliliter of dispersion liquid A 560 silane coupler 0.1mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；To divide Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 1.06 grams of steps (1) In epoxy resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 70 DEG C, 800 revs/min Stirring 1 hour；

60 DEG C, solidify 2 hours；Then carry out hot setting：150 DEG C, 7 hours hardening times.

Embodiment 11

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-45 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 0.5wt.%.Described silicon dioxide hollow nanosphere, is to carry out the silicon dioxide after surface modification through KH-550 silane coupler Hollow nano-sphere, its outer diameter length is about 210nm, and in it, electrical path length is about 100nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.12 gram；Condition in no oxygen Under, described system temperature is maintained at 60 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1.0 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.03mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.10 of preparation in step (1-1) Gram and 0.01mL ammonia, stirring make its mix homogeneously, under the conditions of 60 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.12mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.09 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 4 with the mass ratio of water:5；KH- is added in every milliliter of dispersion liquid A 550 silane coupler 0.06mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 by surface-modified silicon dioxide hollow nanosphere is obtained in 0.875 gram of step (1) In gram epoxy resin, form dispersed system.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 75g/100g, the interpolation of 2- ethyl 4-methylimidazole and epoxy resin is than for 1g/100g for the interpolation of anhydride and epoxy resin.

Carry out low temperature precuring first：80 DEG C, solidify 1 hour；Then carry out hot setting：160 DEG C, hardening time 7 is little When.

Embodiment 12

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-45 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 6wt.%.Described silicon dioxide hollow nanosphere, its outer diameter length is about 230nm, and in it, electrical path length is about 160nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.11 gram；Condition in no oxygen Under, described system temperature is maintained at 70 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1.5 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.04mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.08 of preparation in step (1-1) Gram and 0.02mL ammonia, stirring make its mix homogeneously, under the conditions of 50 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.12mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(2) the silicon dioxide hollow nanosphere being obtained in 10.68 grams of steps (1) is dispersed in 100 grams of epoxy resin In, form dispersed system.

(3) 78 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 78g/100g, the interpolation of 2- ethyl 4-methylimidazole and epoxy resin is than for 2g/100g for the interpolation of anhydride and epoxy resin.

Carry out low temperature precuring first：60 DEG C, solidify 4 hours；Then carry out hot setting：150 DEG C, hardening time 5 is little When.

Embodiment 13

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-51 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 8wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-540 silane coupler Heart nanosphere, its outer diameter length is about 290nm, and in it, electrical path length is about 100nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.09 gram；Condition in no oxygen Under, described system temperature is maintained at 80 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1.5 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.04mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.65 of preparation in step (1-1) Gram and 0.02mL ammonia, stirring make its mix homogeneously, under the conditions of 30 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.14mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.1 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 1 with the mass ratio of water:1；KH- is added in every milliliter of dispersion liquid A 550 silane coupler 0.1mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；To divide Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 by surface-modified silicon dioxide hollow nanosphere is obtained in 14.08 grams of steps (1) In gram epoxy resin, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 60 DEG C, 1100 revs/min Clock stirs 0.5 hour.

(3) 76 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 76g/100g, the interpolation of 2- ethyl 4-methylimidazole and epoxy resin is than for 4g/100g for the interpolation of anhydride and epoxy resin.

Carry out low temperature precuring first：80 DEG C, solidify 1 hour；Then carry out hot setting：170 DEG C, hardening time 4 is little When.

Embodiment 14

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and E-45 bis-phenol A type epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 5wt.%.Described silicon dioxide hollow nanosphere, is to carry out the sky of the silicon dioxide after surface modification through KH-550 silane coupler Heart nanosphere, its outer diameter length is about 240nm, and in it, electrical path length is about 130nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.10 gram；Condition in no oxygen Under, described system temperature is maintained at 80 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1.0 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.01mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.085 of preparation in step (1-1) Gram and 0.02mL ammonia, stirring make its mix homogeneously, under the conditions of 60 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.13mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.07 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 5 with the mass ratio of water:1；KH- is added in every milliliter of dispersion liquid A 550 silane coupler 0.08mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in 100 grams by surface-modified silicon dioxide hollow nanosphere is obtained in 8.5 grams of steps (1) In epoxy resin, form dispersed system.

(3) 70 grams of firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, Then carry out curing reaction, that is, described epoxy resin-hollow silica ball composite is obtained.

Carry out low temperature precuring first：60 DEG C, solidify 2 hours；Then carry out hot setting：150 DEG C, hardening time 8 is little When.

Embodiment 15

A kind of epoxy resin-hollow silica ball composite, including silicon dioxide hollow nanosphere and YDF-165 Type bisphenol F epoxy resin, described silicon dioxide hollow nanosphere, it is scattered in epoxy resin, its addition is epoxy resin 7wt.%.Described silicon dioxide hollow nanosphere, its outer diameter length is about 240nm, and in it, electrical path length is about 120nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds Polyvinylpyrrolidone stirring Make its mix homogeneously, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.16 gram；Condition in no oxygen Under, described system temperature is maintained at 70 DEG C, adds potassium peroxydisulfate, in every gram of deionized water, the quality of potassium peroxydisulfate is 1.5 Milligram；After reaction 8 hours to 12 hours, it is added dropwise over the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 0.03mL, continue anti- The polystyrene emulsion of functionalization should be obtained to complete；

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.08 of preparation in step (1-1) Gram and 0.015mL ammonia, stirring make its mix homogeneously, under the conditions of 50 DEG C, be added dropwise over 50wt% tetraethyl orthosilicate Ethanol solution 0.12mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica after washing The compound particle of polystyrene, adds oxolane, washing removing granules of polystyrene to described compound particle, is vacuum dried, Obtain hollow silica ball；

(2) the silicon dioxide hollow nanosphere being obtained in 11.9 grams of steps (1) is dispersed in 100 grams of epoxy resin In, form dispersed system.

Dispersion condition is under the conditions of 50 DEG C, 200 watts of ultrasonic disperse 1 hour；Then under the conditions of 60 DEG C, 1400 revs/min Clock stirs 0.5 hour.

(3) 70 firming agent are added in the dispersed system prepared to step (2), uniformly mixing vacuum outgass bubble, so After carry out curing reaction, that is, be obtained described epoxy resin-hollow silica ball composite.

Firming agent is methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, wherein methyl hexahydro O-phthalic Than for 70g/100g, the interpolation of 2- ethyl 4-methylimidazole and epoxy resin is than for 3g/100g for the interpolation of anhydride and epoxy resin.

Carry out low temperature precuring first：60 DEG C, solidify 3 hours；Then carry out hot setting：150 DEG C, hardening time 6 is little When.

Embodiment 16

A kind of silicone rubber-hollow silica ball composite, including silicon dioxide hollow nanosphere and bi-component condensation Type room temperature vulcanized silicone rubber, described silicon dioxide hollow nanosphere, it is scattered in bicomponent condensed type room temperature sulfidization silicon rubber, its Addition is the 5wt.% of bicomponent condensed type room temperature sulfidization silicon rubber.Described silicon dioxide hollow nanosphere, is through KH-550 Silane coupler carry out surface modification after silicon dioxide hollow nanosphere, its outer diameter length is about 240nm, and in it, electrical path length is about For 130nm.

The preparation method of described silicone rubber-hollow silica ball composite, comprises the following steps：

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.05 of preparation in step (1-1) Gram and 0.02mL ammonia, stirring make its mix homogeneously, under the conditions of 30 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.18mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(2) it is dispersed in surface-modified silicon dioxide hollow nanosphere is obtained in 5.18 grams of steps (1) In 99.457 grams of bicomponent condensed type room temperature sulfidization silicon rubbers, form dispersed system.

(3) 4.093 grams of firming agent, uniformly mixing vacuum outgass are added in the dispersed system prepared to step (2) Bubble, then carries out curing reaction, that is, described silicone rubber-hollow silica ball composite is obtained.

Firming agent is tetraethyl orthosilicate, wherein the adding of tetraethyl orthosilicate and bicomponent condensed type room temperature sulfidization silicon rubber Plus ratio is 4g/100g, cure under pressure 8 hours at 50 DEG C, that is, obtain silicone rubber-hollow silica ball composite.

Embodiment 17

A kind of silicone rubber-hollow silica ball composite, including silicon dioxide hollow nanosphere and bi-component condensation Type room temperature vulcanized silicone rubber, described silicon dioxide hollow nanosphere, it is scattered in bicomponent condensed type room temperature sulfidization silicon rubber, its Addition is the 3wt.% of bicomponent condensed type room temperature sulfidization silicon rubber.Described silicon dioxide hollow nanosphere, is through KH-550 Silane coupler carry out surface modification after silicon dioxide hollow nanosphere, its outer diameter length is about 240nm, and in it, electrical path length is about For 130nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.05 of preparation in step (1-1) Gram and 0.02mL ammonia, stirring make its mix homogeneously, under the conditions of 50 DEG C, be added dropwise over the second of 50wt% tetraethyl orthosilicate Alcoholic solution 0.18mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica and gather after washing Cinnamic compound particle, adds oxolane, washing removing granules of polystyrene, vacuum drying to described compound particle, obtains To hollow silica ball；

(1-3) coupling agent is adopted to carry out surface modification to the silicon dioxide hollow nanosphere of preparation in step (1-2)：Every In milliliter ethanol water, 0.07 gram of dispersed above-mentioned silicon dioxide hollow nanosphere, obtain silicon dioxide hollow nanosphere/ Alcohol dispersion liquid A, wherein said ethanol water, ethanol is 5 with the mass ratio of water:1；KH- is added in every milliliter of dispersion liquid A 560 silane coupler 0.08mL, continuously stirred 5 hours of room temperature, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Will Dispersion liquid B filters, by residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

(2) it is dispersed in surface-modified silicon dioxide hollow nanosphere is obtained in 3.10 grams of steps (1) In 99.457 grams of bicomponent condensed type room temperature sulfidization silicon rubbers, form dispersed system.

Embodiment 18

A kind of polyurethane-silica Hollow Sphere Composites, including silicon dioxide hollow nanosphere, ethylene glycol and right Phenylene diisocyanate, described silicon dioxide hollow nanosphere, it is scattered in ethylene glycol, its addition is ethylene glycol and different to benzene two The 3wt.% of cyanate quality summation.Described silicon dioxide hollow nanosphere, is to carry out surface through KH-550 silane coupler to change Silicon dioxide hollow nanosphere after property, its outer diameter length is about 240nm, and in it, electrical path length is about 130nm.

The preparation method of described polyurethane-silica Hollow Sphere Composites, comprises the following steps：

(1) silicon dioxide hollow nanosphere modification are prepared：

(1-2) coated silica：For every gram of ethanol, add the polystyrene emulsion 0.05 of preparation in step (1-1) Gram and 0.015mL ammonia, stirring make its mix homogeneously, under the conditions of 30 DEG C, be added dropwise over 50wt% tetraethyl orthosilicate Ethanol solution 0.18mL, reaction 3 hours or longer time, solid-liquid separation simultaneously retains solid phase, obtains coated with silica after washing The compound particle of polystyrene, adds oxolane, washing removing granules of polystyrene to described compound particle, is vacuum dried, Obtain hollow silica ball；

(2) it is dispersed in 31.00 by surface-modified silicon dioxide hollow nanosphere is obtained in 3.81 grams of steps (1) In gram ethylene glycol, form dispersed system.

(3) add 96.00 grams of PPDIs in the dispersed system prepared to step (2), uniformly mix simultaneously Vacuum outgass are steeped, and then carry out curing reaction, that is, described polyurethane-silica Hollow Sphere Composites are obtained.

Firming agent is tetraethyl orthosilicate, the wherein interpolation of ethylene glycol and PPDI ratio for 32g/100g, 90 Cure under pressure 24 hours at DEG C, that is, obtain polyurethane-silica Hollow Sphere Composites.

Embodiment 19

A kind of polyurethane-silica Hollow Sphere Composites, including silicon dioxide hollow nanosphere, ethylene glycol and right Phenylene diisocyanate, described silicon dioxide hollow nanosphere, it is scattered in ethylene glycol, its addition is ethylene glycol and different to benzene two The 5wt.% of cyanate quality summation.Described silicon dioxide hollow nanosphere, is to carry out surface through KH-550 silane coupler to change Silicon dioxide hollow nanosphere after property, its outer diameter length is about 240nm, and in it, electrical path length is about 130nm.

(1) silicon dioxide hollow nanosphere modification are prepared：

(2) it is dispersed in 31.00 by surface-modified silicon dioxide hollow nanosphere is obtained in 6.35 grams of steps (1) In gram ethylene glycol, form dispersed system.

Embodiment 20

By in embodiment 1 to embodiment 19 be obtained epoxy resin-hollow silica ball composite, silicone rubber- Hollow silica ball composite, polyurethane-silica Hollow Sphere Composites, using GB/T 1043-2008 standard Test notch impact strength, result is all in 3～10kJ/m²Between；Using GB/T 9341-2008 standard testing bending moduluses, tie Fruit is all between 2.8～3.3GPa；Using GB/T 50121-2005 standard testing sound insulation property, result all 20～45dB it Between；Using GB/T 1033-2008 standardized test specimen density, result is nearly all in 1.20g/cm³Left and right.

Wherein, epoxy resin-hollow silica ball that embodiment 1, embodiment 2, embodiment 8, embodiment 11 are related to is multiple The mechanical property of condensation material and acoustics damping capacity are shown in Table 1.

The hollow ball of table 1 present invention -- epoxy resin composite material and pure epoxy resin performance comparison

As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not in order to Limit the present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should comprise Within protection scope of the present invention.

Claims

1. a kind of preparation method of polymer matrix composite is it is characterised in that comprise the following steps：

(1) prepare silicon dioxide hollow nanosphere：

(1-1) prepare polystyrene emulsion：Styrene is added in deionized water, adds emulsifier for mixing so that it is mixed all Even, obtain mixed system, in every gram of deionized water, cinnamic quality is 0.06 gram～0.16 gram；Under conditions of no oxygen, Described system temperature is maintained at 50 DEG C～80 DEG C, adds potassium peroxydisulfate, the quality of every gram of deionized water potassium peroxydisulfate is 0.5 Milligram～2 milligrams；After reaction 8 hours to 12 hours, it is added dropwise over the methylacryoyloxyethyl front three of 0.01mL～0.05mL Ammonium chloride, continues reaction to complete, obtains the polystyrene emulsion of functionalization；

(1-2) coated silica：For every gram of ethanol, add 0.01 gram of the polystyrene emulsion of preparation in step (1-1)～ 0.1 gram and 0.01mL～0.02mL ammonia, stirring makes its mix homogeneously, under the conditions of 30 DEG C～60 DEG C, is added dropwise over Ethanol solution 0.08mL～the 0.2mL of 50wt% tetraethyl orthosilicate, reaction 3 hours or longer time, solid-liquid separation simultaneously retains Solid phase, obtains the compound particle of coated with silica polystyrene after washing, add organic solvent, washing to described compound particle Removing granules of polystyrene, vacuum drying, obtain silicon dioxide hollow nanosphere；Described its external diameter of silicon dioxide hollow nanosphere Between 180nm～300nm, its internal diameter is between 80nm～160nm；

(2) according to silicon dioxide hollow nanosphere addition in described composite, the silicon dioxide of preparation in step (1) is empty Heart nanosphere is scattered in polymeric matrix material, forms matrix-hollow silica ball dispersed system；Described titanium dioxide The addition of silicon hollow nano-sphere is 0.1～10wt.% of polymeric matrix material；

(3) add firming agent in the matrix-hollow silica ball dispersion prepared to step (2), carry out cured, that is, Described composite is obtained.

2. preparation method as claimed in claim 1 is it is characterised in that described step (1) also includes following sub-step：

3. preparation method as claimed in claim 2 is it is characterised in that the concrete operations of step (1-3) are：

In every milliliter of ethanol water, silicon dioxide hollow nanosphere 0.01 gram～0.1 prepared by dispersed step (1-2) Gram, obtain silicon dioxide hollow nanosphere/alcohol dispersion liquid A, in described ethanol water, ethanol and the mass ratio of water are 5:1～ 1:5；Add coupling agent in dispersion liquid A, obtain the silicon dioxide hollow nanosphere dispersion liquid B of modification；Dispersion liquid B is filtered, By residue washing and be vacuum dried, the silicon dioxide hollow nanosphere of prepared surface modification.

4. preparation method as claimed in claim 1 is it is characterised in that described step (2) adopts ultrasonic disperse and high-speed stirred Method so that described silicon dioxide hollow nanosphere is dispersed in polymeric matrix material.

5. preparation method as claimed in claim 1 is it is characterised in that described polymeric matrix material is epoxy resin, silicon rubber Glue or polyurethane.