阅读说明：本技术 具有增加的体积电阻率的基于石墨的组合物 (The composition based on graphite with increased volume resistivity ) 是由 F·P·M·莫希 F·达罗萨 于 2018-03-29 设计创作，主要内容包括：一种共混的热塑性组合物,其包括：约20wt％至约99wt％的热塑性聚合物成分；约1wt％至约60wt％的基于石墨的填料成分,所述基于石墨的填料成分包括在基于石墨的填料成分的表面上的至少约0.01wt％的官能团；约0.1wt％至约30wt％的官能剂成分；和约0至约50wt％的导热且电绝缘填料。所述官能剂成分包括与基于石墨的填料成分的表面上的官能团相互作用的官能团,这导致与不包括官能剂成分的基本上相同的导电共混的热塑性组合物的体积电阻率相比,共混的热塑性组合物的体积电阻率至少1×10<Sup>2</Sup>的增加。(A kind of thermoplastic compounds of blending comprising: the thermoplastic polymer components of about 20wt% to about 99wt%；The filler ingredient based on graphite of about 1wt% to about 60wt%, the filler ingredient based on graphite include at least about functional group of 0.01wt% on the surface of the filler ingredient based on graphite；The functional agent ingredient of about 0.1wt% to about 30wt%；About 0 to about 50wt% thermally conductive and electrically insulating filler.The functional agent ingredient includes the functional group with functional group's interaction on the surface of the filler ingredient based on graphite, this causes compared with the volume resistivity of the substantially the same conductive thermoplastic compounds being blended for not including functional agent ingredient, the volume resistivity of the thermoplastic compounds of blending at least 1 × 10 2 Increase.)

1. a kind of thermoplastic compounds of blending comprising:

(a) thermoplastic polymer components of about 20wt% to about 99wt%；

(b) the filler ingredient based on graphite of about 1wt% to about 60wt%, the filler ingredient based on graphite are included in described At least about functional group of 0.01wt% on the surface of filler ingredient based on graphite；

(c) the functional agent ingredient of about 0.1wt% to about 30wt%；With

(d) about 0 to about 50wt% thermally conductive and electrically insulating filler,

Wherein the functional agent ingredient includes interacting with the functional group on the surface of the filler ingredient based on graphite Functional group, this causes and the volume resistance for the substantially the same conductive thermoplastic compounds being blended for not including functional agent ingredient Rate is compared, the volume resistivity of the thermoplastic compounds of the blending at least 1 × 10²Increase.

2. the thermoplastic compounds of blending according to claim 1, wherein the surface of the filler ingredient based on graphite On functional group include the functional group based on oxygen, the functional group based on nitrogen or combinations thereof.

3. the thermoplastic compounds of blending according to claim 2, wherein the filler ingredient based on graphite is located in advance Manage the functional group based on oxygen or the function based on nitrogen on the surface to increase the filler ingredient described based on graphite The content of group.

4. the thermoplastic compounds of blending according to claim 3, wherein passing through plasma process, oxidation technology, height Filler ingredient described in one of warm air technique or ozone process or a variety of pretreatments based on graphite is to increase in the base In the content of functional group or the functional group based on nitrogen based on oxygen described on the surface of the filler ingredient of graphite.

5. the thermoplastic compounds of blending according to any one of claim 1 to 4, wherein the functional agent ingredient includes Component of polymer, the component of polymer include epoxy-functional, maleic anhydride functional groups, amine functional group or combinations thereof.

6. the thermoplastic compounds of blending according to any one of claim 1 to 4, wherein the functional agent ingredient includes Non-polymer low molecular weight compositions, the non-polymer low molecular weight compositions include epoxides, maleic anhydride, amine or its group It closes.

7. a kind of thermoplastic compounds of blending comprising:

(a) thermoplastic polymer components of about 20wt% to about 99wt%；

(b) the pretreated filler ingredient based on graphite of about 1wt% to about 60wt%, pretreated the filling out based on graphite Expect that ingredient includes at least about functional group of 0.01wt% on the surface of the pretreated filler ingredient based on graphite；

(c) the functional agent ingredient of about 0.1wt% to about 30wt%；With

(d) about 0 to about 50wt% thermally conductive and electrically insulating filler,

Wherein

The pretreated filler ingredient based on graphite be pretreated with increase it is described it is pretreated based on the filler of graphite at The content of the functional group on surface divided, and

The functional agent ingredient includes thermoplastic polymer, the thermoplastic polymer include with it is described pretreated based on graphite Filler ingredient surface on functional group's interaction functional group, this causes and do not include pretreated filling out based on graphite The volume resistivity of the substantially the same conductive thermoplastic compounds being blended of material ingredient is compared, the thermoplasticity group of the blending Close the volume resistivity at least 1 × 10 of object²Increase.

8. the thermoplastic compounds of blending according to claim 7, wherein the functional group of the functional agent ingredient includes amine Base, maleic groups, epoxy group, hydroxyl or combinations thereof.

9. the thermoplastic compounds of blending according to claim 7 or 8, wherein the functional agent ingredient include polyamide, Ethylene-methyl acrylate-glycidyl acrylate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer, poly- (second Enol), polybutylene terephthalate (PBT), its copolymer and a combination thereof.

10. the thermoplastic compounds of blending according to any one of claims 7 to 9, wherein the thermoplastic polymer Ingredient and the functional agent ingredient include identical thermoplastic polymer.

11. the thermoplastic compounds of blending according to any one of claims 7 to 9, wherein the thermoplastic polymer Ingredient and the functional agent ingredient include different thermoplastic polymers.

12. the thermoplastic compounds of blending according to any one of claims 7 to 11, pretreated it is based on wherein described Functional group on the surface of the filler ingredient of graphite includes the functional group based on oxygen, the functional group based on nitrogen or combinations thereof.

13. the thermoplastic compounds of blending according to claim 12, wherein by plasma process, oxidation technology, One of high temperature air technique or ozone process or a variety of pretreatment pretreated filler ingredients based on graphite are to increase Functional group or the official based on nitrogen described in adding on the surface of the pretreated filler ingredient based on graphite based on oxygen The content that can be rolled into a ball.

14. the thermoplastic compounds of blending according to any one of claim 1 to 13, wherein described thermally conductive and electrically insulating Filler includes boron nitride, Mg (OH)₂、MgO、CaCO₃, silica, aluminium oxide, alumina silicate, ZnO, ZnS, talcum and a combination thereof.

15. according to claim 1 to the thermoplastic compounds of blending described in any one of 14, wherein the thermoplastic polymer Ingredient include polyolefin compound, polyarylene sulfide compound, polyamide compound, petchem, polycarbonate compound, Polyphenylene ether compound, polyetherimide amine compounds, the copolymer including these any compounds, including these any compounds Blend and a combination thereof.

16. the thermoplastic compounds of blending according to claim 1 or claim 7, wherein the interaction include covalent bond or Noncovalent interaction.

17. a kind of method that the thermoplastic compounds of blending are used for high thermal conductivity and reduced conductivity product, the method Include:

It will be raised including being exposed to according to claim 1 to the product of the thermoplastic compounds of blending described in any one of 16 Constant temperature for a period of time,

Wherein the product is used to need in the application of the thermoplastic compounds of the blending to have at least 0.6 watt of every meter -to open The thermal conductivity of Er Wen (W/mK) and at least 1 × 10⁵The volume resistivity of Ohm-cm.

18. according to the method for claim 17, wherein the raised temperature includes about 40 degrees Celsius (DEG C) to about 250 DEG C Temperature, and the duration includes about 24 hours to about 30 years time.

19. method described in 7 or 18 according to claim 1, wherein the application be consumer-electronics applications, LED illumination application or Electric power application.

20. method described in any one of 7 to 19 according to claim 1, wherein the product is mechanograph.

Technical field

This disclosure relates to composition with increased volume resistivity based on graphite and the product being made from it.

Background technique

In several emerging applications such as electronics, LED illumination and electric power and battery system, heat management is just becoming increasingly It is important.For consumer-elcetronics devices and LED illumination application, heat accumulation during use may reduce device efficiency and may It shortens the working life.From the perspective of user, it is uncomfortable that the heat of accumulation may make equipment touch get up.In order to reduce temperature Degree uses radiator.They disperse heat from source, and heat is spread to very big region by convection current.Nowadays, it dissipates Hot device is commonly made from aluminium, because it represents the good folding between the such as light weight of desired characteristic, thermal conductivity and cost Inner feelings.

When shell/radiator is made by conductive material such as aluminium, insulating materials would generally be by electronic component and radiator It separates to prevent short circuit.It will increase manufacture both complexity and cost including insulating materials.In addition, the material ratio based on metal can The material solution of substitution is more difficult to process, and this reduce the freedom degrees of Element Design.

For example, compared with metal solution, thermoplastic 1) it is more readily processed, this gives in terms of Element Design Bigger freedom degree；2) weight is significantly lighter；3) it is electrically insulated.Therefore, although thermoplastic may need with electrical isolation, lead Hot filler is modified to meet performance requirement, but thermoplastic can usually provide desired characteristic, and representative has Wish the substitute of aluminium and metal.The interested specific filler of one kind is graphite, because it has outstanding thermal conduction characteristic.So And since graphite is conductive, it is therefore necessary to the electric conductivity be inhibited just to be able to satisfy the demand of this specific application area.

In addition, there is the material based on boron nitride for high-termal conductivity and electrical insulating property application.However, boron nitride at This and required high filler load (realize high thermal conductivity) keep its use cost excessively high, this makes the solution for general Logical application can not be as the substitute of aluminium.

Solve these and other disadvantages in terms of by present disclosure.

Summary of the invention

It is related to the thermoplastic compounds being blended in terms of present disclosure, the composition includes: about 20wt% to about The thermoplastic polymer components of 99wt%；The filler ingredient based on graphite of about 1wt% to about 60wt%, should filling out based on graphite Expect that ingredient includes at least about functional group of 0.01wt% on the surface of the filler ingredient based on graphite；About 0.1wt% is to about The functional agent ingredient of 30wt%；About 0 to about 50wt% thermally conductive and electrically insulating filler.Functional agent ingredient includes and is based on graphite Filler ingredient surface on functional group's interaction functional group, this causes and the substantially phase that does not include functional agent ingredient With the conductive thermoplastic compounds being blended volume resistivity compared with, the volume resistivity of the thermoplastic compounds of blending is at least 1×10²Increase.

The aspect of present disclosure further to blending thermoplastic compounds, the composition include: about 20wt% extremely The thermoplastic polymer components of about 99wt%；The pretreated filler ingredient based on graphite of about 1wt% to about 60wt%, this is pre- The filler ingredient based on graphite of processing include on the surface of filler ingredient pretreated based on graphite at least about The functional group of 0.01wt%；The functional agent ingredient of about 0.1wt% to about 30wt%；About 0 to about 50wt% it is thermally conductive and electric absolutely Edge filler.The pretreated filler ingredient based on graphite is pretreated to increase the table of the pretreated filler ingredient based on graphite The content of functional group on face.Functional agent ingredient includes thermoplastic polymer, which includes and pretreated base In the functional group of functional group's interaction on the surface of the filler ingredient of graphite, this causes and does not include pretreated based on stone The volume resistivity of the substantially the same conductive thermoplastic compounds being blended of the filler ingredient of ink is compared, the thermoplasticity of blending The volume resistivity of composition at least 1 × 10²Increase.

Detailed description of the invention

In the attached drawing being not drawn necessarily to scale, identical number can describe similar group in different views Part.Same numbers with different letter suffix can indicate the different instances of similar component.Attached drawing is by way of example and with non-limit The mode of system generally illustrates the various examples discussed in this document.

Figure 1A -1D is to show the exemplary composition formed according to the aspect of present disclosure and does not include functional agent ingredient Reference example table 1A-1D.

Fig. 1 E and 1F are the volume resistivity for showing the composition shown in Figure 1A -1C or thermal conductivity with filler load variations Data figure.

Fig. 2A and 2B be to show the exemplary composition formed according to the aspect of present disclosure and do not include functional agent at The table 2A and 2B for the reference example divided.

Fig. 2 C, 2D, 2E and 2F are the volume resistivity for showing the composition shown in Fig. 2A and 2B or thermal conductivity with filler The figure of the data of load variations.

Fig. 3 is the ginseng for showing the exemplary composition formed according to the aspect of present disclosure and not including functional agent ingredient Examine the table 3 of example.

Fig. 4 is the ginseng for showing the exemplary composition formed according to the aspect of present disclosure and not including functional agent ingredient Examine the table 4 of example.

Fig. 5 is the ginseng for showing the exemplary composition formed according to the aspect of present disclosure and not including functional agent ingredient Examine the table 5 of example.

Fig. 6 A-6C is to show the exemplary composition formed according to the aspect of present disclosure and does not include functional agent ingredient Reference example table 2A-2C.

Fig. 7 is the ginseng for showing the exemplary composition formed according to the aspect of present disclosure and not including functional agent ingredient Examine the table 7 of example.

Specific embodiment

By reference to the described in detail below of present disclosure and including embodiment can be more easily to understand this Disclosure.However, before disclosure and description the compound of the present invention, composition, product, equipment and/or method, it should manage It solves aspect described below and is not limited to specific synthetic method, because they can of course change.It should also be understood that being made herein Term is not intended to be restrictive merely for the purpose of description particular aspects.Although similar to or be equal to and retouch herein Any method and material of the method and material stated may be used to practice or test present disclosure, but reality will now be described Example method and material.

Further, it is understood that being otherwise not intended to unless otherwise clearly stating by any method set forth herein It is construed to that its step is required to execute with specific order.Therefore, do not describe what its step to be followed actually in claim to a method In the case where sequence, or does not have in claims or specification step is in addition expressly recited and be necessarily limited to specific order In the case of, this is not intended to the sequence of deduction in any way.Nevertheless, the step of being presented with given sequence may be considered that generation The one aspect of this method of table.This is suitable for any possible non-express basis for interpretation, this includes: and step or operation stream The related logical problem of the arrangement of journey；The ordinary meaning obtained from grammatical organization or punctuation mark；And described in specification The quantity or type of aspect.

Definition

It should also be understood that terms used herein are not intended to be restrictive merely for the purpose of description particular aspects. In terms of as used in the specification and in the claims, term " including (comprising) " may include " by ... group At (consisting of) " and " substantially by ... form (consisting essentially of) ".Unless otherwise fixed Justice, otherwise all technical and scientific terms used herein has usual with present disclosure those of ordinary skill in the art The identical meaning understood.In this description and in the appended claims, many terms defined herein will be referred to.

It is unless the context clearly indicates otherwise, otherwise singular as used in specification and appended book Form " one (a) ", " one (an) " and " (the) " include plural referents.Thus, for example, referring to " polycarbonate polymerization Object " includes the mixture of two or more carbonate polymers.

As it is used herein, term " combination " includes blend, mixture, alloy, reaction product etc..

Range can be expressed as in this paper from a particular value and/or to another particular value.When such a range is expressed, It on the other hand include from a particular value and/or to another particular value.Similarly, when value is expressed as by use antecedent " about " When approximation, it will be understood that on the other hand the particular value is formed.It will be further understood that, the endpoint of each range is relative to another end Point is all meaningful, and independently of another endpoint.It should also be understood that disclosed herein is many values, and each value exists It is also disclosed other than the value itself herein as " about " particular value.For example, being also disclosed if disclosing value " 10 " " about 10 ".It should also be understood that also disclosing each unit between two specific units.For example, if disclosing 10 and 15, Also disclose 11,12,13 and 14.

As used herein, term " about " and " for or about " refer to that discussed amount or value can be such value, referred to It is set to approximate or the about value some other values.As it is used herein, being generally understood as unless otherwise noted or inferring, otherwise It is the variation of signified nominal value ± 10%.The equivalent knot that the term is intended to that similar value is conveyed to be conducive to describe in claim Fruit or effect.That is, it is to be understood that amount, size, formula, parameter and other quantity and characteristic are not and also need not It is accurate, but can according to need approximate and/or greater or lesser, this reflection tolerance conversion factor, rounds up, surveys Measure error etc. and other factors well known by persons skilled in the art.In general, quantity, size, formula, parameter or other quantity Or characteristic is " about " or " approximate ", regardless of whether clearly so statement.Unless otherwise expressly specified, it should be appreciated that In In the case where using " about " before quantitative values, which further includes specific quantitative values itself.

As used herein, term " optional " or " optionally " refer to that the event then described or situation may be sent out Life may not occur, and the description includes the case where that the wherein event or situation occur and the wherein event or situation Not there is a situation where.For example, phrase " optionally substituted alkyl " refers to that alkyl can be substituted or can not be substituted, and The description includes both substitution and unsubstituted alkyl.

Disclosing can be used for disclosed method and composition, can be used in combination with disclosed method and composition, is available In material, compound, composition and the group of the product for preparing disclosed method and composition or disclosed method and composition Point.Disclosed herein is these and other materials, and it should be understood that when disclose the combinations of these materials, subset, interaction, Group etc. whens, although cannot clearly disclose these compounds it is each individually and collective combinations and displacement with specific reference to, often It is a to be specifically contemplated and describe herein.Therefore, if disclose a kind of filler A, B and C and one kind additive D, E and F, and the example of combination A-D is disclosed, even when not enumerated individually each, but each is also individually to consider with common 's.Therefore, in this example, each of A-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F is combined all specifically to be examined Consider, and is considered to be from A, B and C；D, E and F；And disclosed in the disclosure of example combination A-D.Equally, these Any subset or combination be also specifically contemplated and openly.Thus, for example, the subgroup of A-E, B-F and C-E are specifically examined Consider, and is considered as from A, B and C；D, E and F；And disclosed in the disclosure of example combination A-D.The concept is suitable For all aspects of present disclosure, including but not limited to composition and the method for making and using disclosed composition In step.Therefore, if there is the multiple additional steps that can be executed, then it should be understood that each in these additional steps It is a to be executed together with the combination of any particular aspects of disclosed method or aspect, and quilt is combined as every kind Specifically consider and should be considered disclosing.

In the specification and the appended claims in composition or product special component or component by weight The referring to of meter or number by volume respectively indicate the composition indicated respectively with number by weight or by volume or The weight or volume relationship between ingredient or component and any other ingredient or component in product.Therefore, comprising by weight In the composition for counting 2 parts of component X and 5 parts by weight of component Y, X and Y exist with the weight ratio of 2:5, and in spite of Having additional component includes in the composition, with ratio presence.

As it is used herein, unless expressly stated otherwise, " the weight percent for the term component that otherwise may be used interchangeably Than " and " wt% " be based on include the component preparation or composition total weight.For example, if in composition or product Specific ingredient or component have by weight 8%, then it should be understood that the percentage be relative to by weight 100% it is total Percentage composition.

As it is used herein, term " electroosmotic flow threshold value " traditionally refer in composition based on the filler of Standard graphite at The critical concentration or load divided, wherein the conductivity values of composition significantly increase.Lower than the threshold value, the composition is insulator, And it is higher than the threshold value, the composition becomes conductive.The partial size and geometry of filler ingredient based on graphite are to influence electric osmose Flow the factor of threshold value.

" conduction " material, ingredient, composition, product etc. --- when the term is when being described herein, with less than 10⁸Ohm- The resistivity of centimetre (Ohm-cm).Term " resistivity " can be interchanged with " volume resistivity " described below herein to be made With.

Under --- including but is not limited to high temperature --- as it is used herein, term " interaction " refers in specified conditions May occur in the covalent bond present on polymer, filler, additive or functional agent between functional group, non-covalent phase interaction With or combinations thereof formation.Covalent bond is characterized in that the electronics between functional group is shared and noncovalent interaction can wrap Include but be not necessarily limited to dipole, london dispersion force (London that hydrogen bond, ionic interaction, dipole-dipole, dipole induce Dispersion force) and π effect.

As it is used herein, term " the filler ingredient based on graphite " refers to natural or synthesis graphite material, The surface of partial size with range from 1nm to 500 micron and the functional group comprising > 0.01%.Filler ingredient based on graphite can With include but is not limited to the graphite content of untreated Standard graphite ingredient, corona treatment, acid processing/surface is modified Graphite content comprising graphite, expanded graphite, graphene, carbon fiber, carbon nanotube (CNT), Graphon or combinations thereof.

As it is used herein, term " functional group " refers to what polymer, filler, additive or functionalized agent may include And it is capable of forming any chemical group of covalent bond or noncovalent interaction.

As it is used herein, " functional agent " refers to the additive of polymer or non-polymer low molecular weight, it includes tools Body functional group, this can with the functional group being present on graphite packing surface and potentially with thermoplastic matrix phase interaction With.

As used herein, " substantially the same " composition refer to including ratio identical with composition of the invention and Component but do not include stated component reference composition.Such as, but not limited to, in some aspects of present disclosure, " no The substantially the same conductive thermoplastic compounds being blended including functional agent ingredient " are to include and the thermoplastic being blended of the invention Property the identical ratio of composition and component but not including that functional agent ingredient the conductive thermoplastic compounds being blended.

Every kind of material disclosed herein is commercially available and/or preparation method is known to those skilled in the art 's.

As used herein, the intrinsic thermal conductivity of component is based on document such as " Thermal conductivity of Nonmetallic Solids, " Y.S.Touloukian, R.W.Powell, C.Y.Ho, and P.G.Klemans, IFI/ Plenum:New York-Washington, 1970 or " Thermal Conductivity-Theory, Properties and Applications, " in T.M.Tritt, Ed., Kluwer Academic/Plenum Publishers:New York, 2004 The indicated value of description.As it is used herein, the thermal conductivity of composition is according to ISO 22007-2 (in plane and through plane (through-plane) conductivity) or ASTM E-1461 (run through multiplanar conductive rate) tested as standard.

As used herein volume resistivity at the both ends of sample stick by slotting, then at about -60 degrees Celsius Cold fracture is under (DEG C) to measure.The surface of fracture is handled with silver paint and drying.With multimeter measurement by the resistance of stick, and according to Following formula calculates volume resistivity (using Ohm (Ω)-cm as unit): volume resistivity=(R × w × h/l), and wherein R is electricity It hinders (as unit of Ω), w is the width of the stick as unit of cm, and h is the height of the stick as unit of cm, and l is as unit of cm Sample length (electrical distance).Volume resistivity can be used interchangeably herein with above-mentioned resistivity, and for measuring Volume resistivity/resistivity method is referred to herein as " SABIC method ".

The volume resistivity of untreated and pretreated graphite packing can be used filled with graphite packing and then lead to That crosses application 128 newton (N) forces real polyether-ether-ketone battery to measure.Then the VMP- of Bio-logic is attached a battery to On 300 potentiostats, to apply voltage and measure electric current, this can be further used for the resistance for determining system, and therefore count Calculate volume resistivity.The maximum volume resistivity that can be measured by this method is 1.0 × 10⁸Ω-cm。

Thermoplastic polymer components

Thermoplastic compounds according to the blending of the aspect of present disclosure include thermoplastic polymer components.In some sides In face, thermoplastic polymer components can be organic polymer.Any suitable organic polymer or organic polymer can be used The blend of object.Thermoplastic polymer components can also include polymer, copolymer, terpolymer or including aforementioned organic The combined blend of at least one of polymer.

In specific aspect, thermoplastic polymer components include polyolefin compound, polyarylene sulfide compound, polyamide Compound, petchem, polycarbonate compound, polyphenylene ether compound, polyetherimide amine compounds, polyimides chemical combination Object, the copolymer including these any compounds, including the blend and a combination thereof in these any compounds.Thermoplastic poly Polymer component may include one or more resins.

Exemplary polyolefins compound includes but is not limited to polyethylene (PE) comprising high density polyethylene (HDPE) (HDPE), line Property low density polyethylene (LDPE) (LLDPE), low density polyethylene (LDPE) (LDPE), medium density polyethylene (MDPE) and polypropylene (PP).

The specific exemplary polyolefins compound of aspect suitable for present disclosure includes but is not limited to polyethylene (PE) comprising high density polyethylene (HDPE) (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE) as described above (LDPE), the modified polyethylene of medium density polyethylene (MDPE), glycidyl methacrylate, Maleic anhydride fimctionalized poly- Ethylene, Maleic anhydride fimctionalized elastomeric ethylene copolymers (such as the EXXELOR VA1801 from ExxonMobil and VA1803), ethylene-butene copolymer, ethylene-octene copolymer, vinyl-acrylate copolymer such as ethylene-acrylic acid first Ester, ethylene-ethylacrylate and ethylene butyl acrylate copolymer, the functionalized ethylene-the third of glycidyl methacrylate Olefin(e) acid ester terpolymer, the ethylene acrylate polymers of anhydride functional, the ethylene-octene and acid anhydrides of anhydride functional Functionalized ethylene-butene copolymer, polypropylene (PP) as described above, Maleic anhydride fimctionalized polypropylene, metering system The ester modified polypropylene of acid glycidyl, polyacetals, polyacrylate, polycarbonate, polystyrene, polyester, polyamide, polyamides Amine acid imide, poly aromatic ester, polyarylsulfone (PAS), polyether sulfone, polyphenylene sulfide, polyvinyl chloride, polysulfones, polyimides, polyetherimide are gathered Tetrafluoroethene, polyether-ketone, polyether-ether-ketone, polyether ketone ketone, polyphenyl is simultaneouslyAzoles gathersDiazole, poly- benzothiazine phenothiazine, polyphenyl And thiazole, polypyrazine quinoxaline, polypyromellitimide, polyquinoxaline, polybenzimidazoles, poly- oxindole, polyoxy is for different Yin Diindyl quinoline (polyoxoisoindoline), poly- dioxoisoindolin (polydioxoisoindoline), poly- triazine are poly- to rattle away Piperazine, poly- piperazine, polypyridine, poly- piperidines, polytriazoles, poly- pyrazoles, polypyrrole alkane, poly- carborane, the miscellaneous bicyclononane of polyoxy (polyoxabicyclononane), poly-dibenzofurans, polyphenyl phthalein, polyacetals, polyanhydride, polyvinylether, polyvinyl sulfide are gathered Vinyl alcohol, polyethylene ketone, polyvinyl halides, polyethylene nitrile, polyvinyl ester, polysulfonates, polysulfide, polythioester, polysulfones, Polysulfonamide, polyureas, polyphosphazene, polysilazane, polyurethane etc., or the combination including at least one of aforesaid organic substances.

As it is used herein, " polycarbonate " refers to one or more dihydroxy chemical combination including connecting by carbonic acid ester bond Object, for example, dihydroxy aromatic compounds residue oligomer or polymer；It further include homo-polycarbonate, Copolycarbonate and (total) polyestercarbonate.

Representative polyester includes, for example including polyethylene terephthalate (" PET "), polybutylene terephthalate Ester (" PBT "), polyethylene naphthalate (PEN), polypropylene terephthalate (PTT), poly- (Isosorbide-5-Nitrae-hexamethylene diformazan Base-Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic ester) (PCCD), the copolymer of TPA, EG and secondary glycol, cyclohexanedimethanol (for example, PCTG and ) and TRITAN PETG^TMCopolyesters.

As it is used herein, polyamide be with the polymer of repetitive unit being keyed by amide, and can be with Including aliphatic polyamide (for example, various forms of nylon such as nylon 6 (PA6), nylon66 fiber (PA66) and nylon 9 (PA9)), gather Phthalamide (for example, PPA/ high-performance polyamide) and aromatic polyamides are (for example, para-aramid and meta position aromatics are poly- Amide).

In one aspect, thermoplastic polymer also acts as functional agent ingredient, condition be it include can with such as this paper into The particular functional group of functional group's interaction on the surface of the filler ingredient based on graphite of one step description, for example, but unlimited In amine, maleic anhydride, epoxy and hydroxyl.In certain aspects, Exemplary thermoplastic's polymer of functional agent ingredient can be served as Including but not limited to polyamide (including aromatic polyamides), ethylene-methyl acrylate-glycidyl acrylate copolymer, second Alkene-glycidyl methacrylate copolymer, poly- (vinyl alcohol), polybutylene terephthalate (PBT), its copolymer and its group It closes.

Thermoplastic compounds according to the blending of the aspect of present disclosure include thermoplastic of the about 20wt% to about 99wt% Property component of polymer.In specific aspect, the thermoplastic compounds of blending include thermoplastic poly of the about 20wt% to about 90wt% The thermoplasticity of polymer component, about 20wt% to the thermoplastic polymer components of about 50wt%, about 40wt% to about 90wt% polymerize The thermoplastic polymer components of object ingredient or about 40wt% to about 70wt%.Still into one side, the thermoplastic composition of blending Object includes thermoplastic polymer components of the about 20wt% to about 80wt%.

Filler ingredient based on graphite

Filler ingredient based on graphite used in terms of the present disclosure can synthetically produce or by naturally come Source processing.The partial size of filler ingredient usually in the range of about 0.1 micron (μm) to about 800 microns, and surface include > 0.01% functional group.The graphite content platelet (platelet) of typical smaller size includes more functional groups, larger ruler Very little graphite content particle includes less functional group in the edge of graphite flat surfaces.Graphite content particle can be thin The shape of piece, platelet or sphere, each shape provides the ratio of different length and diameter, and finally provides polymer graphite The thermal conductivity of packing material and the difference of conductivity.In certain aspects, the filler ingredient based on graphite is amorphous graphite, and In in other respects, it is brilliant vein graphite (crystal vein graphite).In specific aspect, the filler based on graphite Ingredient is flake graphite, and wherein flake graphite is usually found to be discrete sheet, range of the diameter at 10-800 microns In and thickness is in 1-150 microns of range and purity is in the range of about 80-99.9% carbon.In another aspect, base In the filler ingredient of graphite be spherical.

Filler ingredient based on graphite can include but is not limited to untreated Standard graphite ingredient, corona treatment Graphite content, acid processing/the modified graphite content in surface comprising graphite, expanded graphite, graphene, carbon fiber, carbon nanometer Manage (CNT), Graphon or combinations thereof.

Filler ingredient based on graphite may include the oxygen official on the edge of composition or on edge or flat surfaces It can group.

Into in one side, the functional group of the filler ingredient based on graphite includes but is not limited to carboxylic acid, hydroxyl, aldehydes or ketones base Group.In certain aspects, the functional group on the edge of graphite packing ingredient or on edge or flat surfaces can be with official The functional group of energy agent ingredient forms covalent bond or noncovalent interaction.In specific aspect, based on the filler of graphite at subpackage Include carboxylic acid functional, and functional agent ingredient includes epoxy, maleic anhydride or amine functional group, and the filler ingredient based on graphite Carboxylic acid functional and the epoxy of functional agent ingredient, maleic anhydride or amine functional group interact.This causes between graphite platelet Separation, and the distance generated between platelet leads to the decline of the increase of bulk volume resistivity and the conductivity of composition. However, it is possible to maintain acceptable thermal conduction characteristic.

In certain aspects, " acceptable thermal conduction characteristic " mean planar direction, through in-plane or in body (bulk) in the one or more in thermoplastic compounds, the thermal conductivity of the thermoplastic compounds of blending or the product being made from it It is at least 0.6 watt every meter-Kelvin (W/m-K).In specific aspect, " acceptable thermal conduction characteristic " means planar side To, in the one or more in in-plane or elastomeric thermoplastic's composition, the thermoplastic compounds of blending or be made from it The thermal conductivity of product be at least 0.9 watt every meter-Kelvin (W/m-K).In in other respects, the acceptable thermal conduction characteristic meaning Be be blended thermoplastic compounds or the product being made from it thermal conductivity for will use the composition/product application be It is sufficiently high.Again into one side, acceptable thermal conduction characteristic means the thermoplastic compounds of blending or is made from it The thermal conductivity of product is in about the 10% of the thermal conductivity of the product made of conventional heat-conducting article.It, can still into one side The thermal conduction characteristic of receiving means the thermoplastic compounds of blending or the thermal conductivity of product that is made from it is by conventional thermally conductive In about the 20% of the thermal conductivity of product made of product or in about 30% or in about 40% or in about 50%.

In certain aspects, the untreated filler ingredient based on graphite can be with other fillers at subassembly.This group Conjunction can produce the electrical isolation product with acceptable thermal conduction characteristic, this is more cost-effective for the user.

Pretreated graphite packing

In certain aspects, the filler ingredient based on graphite can be pretreated to increase the side for being located at graphite packing ingredient The content of the functional group based on oxygen on edge or edge or flat surfaces, the functional group based on nitrogen or combinations thereof.This In aspect, the amount for the functional group that can be used for interacting with functional agent ingredient will increase.

In certain aspects, pretreatment may include on the edge of graphite packing ingredient or on edge or flat surfaces Any work of covalent bond or functional group's positioning with noncovalent interaction will be formed with the functional group of functional agent ingredient Skill.

In one aspect, MAH can be introduced into the edge or flat surfaces of the filler ingredient based on graphite, so that it can be with With the functional group of functional agent ingredient, for example, but be not limited to amine and carboxylic acid group interaction, wherein functional agent ingredient include polymerization Object or non-polymer low molecular weight compositions.

In specific aspect, the thermoplastic compounds of blending may include changing as the MAH of the filler ingredient based on graphite Property graphite and polyamide as thermoplastic polymer components so that the amine end of MAH and polyamide in MAH modified graphite Group directly forms covalent bond.In the specific aspect, the amine end groups group of polyamide will make in the thermoplastic compounds of blending It works for functional agent ingredient.

The graphite packing of corona treatment

In certain aspects, the filler ingredient based on graphite include functional group based on oxygen, based on the functional group of nitrogen or its Combination.In certain aspects, the filler ingredient based on graphite can be pre-processed by plasma process and is based on graphite to increase Filler ingredient surface on the content of the functional group based on oxygen or the functional group based on nitrogen.

The corona treatment of filler ingredient based on graphite is a kind of form that surface is modified, is utilized in ionization stages Specific gas functionalized surfaces are to have functional group on the flat surfaces of graphite and on edge.This cause can with functional agent at The amount for forming the functional residues group of covalent bond or noncovalent interaction is divided to increase.It can be used for the gas of corona treatment Including but not limited to air, oxygen, nitrogen, ammonia (NH₃), argon gas, helium or combinations thereof.

In one aspect, the corona treatment of the filler ingredient granules based on graphite may include with ionization gas meter face Being modified with functionalized surfaces is to have functional group on the flat surfaces of particle and on edge, is followed by including monomer in graphite At the surface of particle the step of generating layer (that is, two-step process).In another aspect, gas/monomer mixture is used for plasma Body processing, wherein modified and generating layer (that is, step process) on the surface of graphite particle simultaneously.This causes can be with functional agent The amount that ingredient forms the functional residues group of covalent bond or noncovalent interaction increases.In these aspects, relative to not locating The filler ingredient based on graphite of reason, for the filler ingredient based on graphite of corona treatment, the stone of corona treatment The bulk resistivity level of black filler can be higher.

Into nitrogen in one side, can be used or ammonia plasma treatment carries out the corona treatment of graphite particle.Use nitrogen Or the flat surfaces and edge of ammonia plasma treatment processing graphite packing will introduce amido or amino acid on it.It is noticeable It is that in one aspect, the introducing of amido, acid etc. can lead to functional group direct phase interaction of these groups with functional agent ingredient With.

It in one aspect, can be by the radio frequency induction that is coupled with low pressure argon plasma to the filler ingredient based on graphite Sample carries out corona treatment.Into in one side, argon can be used as quenching gas, with electrodeless Atmospheric Microwave etc. Gas ions carry out corona treatment to the filler components Sample based on graphite.Into in one side, nitrogen, oxygen still can be used Gas/ar mixture, nitrogen/argon gas mixture or ammonia/ar mixture, with electrodeless Atmospheric Microwave corona treatment Filler components Sample based on graphite.In any of these aspects, other inert gases, including but not limited to helium can be replaced For argon gas.

Therefore, in one aspect, the corona treatment of these graphite particles can increase the filler based on graphite at Point edge on or the oxygen on edge and flat surfaces and/or nitrogen groups degree of functionalization.In these aspects, relative to The bulk resistivity level of the untreated filler ingredient based on graphite, the filler ingredient based on graphite of corona treatment can It is higher.

In certain aspects, the thermoplastic compounds of blending described herein include about 1wt% to about 60wt% or about The filler ingredient based on graphite of the corona treatment of 20wt% to about 50wt%, wherein composition do not include functional agent at Point.In in other respects, the thermoplastic compounds of blending include about 1wt% to about 60wt% or about 20wt% to about 50wt% Corona treatment the filler ingredient based on graphite, wherein composition includes functional agent ingredient.

The graphite packing of acid processing

It in certain aspects, can be by pre-processing the filler ingredient based on graphite using the oxidation technology of sour component.Stone The brilliant acid processing of ink sheet is a kind of using by oxidizing acid, for example, but being not limited to the oxidation of nitric acid, chromic acid, potassium chlorate and sulfuric acid Carry out the modified form in surface.In one aspect, the acid on the flat surfaces and edge or edge of the filler ingredient based on graphite It is modified that the content that can be used for the functional group based on oxygen to interact with functional agent ingredient is caused to increase.

Therefore, in one aspect, the acid modification of the filler ingredient based on graphite increases the filler ingredient based on graphite The degree of functionalization of the oxygen groups of on edge or edge and flat surfaces.In these aspects, it is based on relative to untreated The bulk resistivity level of the filler ingredient of graphite, the modified filler ingredient based on graphite of acid can be slightly higher.

In certain aspects, the thermoplastic compounds of blending described herein include about 1wt% to about 60wt% or about The filler ingredient based on graphite of the acid processing of 20wt% to about 50wt%, wherein composition does not include functional agent ingredient.At it In his aspect, the thermoplastic compounds of blending include the acid processing of about 1wt% to about 60wt% or about 20wt% to about 50wt% The filler ingredient based on graphite, wherein composition includes functional agent ingredient.

The graphite packing of gas treatment

In certain aspects, the filler ingredient based on graphite can be pre-processed by gas treatment, caused based on graphite Filler ingredient edge or edge on or surface on and can be used for the functional group of functional agent ingredient interact function The content of group increases.In certain aspects, gas treatment is high-temperature oxygen or the processing of oxygenous admixture of gas, be can wrap Include air.In certain aspects, high-temperature oxygen or the processing of oxygenous admixture of gas are between about 100 DEG C and about 500 DEG C At a temperature of carry out.Into in one side, gas treatment is ozone treatment.In certain aspects, ozone treatment can be at room temperature Or it is carried out only slight beyond at a temperature of room temperature.In one side, temperature of the ozone treatment between about 100 DEG C and about 300 DEG C Degree is lower to carry out.

In certain aspects, the thermoplastic compounds of blending described herein include about 1wt% to about 60wt% or about The filler ingredient based on graphite of the gas treatment of 20wt% to about 50wt%, wherein composition does not include functional agent ingredient.In In other aspects, the thermoplastic compounds of blending include the gas of about 1wt% to about 60wt% or about 20wt% to about 50wt% The filler ingredient based on graphite of processing, wherein composition includes functional agent ingredient.

Functional agent ingredient

Thermoplastic compounds according to the blending of aspects described herein may include functional agent ingredient.In some respects In, functional agent ingredient can have can be with functional group's shape on the edge of the filler ingredient based on graphite or edge or surface At the functional group of covalent bond or noncovalent interaction, no matter the filler ingredient based on graphite is processed or still not processed. In one aspect, functional agent ingredient may include one or more polymer or copolymer, be modified with comprising functional group, The functional group includes but is not limited to maleic anhydride (MAH) group, epoxy group, amido or combinations thereof.Still into one side, Functional agent ingredient may include non-polymer low molecular weight compositions.In another aspect, non-polymer low molecular weight compositions packet Functional group is included, the functional group includes but is not limited to maleic anhydride (MAH), epoxy group or amido.The function of functional agent ingredient Group can functional group two-way interaction with thermoplastic polymer components and with the filler ingredient based on graphite.And institute as above It discusses, in one side, if thermoplastic polymer components include can be with the functional group of the filler ingredient based on graphite The group (for example, amine end groups group of polyamide thermoplastic component of polymer) of interaction, then thermoplastic polymer components can be with Serve as functional agent ingredient.

In certain aspects, functional agent ingredient based on oxygen and/or functional group based on nitrogen and the filler based on graphite The group (for example, but being not limited to carboxylic acid group) based on oxygen on the edge of ingredient or edge or surface or the base based on nitrogen Group's (for example, but being not limited to amido) forms covalent bond or noncovalent interaction.In certain aspects, based on the filler of graphite at It is untreated for dividing, and the untreated surface or edge of functional agent ingredient and the filler ingredient based on graphite interact. Into in one side, the surface or edge of the filler ingredient based on graphite of functional agent ingredient and surface treatment interact.

Thermoplastic compounds according to the blending of the aspect of present disclosure may include one or more functional agent ingredients. In one aspect, the thermoplastic compounds of blending include the functional agent ingredient of about 0.1wt% to about 30wt%.In other respects In, the thermoplastic compounds of blending include the functional agent ingredient of about 5wt% to about 20wt%.Into in one side, functional agent at Dividing is the ingredient based on epoxy.In specific aspect, the ingredient based on epoxy may include difunctionality/multifunctional glycidyl The epoxy copolymerized object of compound.Exemplary difunctionality/multifunctional glycidyl compound includes but is not limited to ethylene-methyl-prop Olefin(e) acid ethylene oxidic ester, ethylene-methyl acrylate-glyceryl methacrylate, Ethylene-butyl acrylate-metering system Acid glycidyl ester and a combination thereof.

In certain aspects, functional agent ingredient includes maleic anhydride (MAH) group, and MAH group with based on graphite Filler ingredient based on oxygen and/or based on nitrogen functional group interaction.In certain aspects, MAH group may include double Function/multifunctional MAH compound MAH copolymer.Still into one side, MAH group includes the polyethylene, poly- of MAH grafting Propylene, its copolymer or combinations thereof.Purely illustrative functional agent ingredient including MAH group can be withTrade (brand) name obtains Derived from DuPont^TM。

In another aspect, functional agent ingredient includes thermoplastic polymer, the thermoplastic polymer include can be located at Functional group on the surface of filler ingredient based on graphite forms the functional group of covalent bond or noncovalent interaction, for example, but It is not limited to amine, MAH, epoxy and hydroxyl.It includes but is not limited to poly- for being suitable as Exemplary thermoplastic's polymer of functional agent ingredient Amide (including aromatic polyamides), ethylene-methyl acrylate-glycidyl acrylate copolymer, ethylene-methyl methacrylate contracting Water glycerol ester copolymer, poly- (vinyl alcohol), polybutylene terephthalate (PBT), its copolymer and a combination thereof.In certain aspects, Thermoplastic polymer includes thermoplastic polymer identical with thermoplastic polymer components described above.In in other respects, Thermoplastic polymer include it is one or more with it is described above include the thermoplastic polymer in thermoplastic polymer components (one or more) different thermoplastic polymer.

In specific aspect, functional agent ingredient includes thermoplastic polymer, the thermoplastic polymer include can be located at Functional group on the surface of filler ingredient based on graphite forms the functional group of covalent bond or noncovalent interaction, and as above The filler ingredient of the pretreatment based on graphite is to increase on the edge for being located at graphite packing ingredient or edge or flat table The content of functional group on face.In certain aspects, with the substantially phase that does not include the pretreated filler ingredient based on graphite With the conductive thermoplastic compounds being blended volume resistivity compared with, the volume resistance of the thermoplastic compounds of resulting blending Rate can have at least 1 × 10²Increase.

In certain aspects, the thermoplastic compounds of blending described herein include official of the about 0.1wt% to about 30wt% It can agent ingredient.In in other respects, the thermoplastic compounds of blending include the functional agent ingredient of about 5wt% to about 20wt%.

Thermally conductive and electrically insulating filler

The thermoplastic compounds of blending further comprise thermally conductive and electrically insulating filler.This filler can be thermoplastic composition Object provides non-conductive characteristic, and without negatively affecting its thermal conduction characteristic, this may be desired in certain aspects.

In certain aspects, thermally conductive and electrically insulating filler, which has, is greater than 10⁸Ohm- centimetres (Ohm-cm) of intrinsic resistance rate With the intrinsic thermal conductivity for being greater than 1 watt every meter-Kelvin (W/ (m-K)).

In one aspect, thermally conductive and electrically insulating filler includes boron nitride (BN).The suitable nitridation boron compound of one kind is six Side shape boron nitride (h-BN) can be complete h-BN or turbine layered nitride boron (t-BN).Boron nitride can be graininess The form of BN, and can be large-sized BN crystal powder, BN agglomerate, the BN particle of small size, reunion spherical BN powder, BN fiber or combinations thereof.Other thermally conductive and electrically insulating filler materials can of course be used.

In one aspect, the partial size (for example, d90 particle diameter distribution) of thermally conductive and electrically insulating filler can be at about 1 nanometer (nm) To in the range of about 500 microns (μm).In another aspect, thermally conductive and electrically insulating filler can have greater than or equal to about 3 μm, or Partial size greater than or equal to about 5 μm.Herein referred partial size is single heat conduction and electrical isolation filler particles or its any size Agglomerate.In one aspect, thermally conductive and electrically insulating filler has range in the purity of about 95% to about 99.8%.In specific aspect In, wherein thermally conductive and electrically insulating filler is BN, using with partial size (for example, d90 particle diameter distribution) of the range from 3 μm to 50 μm and The thin slice BN of the big single crystal size of BN purity more than 98%.

In in all fields, thermally conductive and electrically insulating filler can include but is not limited to BN, Mg (OH)₂、MgO、CaCO₃, dioxy SiClx, aluminium oxide, alumina silicate, ZnO, ZnS, talcum and a combination thereof.The partial size of thermally conductive and electrically insulating filler can be in about 1nm to about In the range of 500 μm.

In certain aspects, the thermoplastic compounds of blending include about 0 to about 50wt% thermally conductive and electrically insulating filler.In In other aspects, the thermoplastic compounds of blending are including about 0.1wt% to about 50wt% or about 1wt% to about 50wt% or about 2wt% to about 50wt% or about 5wt% to about 50wt% or about 10wt% to about 50wt% or about 15wt% are to about The thermally conductive and electrically insulating filler of 50wt% or about 20wt% to about 50wt%.In specific aspect, the thermoplastic compounds of blending Thermally conductive and electrically insulating filler including about 0 to about 25wt% or about 25wt% to about 50wt%.

Optional additive

Other than thermoplastic polymer resin and filler, the composition of present disclosure can also include being usually incorporated into this Various additives in the thermoplastic compounds of seed type.The mixture of additive can be used.This additive can be mixed Close the right times mixing during being used to form the component of composition.One or more additives include in thermoplastic compounds With the one or more selected features of any mechanograph for assigning thermoplastic compounds He being made from it.It may include in the disclosure The example of additive in content include but is not limited to heat stabilizer, process stabilizing agent, antioxidant, light stabilizer, plasticizer, Antistatic agent, release agent, UV absorbent, lubricant, pigment, dyestuff, colorant, flow improver additive, fire retardant or aforementioned addition One of agent or a variety of combinations.

The characteristic of the thermoplastic compounds of blending

As briefly described, present disclosure relates generally to the thermoplastic compounds being blended, and the composition includes: about The thermoplastic polymer components of 20wt% to about 99wt%；The filler ingredient based on graphite of about 1wt% to about 60wt%, the base In the filler ingredient of graphite include at least about functional group of 0.01wt% on the surface of the filler ingredient based on graphite；About The functional agent ingredient of 0.1wt% to about 30wt%；About 0 to about 50wt% thermally conductive and electrically insulating filler.Functional agent is at subpackage Include the functional group with functional group's interaction on the surface of the filler ingredient based on graphite, this cause with do not include functional agent at The volume resistivity of the substantially the same conductive thermoplastic compounds being blended divided is compared, the body of the thermoplastic compounds of blending Product resistivity at least 1 × 10²Increase.

Compared with the substantially the same conductive thermoplastic compounds being blended for not including functional agent ingredient, there is functional agent The thermoplastic compounds of the blending of the aspect according to present disclosure of ingredient have the characteristic improved, which has With the functional group of functional group's interaction on the surface of the filler ingredient based on graphite.Specifically, with substantially the same The thermoplastic compounds that conduction is blended are compared, and the interaction of functional group provides for the thermoplastic compounds of blending to be dramatically increased Volume resistivity and therefore reduce conductivity.In certain aspects, according to the thermoplastic of the blending of the aspect of present disclosure Property composition lower than electroosmotic flow threshold value or nonconducting, and the thermoplastic compounds of substantially the same blending are higher than electroosmotic flow Threshold value and be therefore conductive.

As described more fully below, in certain aspects, discovery functional agent ingredient and the filler based on graphite are at grouping The interaction of conjunction provides increased volume resistivity for the thermoplastic compounds being blended, while still providing acceptable thermally conductive spy Property.This interaction between the functional group of these components provides the spy of raising in the solution based on graphite of low cost Property, it should be high-termal conductivity based on the solution of graphite, and conductivity does not substantially less than include the substantially the same of functional agent ingredient The conductive thermoplastic compounds being blended.As a result, can according to the thermoplastic compounds of the blending into one side of present disclosure With the high filler ingredient load based on graphite --- otherwise, for substantially the same in the case where no functional agent ingredient Blending thermoplastic compounds, load will be above electroosmotic flow threshold value (and thermoplastic compounds of substantially the same blending To be therefore conductive) --- but it is lower than electroosmotic flow threshold value according to the thermoplastic compounds of the blending of the aspect of present disclosure (that is, being nonconducting).

Manufacturing method

It can be formed according to any conventional method according to the thermoplastic compounds of the blending of aspects described herein.Some In aspect, composition is melt blending.The melt blending of thermoplastic compounds be related to using shearing force, drawing force, compressing force, Ultrasonic energy, electromagnetic energy, thermal energy or the combination including at least one aforementioned power or form of energy, and carried out in processing unit (plant), Wherein above-mentioned power or form of energy are by single screw rod, multiscrew, intermeshing rotating Vortex or contra rotating screw, non-phase Rotating Vortex or contra rotating screw, reciprocating screw, the screw rod with pin, the screw rod with sieve, the bucket with pin, roller, column mutually engaged Fill in (ram), helical rotor or including aforementioned at least one combination.

The melt blending for being related to above-mentioned power can carry out in following machines, such as single screw rod or multi-screw extruder, Buss kneader, Henschel, helicones, Ross mixer, Banbury, roller mill, mould machine such as injection molding machine, vacuum Molding machine, blow moulding machine etc., or at least one combination including aforementioned machines.In one aspect, extrusion is to use twin-screw extrusion What machine was completed.

In one aspect, can first by the thermoplastic polymer components of powder type, pellet form, sheet-form etc. with Filler ingredient, functional agent ingredient based on graphite, optional thermally conductive and electrically insulating filler and optional additive are in Henschel Or dry blend in roller mill, it is then fed in melt blending equipment such as extruder or Buss kneader.May expect will One of these components a variety of are introduced into melt blending equipment with master batch form.In such a process, masterbatch can be existed The downstream for being introduced into the point of thermoplastic polymer components is introduced into melt blending equipment.

Melt blended material is such blend, wherein if thermoplastic polymer components are hemicrystalline organic polymers Object, at least part of thermoplastic polymer components reach the temperature for being greater than or equal to about melting temperature, or if thermoplasticity Polymers compositions is amorphous resin during Blending Processes, and at least part of thermoplastic polymer components, which reaches, to be higher than or wait In the temperature of pour point (for example, glass transition temperature).Dry blends are such blends, wherein if thermoplastic poly Polymer component is hemicrystalline polymer, and the total quality of thermoplastic polymer components is in less than or equal to about melting temperature At a temperature of, or if thermoplastic polymer components be amorphous polymer and wherein thermoplastic polymer components in Blending Processes Period is in substantially free of any any liquid-like fluid, the total quality of thermoplastic polymer components less than or equal to pour point Temperature.As herein defined, solution blending object is such blend, and wherein thermoplastic polymer components are in the Blending Processes phase Between be suspended in any liquid-like fluid such as such as solvent or non-solvent.

If desired, include the blending of thermoplastic polymer components and other components thermoplastic compounds can undergo it is more A blending and forming step.For example, pellet can be squeezed out and is configured to by the thermoplastic compounds of blending first.Then it can incite somebody to action Pellet is fed in mould machine, it can be shaped as any desired shape or product there.It is alternatively possible to will be from single The mouldable composition of melt blending machine is configured to sheet material or stock (strand), and extrusion process after experience, such as annealing, single shaft Or it is biaxially oriented.

In one aspect, for the purpose of coated substrate, can by thermoplastic polymer components, based on the filler of graphite at Divide, functional agent ingredient, optional thermally conductive and electrically insulating filler and optional additive disperse and/or dissolve in the solution.

Into in one side, if it is desired, can make include thermoplastic polymer components, the filler ingredient based on graphite, The thermoplastic compounds experience of the blending of functional agent ingredient, optional thermally conductive and electrically insulating filler and optional additive is multiple total Mix forming step.For example, pellet can be squeezed out and is configured to by the thermoplastic compounds of blending first.It then can be by pellet It is fed in mould machine, it can be shaped as any desired shape or product there.It is alternatively possible to which single melting will be left The thermoplastic compounds of the blending of blender are configured to sheet material or stock, and extrusion process after experience, for example anneal, uniaxially or biaxially Orientation.

In one aspect, hybrid manipulation include by based on graphite filler ingredient and functional agent ingredient be fed in extruder With formed can by further squeeze out or injection molding technology further processing component.In one aspect, extruder is twin-screw Extruder.Into in one side, the direct mixing of the thermoplastic compounds of blending and extrusion can be used to form product.

In certain aspects, after mixing thermoplastic polymer components and functional agent ingredient, by filling out based on graphite Expect that ingredient introduces the thermoplastic compounds being blended.It can be by optional thermally conductive and electrically insulating filler ingredient and based on the filler of graphite Ingredient is fed together or separately.Into in one side, filler ingredient, functional agent ingredient based on graphite and optional thermally conductive and electric Insulating packing ingredient is fed as masterbatch, and wherein masterbatch includes one of these components or a variety of.

Technology well known by persons skilled in the art can be used by the thermoplastic of the blending formed according to the method described in this article Property composition be configured to mouldable materials in storage (stock material) or mouldable product.

Product

As discussed herein, the thermoplastic compounds of the blending of present disclosure can be shaped as product.On the one hand In, which is mechanograph.In certain aspects, during the heat or heat dissipation management which is used to need to be electrically insulated are applied. Electronic device is including but not limited to directly printed on thermoplasticity radiator by example, directly overmolded electronic device such as wraps Cover LED lead frame in the application of formed automobile headlamp, automobile ECU shell, electronic control unit and/or mobile phone it is outer Electronics in shell and frame, IC chip and flash bracket, electronic packaging, thermal interfacial material (TIM), computer and consumer appliances Component, middle end-receiver, solar battery and battery pack such as processor, lamp, LED light, motor, circuit, electronic device Encapsulation, such as coil or shell, solar cell backboard and battery case.

Use the method for the thermoplastic compounds of blending

It can be used in above-mentioned one or more applications by the product that the thermoplastic compounds of blending described herein are formed.In In some aspects, which can be exposed to raised constant temperature for a period of time, and the thermoplastic compounds being blended will have Specific thermal conductivity and volume resistivity requirement, to allow product to maintain its property when being exposed to persistently raised temperature condition Energy.In certain aspects, temperature may be extreme, and the time may be very long.In specific aspect, product can be exposed to about 40 degrees Celsius (DEG C) to about 250 DEG C of raised temperature, and for about 24 hours to about 30 years time.In some aspects In, product is used to need in the application for the thermoplastic compounds being blended with leading at least 0.6 watt every meter-Kelvin (W/mK) Heating rate and at least 1 × 10⁵The volume resistivity of Ohm-cm.

Therefore, it is related to the thermoplastic compounds of blending being used for high thermal conductivity and reduced conduction in terms of present disclosure The method of rate product, this method comprises:

It will include that raised temperature is exposed to according to the product of the thermoplastic compounds of the blending of either side described herein Degree continues for some time,

To have at least 0.6 watt every meter-Kelvin in the application for the thermoplastic compounds that wherein product is used to need to be blended (W/mK) thermal conductivity and at least 1 × 10⁵The volume resistivity of Ohm-cm.

In specific aspect, raised temperature includes about 40 degrees Celsius (DEG C) to about 250 DEG C of temperature, and the duration Including about 24 hours to about 30 years time.

Without being further described, it is believed that description herein can be used to utilize present disclosure in those skilled in the art. Including following instance, to provide additional guidance to the those skilled in the art for practicing disclosure claimed.It is provided Example be only the representative of work, and facilitate the introduction of present disclosure.Therefore, these examples limit in any way unintentionally Present disclosure processed.

Although can be in specific legal classification, for example present disclosure is described and claimed as in the legal classification of system Aspect, but this is used merely for convenience, and it will be apparent to one skilled in the art that can describe in any legal classification With each aspect of claimed present disclosure.Unless expressly stated otherwise, being otherwise never intended to will be set forth herein any Method or aspect are construed to that its step is required to execute with particular order.Therefore, in claim to a method not in claims Or clearly stated in specification in the case that step will be restricted to particular order, this is not intended to infer in any way suitable Sequence.This is suitable for any possible non-express basis for interpretation, asks including logic related with the arrangement of step or operating process Topic, described in the ordinary meaning or specification obtained from grammatical organization or punctuation mark in terms of quantity or type.

In entire the application, various publications are referred to.Disclosures of these publications are by reference with its entirety It is incorporated herein, so that the state of its fields is described more fully with.Discussed in sentence for the documents of reference The material for including in documents, disclosed documents also by reference by individually and be specifically incorporated into herein.Herein In any content should be construed as recognizing that the disclosure is had no right by first disclosure and earlier than such publication.In addition, Publication date provided herein may be different from the practical publication date, and the practical publication date may need independent confirmation.

Aspect

In in all fields, this disclosure relates to and including at least following aspects.

Aspect 1: a kind of thermoplastic compounds of blending comprising following, formed or be substantially made of following by following:

(a) thermoplastic polymer components of about 20wt% to about 99wt%；

(b) the filler ingredient based on graphite of about 1wt% to about 60wt% is somebody's turn to do the filler ingredient based on graphite and is included in base In at least about functional group of 0.01wt% on the surface of the filler ingredient of graphite；

(c) the functional agent ingredient of about 0.1wt% to about 30wt%；With

(d) about 0 to about 50wt% thermally conductive and electrically insulating filler,

Wherein functional agent ingredient includes the function with functional group's interaction on the surface of the filler ingredient based on graphite Group, this causes and the volume resistivity phase for the substantially the same conductive thermoplastic compounds being blended for not including functional agent ingredient Than the volume resistivity of the thermoplastic compounds of blending at least 1 × 10²Increase.

Aspect 2: according to the thermoplastic compounds of blending described in aspect 1, wherein thermoplastic polymer components include polyene Hydrocarbon compound, polyarylene sulfide compound, polyamide compound, petchem, polycarbonate compound, polyphenylene oxide chemical combination Object, polyetherimide amine compounds, the copolymer including these any compounds, the blend including these any compounds and A combination thereof.

Aspect 3: the thermoplastic compounds of the blending according to aspect 1 or 2, wherein the table of the filler ingredient based on graphite Functional group on face includes the functional group based on oxygen, the functional group based on nitrogen or combinations thereof.

Aspect 4: according to the thermoplastic compounds of blending described in aspect 3, wherein the filler ingredient based on graphite is located in advance Manage the content of the functional group based on oxygen or the functional group based on nitrogen on the surface to increase the filler ingredient based on graphite.

Aspect 5: according to the thermoplastic compounds of blending described in aspect 3, wherein the functional group based on oxygen includes carboxylic acid official It can group.

Aspect 6: according to the thermoplastic compounds of blending described in aspect 3, wherein the functional group based on nitrogen includes amine function Group.

Aspect 7: the thermoplastic compounds of the blending according to either side in aspect 3 to 6, wherein passing through plasma Technique pre-process functional group on surface of the filler ingredient based on graphite to increase the filler ingredient based on graphite based on oxygen or The content of functional group based on nitrogen.

Aspect 8: according to the thermoplastic compounds of blending described in aspect 7, wherein the plasma process is environment etc. Ionomer technology.

Aspect 9: the thermoplastic compounds of the blending according to either side in aspect 3 to 6, wherein passing through oxidation technology It pre-processes the functional group on surface of the filler ingredient based on graphite to increase the filler ingredient based on graphite based on oxygen or is based on The content of the functional group of nitrogen.

Aspect 10: according to the thermoplastic compounds of blending described in aspect 9, wherein being located in advance with sour component by oxidation technology Manage the filler ingredient based on graphite.

Aspect 11: according to the thermoplastic compounds of blending described in aspect 10, wherein the sour component includes nitric acid, chromium Acid, potassium chlorate, sulfuric acid or combinations thereof.

Aspect 12: the thermoplastic compounds of the blending according to either side in aspect 1 to 11, wherein functional agent ingredient Including component of polymer, which includes epoxy-functional, maleic anhydride functional groups, amine functional group or combinations thereof.

Aspect 13: the thermoplastic compounds of the blending according to either side in aspect 1 to 11, wherein functional agent ingredient Including non-polymer low molecular weight compositions, which includes epoxides, maleic anhydride, amine or its group It closes.

Aspect 14: the thermoplastic compounds of the blending according to either side in aspect 1 to 13, wherein functional agent ingredient It interacts with the functional group of the filler ingredient based on graphite.

Aspect 15: according to the thermoplastic compounds of blending described in aspect 14, wherein functional agent ingredient and based on graphite Interaction between the functional group of filler ingredient includes covalent bond or noncovalent interaction.

Aspect 16: the thermoplastic compounds of the blending according to either side in aspect 1 to 15, wherein thermally conductive and electric exhausted Edge filler includes boron nitride, Mg (OH)₂、MgO、CaCO₃, silica, aluminium oxide, alumina silicate, ZnO, ZnS, talcum and its group It closes.

Aspect 17: a method of the thermoplastic compounds of blending are used for high thermal conductivity and reduced conductivity product, This method include it is following, formed or be substantially made of following by following:

It will include that the product of thermoplastic compounds of the blending according to either side in aspect 1 to 16 is exposed to raising Constant temperature for a period of time,

To have at least 0.6 watt of every meter -Kai Er in the application for the thermoplastic compounds that wherein product is used to need to be blended The thermal conductivity and at least 1 × 10 of literary (W/mK)⁵The volume resistivity of Ohm-cm.

Aspect 18: according to method described in aspect 17, wherein raised temperature includes about 40 degrees Celsius (DEG C) to about 250 DEG C Temperature, and the duration includes about 24 hours to about 30 years time.

Aspect 19: the method according to aspect 17 or 18, wherein application be consumer-electronics applications, LED illumination application or Electric power application.

Aspect 20: the method according to either side in aspect 17 to 19, wherein product is mechanograph.

Aspect 21: a kind of thermoplastic compounds of blending comprising following, be made of or following substantially by following group At:

(a) thermoplastic polymer components of about 20wt% to about 99wt%；

(b) the pretreated filler ingredient based on graphite of about 1wt% to about 60wt%, this is pretreated based on graphite Filler ingredient includes at least about functional group of 0.01wt% on the surface of the filler ingredient pretreated based on graphite；

(c) the functional agent ingredient of about 0.1wt% to about 30wt%；With

(d) about 0 to about 50wt% thermally conductive and electrically insulating filler,

Wherein the pretreated filler ingredient based on graphite be pretreated with increase it is pretreated based on the filler of graphite at The content of the functional group on surface divided, and

Functional agent ingredient includes thermoplastic polymer, which includes and the pretreated filler based on graphite The functional group of functional group's interaction on the surface of ingredient, this causes and does not include the pretreated filler ingredient based on graphite The volume resistivities of the substantially the same conductive thermoplastic compounds being blended compare, the volume of the thermoplastic compounds of blending Resistivity at least 1 × 10²Increase.

Aspect 22: according to the thermoplastic compounds of blending described in aspect 21, wherein the functional group of functional agent ingredient includes Amido, maleic groups, epoxy group, hydroxyl or combinations thereof.

Aspect 23: the thermoplastic compounds of the blending according to aspect 21 or 22, wherein functional agent ingredient includes polyamides Amine, ethylene-methyl acrylate-glycidyl acrylate copolymer, gather at ethylene-methyl methacrylate glycidyl ester copolymer (vinyl alcohol), polybutylene terephthalate (PBT), its copolymer and a combination thereof.

Aspect 24: the thermoplastic compounds of the blending according to either side in aspect 21 to 23, wherein thermoplastic poly Polymer component and functional agent ingredient include identical thermoplastic polymer.

Aspect 25: the thermoplastic compounds of the blending according to either side in aspect 21 to 23, wherein thermoplastic poly Polymer component and functional agent ingredient include different thermoplastic polymers.

Aspect 26: the thermoplastic compounds of the blending according to either side in aspect 21 to 25, wherein pretreated Functional group on the surface of filler ingredient based on graphite includes the functional group based on oxygen, the functional group based on nitrogen or combinations thereof.

Aspect 27: according to the thermoplastic compounds of blending described in aspect 26, wherein the functional group based on oxygen includes carboxylic acid Functional group.

Aspect 28: according to the thermoplastic compounds of blending described in aspect 26, wherein the functional group based on nitrogen includes amine official It can group.

Aspect 29: the thermoplastic compounds of the blending according to either side in aspect 26 to 28, wherein by it is equal from Plasma process pre-processes the pretreated filler ingredient based on graphite to increase the pretreated filler ingredient based on graphite Surface on the functional group based on oxygen or the functional group based on nitrogen content.

Aspect 30: according to the thermoplastic compounds of blending described in aspect 29, wherein plasma process be environment etc. from Plasma process.

Aspect 31: the thermoplastic compounds of the blending according to either side in aspect 26 to 28, wherein passing through oxidation Technique pre-processes the pretreated filler ingredient based on graphite to increase the table of the pretreated filler ingredient based on graphite The content of the functional group based on oxygen on face or the functional group based on nitrogen.

Aspect 32: according to the thermoplastic compounds of blending described in aspect 31, wherein pre- by oxidation technology with sour component Handle the pretreated filler ingredient based on graphite.

Aspect 33: according to the thermoplastic compounds of blending described in aspect 32, wherein sour component includes nitric acid, chromic acid, chlorine Sour potassium, sulfuric acid or combinations thereof.

Aspect 34: the thermoplastic compounds of the blending according to either side in aspect 21 to 33, wherein functional agent at Divide and interacts with the functional group of the pretreated filler ingredient based on graphite.

Aspect 35: according to the thermoplastic compounds of blending described in aspect 34, wherein functional agent ingredient and pretreated base Interaction between the functional group of the filler ingredient of graphite includes covalent bond or noncovalent interaction.

Aspect 36: the thermoplastic compounds of the blending according to either side in aspect 21 to 35, wherein thermally conductive and electric Insulating packing includes boron nitride, Mg (OH)₂、MgO、CaCO₃, silica, aluminium oxide, alumina silicate, ZnO, ZnS, talcum and its group It closes.

Aspect 37: the thermoplastic compounds of the blending according to either side in aspect 21 to 36, wherein thermoplastic poly Polymer component includes polyolefin compound, polyarylene sulfide compound, polyamide compound, petchem, polycarbonate Close object, polyphenylene ether compound, polyetherimide amine compounds, the copolymer including these any compounds including these any changes Close the blend and a combination thereof of object.

Aspect 38: the method that the thermoplastic compounds of blending are used for high thermal conductivity and reduced conductivity product, the party Method include it is following, formed or be substantially made of following by following:

It will include that the product of thermoplastic compounds of the blending according to either side in aspect 21 to 37 is exposed to liter High constant temperature for a period of time,

To have at least 0.6 watt of every meter -Kai Er in the application for the thermoplastic compounds that wherein product is used to need to be blended The thermal conductivity and at least 1 × 10 of literary (W/mK)⁵The volume resistivity of Ohm-cm.

Aspect 39: according to method described in aspect 38, wherein raised temperature includes about 40 degrees Celsius (DEG C) to about 250 DEG C Temperature, and the duration includes about 24 hours to about 30 years time.

Aspect 40: the method according to aspect 38 or 39, wherein application be consumer-electronics applications, LED illumination application or Electric power application.

Aspect 41: the method according to either side in aspect 38 to 40, wherein product is mechanograph.

Aspect 42: the thermoplastic compounds of the blending according to either side in aspect 3 to 6, wherein passing through plasma One of body technology, oxidation technology, high temperature air technique or ozone process or a variety of filler ingredients of the pretreatment based on graphite The functional group based on oxygen on surface to increase the pretreated filler ingredient based on graphite or the functional group based on nitrogen contain Amount.

Aspect 43: the thermoplastic compounds of the blending according to either side in aspect 26 to 28, wherein by it is equal from One of plasma process, oxidation technology, high temperature air technique or ozone process or a variety of pretreatments are described pretreated is based on Functional group based on oxygen on surface of the filler ingredient of graphite to increase the pretreated filler ingredient based on graphite is based on The content of the functional group of nitrogen.