Composite filled type heat-conducting plastic of a kind of micro-nano based on vibration moulding and preparation method thereof
Technical field
The present invention relates to a kind of composition of high-molecular compound, and in particular to a kind of micro-nano based on vibration moulding is compound
HEAT-CONDUCTING PLASTICS FILLED WTTH PARTICLES and preparation method thereof.
Background technology
Heat Conduction Material is a kind of important functional material, and it has in the field such as national defense industry and national economy widely should
With.Heat conductivility is also of interest by people more and more as one highly important physical property of material.Heat Conduction Material energy
Accelerate the heat transfer efficiency of radiating original paper, so as to improve the use value of product and service life.Conventional thermal conductive material is mostly metal,
Because corrosion resistance is very poor, processing and forming is not easy to, can not meet to live and produce the requirement to Heat Conduction Material all the more, so need
Develop new heat conduction functional material.
High polymer material possesses the excellent combination properties such as light, easy processing is molded, cost is cheap, can overcome conventional pilot
The defects of hot material and the use demand for fully meeting above-mentioned application field, so gradually showing up prominently in this field.But by
It is usually to be combined by molecular separating force in high polymer material, is all the non-conductor of heat, even thermal conductivity averagely only has in room temperature
0.1-1W/mK, itself heat conductivility is often poor, significantly limit the heat diffusion capabilities of high polymer, therefore height is led
Hot composite is developed into key.Study through substantial amounts of experiment and repeatedly, find to fill out using the heat filling of high heat conductance
Fill polymeric matrix and prepare composite, the thermal conductivity of high polymer material can be effectively improved, the heat conduction high score so obtained
Sub- material price is cheap, and technique or formula are easy to adjust, and available for a variety of application fields, this turns into thermal conductive polymer composite
Main direction of studying.
Want to assign high polymer material excellent thermal conductivity, mainly pass through the side such as blending, melt blended and solution blending
Method fills the filler of good heat conductivity in high polymer material.In addition, while the thermal conductivity of filler raising material is added,
The mechanical property of matrix material must be ensured.Therefore, how to make that the heat conduction network in system is formed to the full extent and reaching has
Effect thermal conductive and do not influence the system mechanical property be research and develop HEAT-CONDUCTING PLASTICS FILLED WTTH PARTICLES key issue.Existing heat conduction
Plastics are generally difficult to accomplish existing excellent thermal conductivity, meet the higher mechanical property of heat-conducting plastic again.
The content of the invention
Both there is excellent thermal conductivity it is an object of the invention to provide a kind of, the heat conduction with higher force performance again is moulded
Material, another object of the present invention is to provide a kind of method for preparing above-mentioned heat-conducting plastic.
To reach above-mentioned purpose, the present invention provides following base case one:
The composite filled type heat-conducting plastic of micro-nano based on vibration moulding, the mass percent of its various raw material are:Matrix tree
Fat 20-90%, micro-nano composite heat-conducting filler 10-80%;In addition in terms of total amount, also containing toughener 0.2-1%, coupling agent 1-
3%th, antioxidant 0.1-0.5%, lubricant 0.1-1.5%;The micro-nano composite heat-conducting filler is that mass ratio is 1-9:1 scale
The mixture of graphite and nano-graphite.
The general meter method of the art is used in the present invention program, the mass percent of raw material is calculated, only calculates matrix
Resin and heat filling, without toughener, coupling agent, antioxidant and lubricant are counted, because as a whole, toughness reinforcing
Agent, coupling agent, the amount of antioxidant and lubricant are less.
The advantages of this programme is:The present invention is using crystalline flake graphite and nano-graphite form micron, nano composite heat conduction is filled out
Material, and extraneous vibration field, make matrix resin be mixed with micro-nano compounded mix more uniform, the compound filler of micro-nano is easier to be formed
Heat conduction network chain, under low loading, while ensureing the superiority of matrix plastic mechanical property, you can it is high to obtain heat transfer efficiency
Heat-conducting plastic, it can be widely applied to electric and the case material of medical field and packaging material, auto parts machinery and machinery and set
In standby.
Prioritization scheme 1, the further optimization to base case, the mass percent of its various raw material are:Matrix resin 40-
70%, micro-nano composite heat-conducting filler 30-60%;In addition in terms of total amount, also containing toughener 0.2-0.8%, coupling agent 1-2%,
Antioxidant 0.2-0.4%, lubricant 0.2-0.8%;The micro-nano composite heat-conducting filler is that mass ratio is 1-4:1 crystalline flake graphite
With the mixture of nano-graphite.The heat conductivility and mechanical property of the heat-conducting plastic prepared under said ratio are more preferably.
Prioritization scheme 2, the further optimization to base case one, the mass percent of its various raw material are:Matrix resin
60%, micro-nano composite heat-conducting filler 40%;In addition in terms of total amount, also containing toughener 0.4%, coupling agent 1.5%, antioxidant
0.3%th, lubricant 0.3%;The micro-nano composite heat-conducting filler is that mass ratio is 2:The mixing of 1 crystalline flake graphite and nano-graphite
Thing.Inventor has found that the heat conductivility and mechanical property of the heat-conducting plastic prepared under said ratio are optimal through experiment.
Prioritization scheme 3, the further optimization to base case one, the micro-nano composite heat-conducting filler are crystalline flake graphite and received
Meter Shi Mo mixture, a diameter of 100nm of the nano-graphite.Compared with mixing filling can be such that small particle is formed with big particle diameter
Closely accumulation, advantageously forms more effective heat conduction network, and the built between different-grain diameter particle can change, using this
Diameter, then by adjusting the proportioning of micro-nano structure, best cooperation between particle can be obtained, obtains optimal bridge formation effect.
The present invention also provides following base case two:
A kind of preparation method of the composite filled type heat-conducting plastic of micro-nano based on vibration moulding, comprises the following steps:
S1. following raw material is proportionally prepared:It is matrix resin, micro-nano composite heat-conducting filler, toughener, coupling agent, anti-
Oxygen agent and lubricant;
S2. first the surface of crystalline flake graphite and nano-graphite is pre-processed with coupling agent, adds matrix resin, toughness reinforcing
Agent, lubricant and antioxidant, the composite filled type heat-conducting plastic pellet of micro-nano is prepared using melt blending extrusion molding;
S3. pellet injection molding step S2 extruded, when beads fuse, oscillator field is applied to material, makes melting matrix
Resin mutually moves arrangement with micro-nano composite heat-conducting filler and reaches uniform close.
The advantages of this programme is:The present invention by the compound action vibrated and sheared by material extraneous vibration field, being made
Filler and matrix material it is well mixed and close, under low loading, you can so that the thermal conducting path that heat filling is formed
It is further perfect, so that the thermal conductivity of composite improves rapidly, the purpose of low loading high heat conduction is realized, is greatly carried
High properties of product.
Prioritization scheme 4, the further optimization to base case two, oscillator field vibration frequency is 1-30Hz in step S3.This
The inventor of invention through experiment find, oscillator field vibration frequency within the above range when, the purpose of the present invention can be reached.
Prioritization scheme 5, the further optimization to prioritization scheme 4, oscillator field vibration frequency is 12Hz in step S3.Vibration frequency
Rate is bigger, and thermal conductivity is better, and more than 12Hz thermal conductivitys tend to be steady, but tensile strength can decline, so considering, oscillator field
Best results when frequency is 12Hz.
Prioritization scheme 6, the further optimization to base case two, the surface of crystalline flake graphite and nano-graphite in step S2
It is as crystalline flake graphite and the surface modifier of nano-graphite from titanate coupling agent TMC-931 to carry out pretreatment.Using titanium
When acid esters coupling agent TMC-931 is handled, the heat conductivility and mechanical property of the heat-conducting plastic finally given are more preferably.
Prioritization scheme 7, the further optimization to base case two, step S2 method are as follows:
S21. the surface of crystalline flake graphite and nano-graphite is pre-processed with coupling agent;
S22. mixed with high-speed mixer, pretreated crystalline flake graphite and nano-graphite are first poured into mixed at high speed
In machine, send out compound crystalline flake graphite and nano-graphite and the coupling agent on surface using the high temperature and whipping process of high-speed mixer
Raw reaction, heat mixed 8-12 minutes stop;
S23. plastic substrate is added, after high mixer is cooled to room temperature, adds toughener, lubricant and antioxidant.
In this programme, high-speed mixer carries out Combined Processing, energy using high-speed mixer to crystalline flake graphite and nano-graphite
Both composite effects are enough effectively improved, so as to ensure the heat conduction of heat-conducting plastic and mechanical property;In addition, high mixer is cooled to room temperature
Toughener, lubricant and antioxidant are added afterwards, can play the maximum efficiency of toughener, lubricant and antioxidant.
Prioritization scheme 8, the further optimization to any one of prioritization scheme 4-7, step S3 method are as follows:
S31. pellet and plastic substrate are well mixed again, are heated to molten condition and stably;
S32. oscillator field is applied to the composite filled type heat-conducting plastic of micro-nano of melting, by vibrating and shearing compound action reality
Now certain mixed effect.
In this programme, pellet and plastic substrate are well mixed again, can fill out plastic substrate and micro-nano composite heat-conducting
Material fully mixes, and when subsequently applying oscillator field, micro-nano composite heat-conducting filler can be arranged in the knot of uniform close in plastic substrate
Structure, so as to increased thermal conductivity energy and mechanical property.
Brief description of the drawings
Fig. 1 is 1-5 of embodiment of the present invention micro-nano compounded mix with comparison heat-conducting plastic material heat conductivility figure;
Fig. 2 is the embodiment of the present invention 1, embodiment 6-11 vibration field frequencies range to heat-conducting plastic material heat conductivility figure.
Embodiment
Below by embodiment, the present invention is further detailed explanation, but embodiment is not done to the present invention
Any type of restriction.Unless stated otherwise, the present invention use reagent, method and apparatus for the art conventional reagent,
Method and apparatus.Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
In the present embodiment, matrix resin used is polyethylene terephthalate, and toughener used is SEBS-g-
MA, coupling agent used are titanate coupling agent, and antioxidant used is antioxidant 1010, and lubricant used is PETS.
It is described in detail below by taking embodiment 1 as an example, the proportioning and index of other embodiment embody in table 1, other
The processing step of embodiment is same as Example 1.
Embodiment 1
A kind of composite filled type heat-conducting plastic of micro-nano based on vibration moulding, the quality of its various raw material are:Gather to benzene two
Formic acid glycol ester (PET) 60g, micro-nano composite heat-conducting filler 40g;In addition in terms of total amount, also contain containing toughener SEBS-g-MA
Measure as 0.8g, titanate coupling agent 2g, antioxidant 1010 content are 0.3g, lubricant PETS contents are 1g;The micro-nano is compound
Heat filling is that mass ratio is 2:1 crystalline flake graphite and the mixture of nano-graphite.
The preparation method of heat-conducting plastic described in the present embodiment, comprises the following steps:
S1. following raw material is prepared according to aforementioned proportion:Polyethylene terephthalate (PET), micro-nano composite heat-conducting
Filler, toughener SEBS-g-MA, titanate coupling agent, antioxidant 1010 and lubricant PETS;
S21. the surface of crystalline flake graphite and nano-graphite is pre-processed with coupling agent;
S22. mixed with high-speed mixer, pretreated crystalline flake graphite and nano-graphite are first poured into mixer
In, compound crystalline flake graphite and nano-graphite and the coupling agent on surface occurs using the high temperature and whipping process of high-speed mixer
Reaction, heat stop for mixed general ten minutes or so;
S23. polyethylene terephthalate (PET) pellet is added, after high mixer is cooled to room temperature, adds toughener
SEBS-g-MA, lubricant PETS and antioxidant 1010.
S31. pellet material and polyethylene terephthalate (PET) pellet are well mixed again, are heated to molten
State and stably;
S32. 12Hz oscillator field is applied to the composite filled type heat-conducting plastic of micro-nano of melting, it is compound by vibrating and shearing
Certain mixed effect is realized in effect, and the thick rectangular flats of 1mm are obtained by hot-forming.
Table 1
The thermal conductivity of the sample prepared respectively in testing example 1-5, is obtained such as the test result of accompanying drawing 1.
The tensile strength of the sample prepared respectively in testing example 1, embodiment 6-11, is obtained shown in table 2 and accompanying drawing 2
As a result.
Impact strength, the tensile strength of the sample prepared respectively in testing example 1, embodiment 12-15, obtain table 3
Shown result.
Table 2
Table 3
1st, in embodiment 1-5, the mass ratio difference of micro-nano compounded mix is differed only in, accompanying drawing 1 is embodiment 1-5 heat conduction
The performance test results.It was found from from accompanying drawing 1, the heat filling mixing of micro-nano compound structure is filled into its good heat conductivity in matrix
In the traditional common micro-scaled filler of exclusive use.This is due to compared with mixing filling can be such that small particle is formed with big particle diameter conductive particle
Closely accumulation, advantageously forms more effective heat conduction network.When micro-nano compounded mix proportioning is 2:When 1, composite is led
Hot property is optimal, and its thermal conductivity is up to 1.420Wm-1K-1.This is due under the proportioning, and best match somebody with somebody is achieved between particle
Close, obtain optimal network structure.
2nd, in embodiment 1, embodiment 6-11, differ only in the preparation process of sample, the vibration field frequencies range of use
Difference, table 2 are embodiment 1, embodiment 6-11 mechanical experimental results, and accompanying drawing 2 is embodiment 1, embodiment 6-11 thermal conductivity
Can test result.From table 2 it can be seen that when the vibration frequency of oscillator field reaches 12Hz, the mechanical property of heat-conducting plastic is optimal;
It was found from from accompanying drawing 2, with the increase of the vibration field frequencies range of application, the heat conductivility of composite is better, when the vibration of application
When field frequencies range tends to 12Hz, the heat conductivility of composite rises and tended towards stability, and its thermal conductivity is up to 1.420Wm-1K-1.This
It is due to that sample mixed effect is better with the increase of vibration field frequencies range, filler is scattered about uniformly, easier formation network knot
Structure.To sum up it can be found that the vibration frequency of oscillator field is optimal for 12Hz effect.
3rd, in embodiment 1, embodiment 12-15, difference essentially consists in, and the loading of micro-nano compounded mix is different, can from table 3
To find out, when the loading of micro-nano compounded mix is 40g (i.e. accounting 40%), mechanical property is optimal.
Above-described is only embodiments of the invention, and the general knowledge such as known characteristic does not describe excessively herein in scheme.
It should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise, some changes can also be made
Shape and improvement, these should also be considered as protection scope of the present invention, these effects and patent for implementing all without the influence present invention
Practicality.The scope of protection required by this application should be based on the content of the claims, the specific embodiment party in specification
The records such as formula can be used for the content for explaining claim.