CN109929136A - Modified hollow microsphere and its preparation method and application - Google Patents
Modified hollow microsphere and its preparation method and application Download PDFInfo
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- CN109929136A CN109929136A CN201711374782.5A CN201711374782A CN109929136A CN 109929136 A CN109929136 A CN 109929136A CN 201711374782 A CN201711374782 A CN 201711374782A CN 109929136 A CN109929136 A CN 109929136A
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Abstract
The invention discloses a kind of modified hollow microspheres and its preparation method and application.The present invention is modified the organic compound that hollow microsphere includes hollow microsphere matrix and is incorporated on the hollow microsphere matrix, the organic compound molecule general structure is A1-D-A2, wherein, the A1 and A2 is respectively hydrophilic radical, and the D is the symmetrical organic group of molecular structure.The application of the modified hollow microsphere includes the application in packaging plastic and encapsulating structure.The modified hollow microsphere of the present invention absorbs hydrone ability and nanoparticle adsorption capacity is strong, the thermal conductivity of the packaging plastic containing the modified hollow microsphere of the present invention and the ability of capture hydrone can be effectively improved, so as to significantly improve the operation is stable and the service life of encapsulating structure.
Description
Technical field
The invention belongs to technical field of electronic encapsulation, and in particular to a kind of modified hollow microsphere and preparation method thereof and answer
With.
Background technique
The service life of electronic component is very important a parameter.In the service life for improving electronic component, reach commercial water
Flat, encapsulation is a vital link.For electronic component, encapsulation is not only to prevent the physical protections such as scuffing,
More importantly prevent steam in external environment, the infiltration of oxygen.Steam in these environment penetrates into device inside, can add
The aging of fast device.Therefore the encapsulating structure of electronic component must have the function of good permeation barrier.
Currently, in the encapsulation process of commercial electronic component, packaging plastic is generally used.Common ultraviolet cured adhesive at present
It is packaged, to completely cut off damage of the water oxygen to device.But for electronic component, the stability of electronic component is influenced
There are several factors, such as other than water oxygen factor, further includes the factors such as dust, pressure, temperature.Wherein, temperature is always shadow
An important factor for ringing electronic component stability and service life can destroy electronic component knot as temperature device internal temperature increases
Structure.Therefore, temperature is an important factor for causing electronic component to fail, if can cause electronic component without reasonable heat dissipation design
Thermal failure, seriously limit the application and development of electronic component.
However, although existing packaging plastic such as ultraviolet cured adhesive, which is packaged, has good insulating effect to water oxygen,
It is presence of the packaging plastic due to ester group inside macromolecular chain of such as ultraviolet cured adhesive, meets acid, alkali facile hydrolysis, thus resistance to Jie
Matter and water resistance are poor, easily-deformable in the environment of high temperature and humidity, and its heating conduction and heat dissipation performance are undesirable, do not have
Method meets the needs of device.
Summary of the invention
It is an object of the invention to overcome the deficiency of the prior art, a kind of modified hollow microsphere and its preparation are provided
Method, to solve the technical problem of existing hollow microsphere absorption and capture ability deficiency.
Another object of the present invention is to overcome the deficiency of the prior art, a kind of packaging plastic is provided, it is existing to solve
Packaging plastic heating conduction and the undesirable technical problem of heat dissipation performance.
Another object of the present invention is to overcome the deficiency of the prior art, a kind of encapsulating structure is provided, it is existing to solve
There is encapsulating structure to lead to electronic component performance stability and service life undesirable technology since thermally conductive and heat dissipation performance is undesirable
Problem.
In order to realize that the goal of the invention, one aspect of the present invention provide a kind of modified hollow microsphere.In the modification
Empty microballoon includes hollow microsphere matrix and the organic compound that is incorporated on the hollow microsphere matrix, the organic compound
General formula of molecular structure is A1-D-A2, wherein the A1 and A2 is respectively electron-withdrawing group, and the D is that molecular structure is symmetrical
Organic group.
Another aspect of the present invention provides a kind of preparation method of modified hollow microsphere.The preparation method includes as follows
Step:
Surface grafting processing is carried out to hollow microsphere matrix, organic compound is made to be grafted to hollow microsphere surface, forms table
Face is combined with the hollow microsphere of organic compound, and the general structure of the organic compound is A1-D-A2, the A1 and A2 points
Not Wei electron-withdrawing group, the D be the symmetrical organic group of molecular structure.
Further aspect of the present invention provides a kind of packaging plastic.The packaging plastic includes adhesive components, further includes heat dissipation
Nanoparticle and hollow microsphere, the radiation nano particle and hollow microsphere are dispersed in the adhesive components；Wherein,
The hollow microsphere is the modified hollow microsphere of the present invention.
Another aspect of the invention provides a kind of encapsulating structure.The encapsulating structure includes electronic component and for encapsulating
The encapsulated layer of the electronic component, the encapsulated layer include the packaging plastic of the present invention after solidifying.
Compared with prior art, the modified hollow microsphere of the present invention is modified hollow microsphere matrix using A1-D-A2,
On the one hand the dipole polarization degree of hollow microsphere matrix is increased, modified microballoon shows strong absorption hydrone ability；Another party
Face increases the adsorption capacity of hollow microsphere matrix；In another aspect, being capable of providing group since A1-D-A2 has symmetrical structure
Or a greater degree of vibration of link.Improve the thermal conductivity of modified hollow microsphere.
A1-D-A2 compound is directly grafted on hollow microsphere matrix by the modified hollow microsphere preparation method of the present invention, energy
Enough dipole polarization degree for effectively increasing hollow microsphere matrix and adsorption capacity and thermal conductivity.In addition, present invention modification is hollow micro-
Ball preparation method condition is easily-controllable, and the modification hollow microsphere performance of preparation is stablized, and reduces production cost.
Radiation nano particle and the modified hollow microsphere of the present invention are dispersed in the adhesive components by packaging plastic of the present invention
It is interior, the high heat-transfer performance of the radiation nano particle is carried using the modified hollow microsphere of the present invention, and it is whole to improve packaging plastic of the present invention
The lasting heat-sinking capability of body is stablized so as to which the operating temperature of packed electronic component is effectively ensured.Simultaneously as this hair
Bright modified hollow microsphere, which has, shows strong water molecules ability, can effectively absorb the packed electronic component course of work
The hydrone of middle generation guarantees the stability of the work of electronic component, extends the service life of packed electronic component.
Encapsulating structure of the present invention due to being packaged to electronic component using packaging plastic of the present invention, formed and encapsulated
Glue-line can effectively export the heat that the work of packed electronic component generates in time, keep the electronic component operating temperature
It is constant；Meanwhile the hydrone generated in the electronic component course of work can effectively be packaged glue and absorb, described in guarantee
The stability of the work of electronic component extends the service life of electronic component.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of encapsulating structure of the embodiment of the present invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to solve
The present invention is released, is not intended to limit the present invention.
On the one hand, packaging plastic of the embodiment of the present invention.The packaging plastic include adhesive components and radiation nano particle and
Hollow microsphere, the radiation nano particle and hollow microsphere are dispersed in the adhesive components.
Wherein, matrix component of the adhesive components as packaging plastic contained by the packaging plastic, since adhesive components are
Insulator does not have the free electron that can largely move, and the phonon free path in its structure is also comparable small.When described
After adhesive components are cured reaction, adhesive strand is cross-linked into reticular structure, and the space structure between macromolecular chain is
One of the main reason for its heat conductivity is poor, therefore adhesive is usually the extremely low material of thermal conductivity.And to the adhesive group
After dividing the mixing radiation nano particle and hollow microsphere, for the hollow microsphere as carrier, being on the one hand will at least partly
The radiation nano particle is fixed on the hollow microsphere, prevents the reunion of the radiation nano particle, improves described dissipate
The dispersion degree of hot nanoparticle；On the other hand the compound that the radiation nano particle and hollow microsphere are formed can regulate and control envelope
Package material hankers duty factor, reduces packed electronic component and encapsulates the thermal resistance between bed boundary, so as to improve encapsulation
The heat-sinking capability of layer；In another aspect, can effectively absorb packed electronic component work due to the presence of the hollow microsphere
The moisture of middle generation, therefore, synergistic effect of the packaging plastic by the radiation nano particle and hollow microsphere, Neng Gouyou
Effect guarantees the stability and service life of packed electronic component work.
The adhesive components can be common adhesive in encapsulation field, such as in a particular embodiment, the gluing
Agent component can be with but not just at least one of UV optic-solidified adhesive, epoxies packaging plastic, organic silicon packaging plastic.
Radiation nano particle and hollow microsphere contained by the packaging plastic constitute thermally conductive dopant material, assign the envelope
Fill the excellent thermally conductive and heat dissipation performance of glue.Wherein, the hollow microsphere has porous structure and hot hollow nature, therefore, described
Hollow microsphere has good adsorption capacity, can by the radiation nano particle at least partly it is even all of be adsorbed on it is described
On hollow microsphere, in this way, on the one hand can reduce or even prevent the reunion of the radiation nano particle, it is allowed to be dispersed in institute
It states in adhesive components.On the other hand since the hollow microsphere has a good hollow performance, the institute of its absorption when heated hollow
It states radiation nano particle to be further filled into encapsulated layer, and forms thermally conductive grid, improve the heat-sinking capability of encapsulated layer.
Inventor has found under study for action, adjusts the ratio and the heat dissipation of the radiation nano particle and hollow microsphere
When content in the packaging plastic of nanoparticle and hollow microsphere, influences whether the heating conduction of the packaging plastic, such as work as
It controls the radiation nano particle and accounts for the radiation nano particle and when 10% or more hollow microsphere total weight, the packaging plastic
Thermal conductivity significantly increase.In addition, since the hollow microsphere also has water imbibition, the hollow microsphere is to hydrone
There are certain competitive relations with nanoparticle, in order to balance the water generated when the hollow microsphere capture electronic component work
Molecule, therefore, in an embodiment, the radiation nano particle and hollow microsphere total weight are in the content of the packaging plastic
10%~30%, the radiation nano particle accounts for the 10%~40% of the radiation nano particle and hollow microsphere total weight.
Wherein, the radiation nano particle is attracted in the surface or its porous structure of the hollow microsphere, because
This controls 20~30nm of the radiation nano particle diameter in one embodiment.It on the one hand can effectively be attracted in this way
On the hollow microsphere, in surface or porous structure including the hollow microsphere；On the other hand, it is capable of increasing the heat dissipation
The amount of being adsorbed of nanoparticle, while can effectively make the radiation nano particle-filled to after adhesive solidification
In macromolecular chain network, to significantly improve the dispersion degree of the radiation nano particle and improve leading for the packaging plastic
Heat and thermal diffusivity.In another embodiment, the radiation nano is in metal nanoparticle and metal oxide nanoparticles
It is at least one.In a particular embodiment, the metal nanoparticle can be with but not just at least one of silver, aluminium, copper, nickel
Metal nanoparticle；The metal oxide nanoparticles can be with but not just at least one of silver, aluminium, copper, nickel metal oxygen
Compound nanoparticle.This nanoparticle all has excellent heat dissipation performance and is easily adsorbed by the hollow microsphere.
The hollow microsphere, which can be, directly selects conventional hollow microsphere, and therefore, the material of the hollow microsphere can be with
It is high molecular polymer.As in an embodiment, the material of the hollow microsphere is specifically that the material of high molecular polymer can be
Aqueous polyurethane, polystyrene, polypyrrole-chitosan, chitosan, PET, polyvinyl alcohol and polyacrylate etc..In order to make
The hollow microsphere can effectively adsorb the radiation nano particle and can be uniform and stable be dispersed in the adhesive base
In body component, in one embodiment, the partial size for controlling the hollow microsphere is 300~600nm.
Since the hollow microsphere is to the absorption of the radiation nano particle, dispersion and to encapsulation electronic component work
The capture of the hydrone of middle generation all has an impact.In order to improve the hollow microsphere to the absorption of the radiation nano particle, point
It dissipates, and improves capture ability of the hollow microsphere to the hydrone generated in encapsulation electronic component work.The present invention is implemented
Example additionally provides a kind of modified hollow microsphere.It that is to say using the modified hollow microsphere and substitute in packaging plastic described above
The hollow microsphere.
In one embodiment, the modified hollow microsphere includes hollow microsphere matrix and is incorporated in the hollow microsphere matrix
On organic compound, the organic compound molecule general structure be A1-D-A2.
Wherein, the hollow microsphere matrix can be the hollow microsphere matrix as described above.It can directly be selected
With conventional hollow microsphere, therefore, the material of the hollow microsphere matrix can be high molecular polymer.In a such as embodiment, institute
It can be aqueous polyurethane, polystyrene, poly- pyrrole that the material for stating hollow microsphere matrix, which is specifically the material of high molecular polymer,
Cough up-chitosan, chitosan, PET, polyvinyl alcohol and polyacrylate etc..In order to enable the hollow microsphere matrix can have
Effect adsorb the radiation nano particle and can be uniform and stable be dispersed in the adhesive matrix component, in an embodiment
In, the partial size for controlling the hollow microsphere matrix is 300~600nm.
It is incorporated in organic compound molecule knot modified to the hollow microsphere matrix surface on the hollow microsphere matrix
In structure general formula A1-D-A2, as electron-withdrawing group (acceptor), such as respectively hydrophilic radical is implemented one by the A1 and A2
In example, the electron-withdrawing group is any one of carboxyl, aldehyde radical, ester group, sulfydryl, nitro, sulfonic group, hydroxyl.In addition, institute
It states A1 and A2 can be the same or different.The hydrophilic radical A1 and A2 is in addition to effectively increasing the hollow microsphere matrix point
The dipole polarization degree of son so that the hollow microsphere matrix shows strong water molecules ability, thus improve its absorb (or
Capture) by the hydrone that is generated in the work of envelope electronic component, to avoid hydrone to electronic component job stability and service life
It adversely affects.The D is implemented as electron-donating group (donor), for example symmetrical organic group of molecular structure one
In example, the symmetrical organic group of molecular structure is any one of substitution or unsubstituted carbazole, triphenylamine.One
In specific embodiment, A1, A2 and D group are connected by conjugated structure (such as pi bond), and such as general formula A1-D-A2 is general formula
A1-π-D-π-A2。
Therefore, in one embodiment, the A1-D-A2 compound be shown in following L1-L6 in molecular structural formula at least
It is a kind of:
In addition, the A1-D-A2 compound can will be powered according to using wittig reaction preparation by aldol condensation
Subbase group D such as carbazole and trianilino group are connect with hydrophilic radicals such as electron-withdrawing group A such as hydroxyl, amino, carboxyl.Specific
In embodiment, such as L6 molecule is prepared according to the synthetic route of following reaction formula:
In one embodiment, the hollow microsphere matrix is by described hollow micro- in conjunction with the A1-D-A2 compound
The grafted moiety of ball matrix surface and A1 the or A2 group copolymerization of the A1-D-A2 are attached.By chemical bond by A1-D-
A2 compound is attached with the hollow microsphere matrix, to effectively improve the A1-D-A2 compound described hollow micro-
Bond strength on ball matrix.
In this way, the organic compound that the symmetrical structure general formula is A1-D-A2 is incorporated in the hollow microsphere matrix table
Face is modified the hollow microsphere matrix, on the one hand increases effectively capture of the modified hollow microsphere to hydrone
Ability；On the other hand effectively enhance the adsorption strength to the radiation nano particle, such as contained carboxylic group, sulfydryl base
Group hydrophilic radical and the radiation nano particle between weak force, thus enhance the radiation nano particle and it is described in
Adsorption strength between empty microballoon matrix.When heated, the radiation nano particle can partially dissociate, using between component
Interaction can cooperate with heat dissipation.The compound of third, the A1-D-A2 structure has big dipole polarization degree, is formed micro-
After ball, symmetrical structure is capable of providing group or links the vibration of bigger degree, obtains better thermal conductivity；4th, enhancing
The stability of dispersibility and dispersion of the modified hollow microsphere in the adhesive, while being effectively improved the packaging plastic
Duty factor of hankering be allowed to match with the duty factor of hankering of packed electronic component, reduce packed electronic component and encapsulated layer
Thermal resistance between interface, to improve encapsulated layer integral heat sink ability.
Based on modified hollow microsphere described in the embodiment of the present invention above, of the present invention to additionally provide the modification hollow
The preparation method of microballoon.The modified hollow microsphere preparation method includes the following steps:
Surface grafting processing is carried out to hollow microsphere matrix, organic compound is made to be grafted to hollow microsphere surface, forms table
Face is combined with the hollow microsphere of organic compound, and the general structure of the organic compound is A1-D-A2, the A1 and A2 points
Not Wei electron-withdrawing group, the D be the symmetrical organic group of molecular structure.
In one embodiment, surface grafting processing is carried out to the hollow microsphere matrix, makes organic compound and is grafted to
The step of hollow microsphere surface includes:
Prepare the organic solution containing isocyanate group；
Hollow microsphere and catalyst are added into the organic solution containing isocyanate group, makes hollow microsphere and isocyanic acid
The organic matter of base reacts, and obtains the hollow microsphere of isocyanate group activation；
The hollow microsphere that the isocyanate group activates is reacted with the organic compound.
Wherein, in one embodiment, the organic matter of the isocyanate group can be with but not just for 4,4 '-diphenyl
Methane diisocyanate, phenylisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, Toluene-2,4-diisocyanate, 6- diisocyanate, 3,3 '-diformazans
At least one of base diphenyl-methane, 4,4 '-diisocyanate.In another embodiment, the catalyst is dibutyl
Dilaurate tin, triethylenediamine, N-ethylmorpholine, N, N'- diethyl piperazine, N, N '-diethyl -2- methyl piperazine, N,
At least one of N'- is bis--(α-hydroxypropyl) -2- methyl piperazine.
In another embodiment, surface grafting processing is carried out to the hollow microsphere matrix, makes organic compound and grafting
Include: to the step of hollow microsphere surface
It prepares and contains hollow microsphere solution；
Graft initiator is added into hollow microsphere solution, carries out constant temperature isothermal holding, adds the organic compound
Carry out copolyreaction.
Wherein, in one embodiment, the graft initiator is ammonium ceric nitrate, potassium peroxydisulfate, ammonium persulfate-Asia
At least one of sodium bisulfate, N- diethylaniline.
Above-mentioned chemical graft process to be grafted the isocyanate functional base being activated in the hollow microsphere matrix surface
Group.Or make to generate free radical in the hollow microsphere matrix surface using graft initiator.In addition, to described hollow micro-
The grafting that ball matrix carries out is handled other than above-mentioned chemical graft process, can also be connect using radiation graft process, plasma
Branch method, ultraviolet radiation graft method carry out grafting processing to the hollow microsphere matrix.
Wherein, the radiation graft process can be such that
First polymer (hollow microsphere) is radiated under vacuum conditions, makes to generate free radical on polymer；So
It is immersed in the monomer (being the organic compound) or its solution for having removed air afterwards, monomer is under radiation condition
Also it can generate free radicals, radiate the free radical and monomer reaction of generation in post-consumer polymer through placing, generate graft copolymer.
The plasma grafting method can be such that
Corona treatment first is carried out to polymer (hollow microsphere), is drawn using the living radical that surface generates
Bill body (being the organic compound) carries out graft copolymerization on the surface of the material.
The ultraviolet radiation graft method is that can be such that
With the mechanism of the radiation graft process and plasma grafting method, be make under the action of uv light it is described hollow
Microballoon molecular chain rupture, generates free radicals, and then with the organic compound monomer reaction, generates graft copolymer.
By being grafted processing surface to the hollow microsphere matrix, so that being grafted pole in the hollow microsphere matrix surface
Property group, specifically can be with the polar group that A1 or A2 group is copolymerized in the A1-D-A2 compound, such as
It can be free radical or ion etc..
Copolyreaction through surface grafting treated the hollow microsphere matrix and the A1-D-A2 compound can be with
Depending on the condition types of radicals of copolyreaction.After copolyreaction, the A1-D-A2 compound is incorporated in described
Empty microballoon matrix surface realizes the modification to the hollow microsphere matrix.
Such as in one embodiment, when the hollow microsphere matrix is polyurethane hollow microsphere, in above-described embodiment
Described, the polyurethane hollow microsphere and the A1-D-A2 compound are subjected to copolyreaction in the presence of a catalyst；
In another embodiment, when the hollow microsphere matrix is chitosan hollow microballoon, in above-described embodiment
Described, the chitosan hollow microballoon is subjected to copolyreaction in the effect of initiator and the A1-D-A2 compound.
Based on packaging plastic described above, the packaging plastic can be prepared by the following method:
By radiation nano particle contained by the packaging plastic and the hollow microsphere or the modified hollow microsphere
Mixed processing is carried out with the adhesive.
Preferably, first the radiation nano particle and the hollow microsphere or the modified hollow microsphere are mixed
Then conjunction processing is added adhesive and carries out mixed processing.
Wherein, first the radiation nano particle is mixed with the hollow microsphere or the modified hollow microsphere
Processing can carry out as follows:
The hollow microsphere or the modified hollow microsphere are configured to solution, the radiation nano grain is then added
Son, which be sufficiently mixed processing or the radiation nano particle source is added, to be reacted, after carry out being filtered, washed and dried place
Reason.In this way, the radiation nano particle and the hollow microsphere or the modified hollow microsphere are first subjected to mixed processing,
So that the radiation nano particle, which first carries out assembling with the hollow microsphere or the modified hollow microsphere, forms compound,
It that is to say so that the radiation nano particle is first adsorbed and the hollow microsphere or the modified hollow microsphere as far as possible
Surface or porous structure in, to effectively reduce or even avoid the agglomeration of the radiation nano particle, thus
Significantly improve the dispersibility of the radiation nano particle.When by the radiation nano particle and the hollow microsphere or described
Modified hollow microsphere carries out assembling and is formed after compound mixes with adhesive, enables to the radiation nano particle and described
Hollow microsphere or the modified hollow microsphere are evenly dispersed and form stable dispersion, not only make the packaging plastic
Stability is good, and thermal conductivity is high, and the ability of the encapsulated layer thermal conductivity and capture hydrone formed is stablized.
On the other hand, the embodiment of the invention also provides a kind of encapsulating structures.The encapsulating structure includes electronic component 1
With the encapsulation glue-line 2 for encapsulating the electronic component, as shown in Figure 1.Wherein, after encapsulation glue-line 2 includes cover board 21 and solidifies
Encapsulation glue-line 22.The encapsulation glue-line 22 is arranged in electronic component 1 and needs packed position and the cover board 21, realizes
Bonding to encapsulating and realizing the cover board 21 position packed with the needs of electronic component 1 described in the electronic component 1.Shape
Packaging plastic at the encapsulation glue-line 22 is packaging plastic described above.Specifically as described above includes the gluing
Agent component and the radiation nano particle being dispersed in the adhesive components and the hollow microsphere or the modification
Hollow microsphere.In order to save length, no longer packaging plastic and its each component described above are repeated herein.Therefore, described
Encapsulating structure due to being packaged to electronic component 1 using packaging plastic described above, be packaged in the work of electronic component 1
The heat of generation passes through the encapsulation glue-line 22 after solidifying in time and exports outward, to ensure that packed electronic component 1 works temperature
That spends is constant.Simultaneously as being dispersed with the hollow microsphere or the modified hollow microsphere, therefore, energy in encapsulation glue-line 22
It is enough in time to capture the hydrone generated in packed electronic component 1, it that is to say and absorbed by the encapsulation glue-line 22, guarantee electricity
The job stability of subcomponent 1 extends the service life of packed electronic component 1.In a particular embodiment, the electronics member
Part 1 can be using but not as good as you as light emitting diode, such as QLED, OLED.
Now in conjunction with specific example, the present invention will be described in further detail.
1. modified hollow microsphere embodiment
Embodiment 11
The present embodiment provides a kind of modified hollow microspheres and preparation method thereof.The modified hollow microsphere includes polyurethane
Hollow microsphere matrix and the L1 compound described above being incorporated on the polyurethane hollow microsphere matrix.
Modification hollow microsphere described in the present embodiment 11 is prepared as follows acquisition:
(1) preparation of polyurethane hollow microsphere matrix: hot hollow microsphere is prepared using Pickering suspension polymerization, is claimed
Take 0.5g nanometers of Mg (OH)2、0.25g NaCl、0.01g NaNO2It is dissolved in 50mL deionized water, stirs 15 minutes and be uniformly mixed
Water phase as suspension polymerisation；Weigh 14g acrylonitrile, 4g methyl methacrylate, 2g butyl acrylate, 0.08g trihydroxy methyl
It stirs 30 minutes and is uniformly mixed as oil under propane trimethyl acrylic ester, 0.4g azodiisobutyronitrile, 7g isooctane room temperature
Phase；Use high-shear emulsion machine with 10000rpm emulsifying 5 minutes under ice-water bath after water phase and oil are mixed；It will be equal
Suspension emulsion after matter pours into autoclave, nitrogen is led to after sealing rapidly to exclude air in kettle, controls and initially press in kettle
Power is between 0.3MPa, and starting heats and sets reaction temperature at 62 DEG C or so, and revolving speed control is in 150~350rpm, reaction 12
Pressure release discharges after~16 hours, is dehydrated to obtain hot hollow microsphere, then it is washed, be dehydrated and be dried to obtain in powdered polyurethane
Empty microballoon；
(2) modification to polyurethane hollow microsphere matrix: the polyurethane hollow microsphere matrix 1g for taking step (1) to prepare is used
Toluene washing ultrasound, removes the impurity of microsphere surface；The toluene solution for measuring 20mL is added in flask, according to 7.5%
The toluene solution of the triethylamine of MDI (4,4`- methyl diphenylene diisocyanate) and 2.5% is matched to be added to the toluene of 20mL
MDI and triethylamine and polyurethane hollow microsphere matrix, lead to nitrogen remove oxygen, 50 DEG C isothermal reaction 24 hours, washed with toluene
Surface grafting, which can be obtained, the polyurethane hollow microsphere matrix of isocyanate functional groups of activation；Then by the poly- ammonia after grafting
Ester hollow microsphere matrix is added in 20mL toluene solution, and 1 drop DBDTL (acid dibutyl tin) is added dropwise as catalysis
Agent, and the L1 compound of 0.3g is added, after 50 DEG C are sufficiently reacted for constant temperature copolyreaction 6 hours therewith, three are washed with toluene
It is secondary, unreacted small molecule is removed, L1 modified polyurethane hollow microsphere can be obtained.
Embodiment 12
The present embodiment provides a kind of modified hollow microspheres and preparation method thereof.The modified hollow microsphere includes polyurethane
Hollow microsphere matrix and the L3 compound described above being incorporated on the polyurethane hollow microsphere matrix.
Modification hollow microsphere described in the present embodiment 12 is prepared as follows acquisition:
(1) preparation of polyurethane hollow microsphere matrix: referring to the step of embodiment 11 prepared by (1)；
(2) modification to polyurethane hollow microsphere matrix: referring to the step of embodiment 11 prepared by (2), and difference is to use
L3 is modified the polyurethane hollow microsphere matrix；Wherein, modification side of the L3 compound to polyurethane hollow microsphere matrix
Method is as described in Example 11.
Embodiment 13
The present embodiment provides a kind of modified hollow microspheres and preparation method thereof.The modified hollow microsphere includes chitosan
Hollow microsphere matrix and the L5 compound described above being incorporated on the chitosan hollow microballoon matrix.
Modification hollow microsphere described in the present embodiment 13 is prepared as follows acquisition:
(1) chitosan hollow microsphere is obtained；
(2) modification to the poly- hollow microsphere of poly- shell:
In deionized water by the dispersion of 1g chitosan, 60 DEG C of heated at constant temperature stir one hour, are warming up to 70 DEG C of addition nitric acid
Cerium ammonium constant temperature one hour, makes on chitosan in Portugal's amine saccharide ring on 2,3 positions one of two carbon atoms to be oxidized, the fracture of carbon key,
It is generated free radicals on not oxidized hydroxyl carbon atom；Then 0.3g L5 is being added dropwise into deionized water into solution, instead
It answers 24 hours, unsaturated carbon-carbon double bond naturally cools in chitosan free radical attack L5 small molecule to be copolymerized
Room temperature, carrying out washing treatment remove unreacted small molecule, and L5 modification of chitosan hollow microsphere can be obtained.
2. packaging plastic embodiment
Embodiment 21
The present embodiment provides a kind of packaging plastic and its preparation methods.The packaging plastic includes UV solidification glue and is dispersed in institute
State the modified polyurethane hollow microsphere that silver nanoparticle and embodiment 11 in UV solidification glue provide；Wherein, the silver nanoparticle and modification
The weight ratio of polyurethane hollow microsphere is 0.1:1, and the silver nanoparticle and modified polyurethane hollow microsphere total amount are in the packaging plastic
In the amount of mixing be 15%.
The packaging plastic is prepared as follows:
(1) Nano silver grain/modified polyurethane hollow microsphere structural composites: nanoparticle selects silver nanoparticle, selects second
Glycol is as solvent, while ethylene glycol can also act as the effect of reducing agent.Wherein modified polyurethane hollow microsphere can be used as
Protective agent prevents Nano silver grain from reuniting.Specifically take AgNO30.1g is added in ethylene glycol (2mL), is heated to 120 DEG C of perseverances
The modified polyurethane hollow microsphere 1g (ethylene glycol solution) dissolved in advance is added drop-wise to AgNO by warm 10min3In, 50 μ are added
LNaCL (8×10-2Mol/L) solution, 100 DEG C of reaction 30min.It is washed 3 times, is dried in vacuo with ethyl alcohol and acetone alternating centrifugal
Nano silver grain/modified polyurethane hollow microsphere structural composites can be obtained.
(2) Nano silver grain/modified polyurethane hollow microsphere structural composites prepared by step (1) are proportionally filled
It is dispersed in UV solidification glue.
Embodiment 22
The present embodiment provides a kind of packaging plastic and its preparation methods.The packaging plastic includes UV solidification glue and is dispersed in institute
State the modified polyurethane hollow microsphere that silver nanoparticle and embodiment 12 in UV solidification glue provide；Wherein, the silver nanoparticle and modification
The weight ratio of polyurethane hollow microsphere is 0.1:1, and the silver nanoparticle and modified polyurethane hollow microsphere total amount are in the packaging plastic
In the amount of mixing be 15%.
The preparation method that the present embodiment packaging plastic is referred to the packaging plastic in embodiment 21 is prepared.
Embodiment 23
The present embodiment provides a kind of packaging plastic and its preparation methods.The packaging plastic includes UV solidification glue and is dispersed in institute
State the polyurethane hollow microsphere not being modified that the silver nanoparticle and embodiment 11 in UV solidification glue provides；Wherein, the silver nanoparticle
Weight ratio with the polyurethane hollow microsphere not being modified is 0.1:1, and the silver nanoparticle is hollow micro- with the polyurethane not being modified
Mix amount of the ball total amount in the packaging plastic is 15%.
The preparation method that the present embodiment packaging plastic is referred to the packaging plastic in embodiment 21 is prepared.
Embodiment 24
The present embodiment provides a kind of packaging plastic and its preparation methods.The packaging plastic includes UV solidification glue and is dispersed in institute
State the modification of chitosan hollow microsphere that silver nanoparticle and embodiment 13 in UV solidification glue provide；Wherein, the silver nanoparticle and modification
The weight ratio of chitosan hollow microballoon is 0.1:1, and the silver nanoparticle and modification of chitosan hollow microsphere total amount are in the packaging plastic
In the amount of mixing be 15%.
The preparation method that the present embodiment packaging plastic is referred to the packaging plastic in embodiment 21 is prepared.
Embodiment 25
The present embodiment provides a kind of packaging plastic and its preparation methods.The packaging plastic includes UV solidification glue and is dispersed in institute
State the chitosan hollow microballoon not being modified obtained in the silver nanoparticle and embodiment 13 in UV solidification glue；Wherein, the silver is received
The weight ratio for the chitosan hollow microballoon that meter Yu Wei is modified is 0.1:1, the silver nanoparticle and the chitosan hollow not being modified
Mix amount of the microballoon total amount in the packaging plastic is 15%.
Embodiment 26
The present embodiment provides a kind of packaging plastic and its preparation methods.The packaging plastic includes UV solidification glue and is dispersed in institute
State the chitosan hollow microballoon not being modified obtained in the silver nanoparticle and embodiment 13 in UV solidification glue；Wherein, the silver is received
The weight ratio for the chitosan hollow microballoon that meter Yu Wei is modified is 0.3:1, and the silver nanoparticle and modification of chitosan hollow microsphere are total
Measuring the amount of mixing in the packaging plastic is 30%.
The preparation method that the present embodiment packaging plastic is referred to the packaging plastic in embodiment 21 is prepared.
The packaging plastic provided the embodiment 21 to 26 is packaged electronic device, and the thickness for encapsulating glue-line is identical,
And correlated performance test is carried out to test packaging part respectively at identical conditions, test is learnt, the packaging part heat dissipation effect
Good, packed electronic device temperature is stablized.Wherein, it is dissipated using the packaging part that embodiment 21,22,24 and 26 packaging plastics encapsulate
Thermal effect is better than the packaging part heat dissipation effect of embodiment 23 and 25, and the packaging part of embodiment 21,22,24 and 26 packaging plastics
Stability and service life to be more than embodiment 23 and 25, this is because the also tool of embodiment 21,22,24 and 26 packaging plastics
There are good water absorbing properties, further completely cuts off steam effect, improve packaging part stability and service life.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (16)
1. a kind of modified hollow microsphere, it is characterised in that: including hollow microsphere matrix and be incorporated on the hollow microsphere matrix
Organic compound, the organic compound molecule general structure be A1-D-A2, wherein the A1 and A2 is respectively electrophilic
Group, the D are the symmetrical organic group of molecular structure.
2. modified hollow microsphere according to claim 1, it is characterised in that: the electron-withdrawing group is carboxyl, aldehyde radical, ester
Any one of base, sulfydryl, nitro, sulfonic group, hydroxyl；And/or
The symmetrical organic group of molecular structure is any one of substitution or unsubstituted carbazole, triphenylamine.
3. modified hollow microsphere according to claim 2, it is characterised in that: the A1-D-A2 compound is following L1-L6
At least one of shown molecular structural formula:
4. modified hollow microsphere according to claim 1 to 3, it is characterised in that: the hollow microsphere matrix with it is described
A1-D-A2 compound is in conjunction with A1 the or A2 base for being the grafted moiety by the hollow microsphere matrix surface with the A1-D-A2
Group's copolymerization is attached；And/or
The material of the hollow microsphere matrix is high molecular polymer.
5. a kind of preparation method of modified hollow microsphere, which comprises the steps of:
Surface grafting processing is carried out to hollow microsphere matrix, organic compound is made to be grafted to hollow microsphere surface, forms surface knot
The hollow microsphere for having organic compound is closed, the general structure of the organic compound is that A1-D-A2, the A1 and A2 are respectively to inhale
Electron group, the D are the symmetrical organic group of molecular structure.
6. preparation method according to claim 5, it is characterised in that: carried out at surface grafting to the hollow microsphere matrix
Reason, makes the organic compound include: with the step of being grafted to hollow microsphere surface
Prepare the organic solution containing isocyanate group；
Hollow microsphere and catalyst are added into the organic solution containing isocyanate group, make hollow microsphere and isocyanate group has
The reaction of machine object, obtains the hollow microsphere of isocyanate group activation；
The hollow microsphere that the isocyanate group activates is reacted with the organic compound.
7. preparation method according to claim 6, it is characterised in that: the organic matter of the isocyanate group is 4,4 '-hexichol
Dicyclohexylmethane diisocyanate, phenylisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, Toluene-2,4-diisocyanate, 6- diisocyanate, 3,3 '-diformazans
At least one of base diphenyl-methane, 4,4 '-diisocyanate；And/or
The catalyst be acid dibutyl tin, triethylenediamine, N-ethylmorpholine, N, N'- diethyl piperazine, N,
At least one of N '-diethyl -2- methyl piperazine, N, N'- is bis--(α-hydroxypropyl) -2- methyl piperazine.
8. preparation method according to claim 5, it is characterised in that: carried out at surface grafting to the hollow microsphere matrix
Reason, makes the organic compound include: with the step of being grafted to hollow microsphere surface
It prepares and contains hollow microsphere solution；
Graft initiator is added into hollow microsphere solution, carries out constant temperature isothermal holding, adds the organic compound and carries out
Copolyreaction.
9. preparation method according to claim 8, it is characterised in that: the graft initiator is ammonium ceric nitrate, persulfuric acid
At least one of potassium, ammonium persulfate-sodium bisulfite, N- diethylaniline.
10. a kind of packaging plastic, including adhesive components, it is characterised in that: it further include radiation nano particle and hollow microsphere, it is described
Radiation nano particle and hollow microsphere are dispersed in the adhesive components；Wherein, the hollow microsphere is claim 1-4
Any modification hollow microsphere or the modification hollow microsphere prepared by any preparation method of claim 5-7.
11. packaging plastic according to claim 10, it is characterised in that: at least partly described radiation nano particle is to be adsorbed on
On the modified hollow microsphere.
12. packaging plastic according to claim 10, it is characterised in that: the radiation nano particle and hollow microsphere total weight
It is 10%~30% in the content of the packaging plastic, the radiation nano particle accounts for the radiation nano particle and hollow microsphere is total
The 10%~40% of weight.
13. packaging plastic according to claim 10, it is characterised in that: the partial size of the radiation nano particle be 20~
30nm；And/or
The partial size of the hollow microsphere is 300~600nm.
14. any packaging plastic of 0-13 according to claim 1, it is characterised in that: the radiation nano is metallic nanoparticle
At least one of son and metal oxide nanoparticles；And/or
The adhesive is at least one of UV optic-solidified adhesive, epoxies packaging plastic, organic silicon packaging plastic.
15. packaging plastic according to claim 14, it is characterised in that: the metal nanoparticle is silver, in aluminium, copper, nickel
At least one metal nanoparticle；
The metal oxide nanoparticles are at least one of silver, aluminium, copper, nickel metal oxide nanoparticles.
16. a kind of encapsulating structure, the encapsulated layer including electronic component and for encapsulating the electronic component, it is characterised in that: institute
Stating encapsulated layer includes any packaging plastic of claim 10-15 after solidifying.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007023982A1 (en) * | 2007-05-11 | 2008-11-13 | Jowat Ag | Low density melt adhesive, useful e.g. in wood or furniture processing, contains expanded hollow microspheres in reactive or non-reactive base polymer, e.g. polyurethane |
| CN101519576A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for preparing packaging adhesive used for high-transmittance high-power light emitting diode |
| CN101657502A (en) * | 2007-04-16 | 2010-02-24 | 陶氏康宁公司 | Condensation curable compositions having improved self adhesion to substrates |
| CN103811634A (en) * | 2014-01-26 | 2014-05-21 | 佛山市国星光电股份有限公司 | Packaging adhesive surface matted LED (light-emitting diode) device, packaging method thereof and LED display screen |
| DE102016103676A1 (en) * | 2016-03-01 | 2017-09-07 | Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen | The power semiconductor module |
-
2017
- 2017-12-15 CN CN201711374782.5A patent/CN109929136B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101657502A (en) * | 2007-04-16 | 2010-02-24 | 陶氏康宁公司 | Condensation curable compositions having improved self adhesion to substrates |
| DE102007023982A1 (en) * | 2007-05-11 | 2008-11-13 | Jowat Ag | Low density melt adhesive, useful e.g. in wood or furniture processing, contains expanded hollow microspheres in reactive or non-reactive base polymer, e.g. polyurethane |
| CN101519576A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for preparing packaging adhesive used for high-transmittance high-power light emitting diode |
| CN103811634A (en) * | 2014-01-26 | 2014-05-21 | 佛山市国星光电股份有限公司 | Packaging adhesive surface matted LED (light-emitting diode) device, packaging method thereof and LED display screen |
| DE102016103676A1 (en) * | 2016-03-01 | 2017-09-07 | Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen | The power semiconductor module |
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