CN103862589B - A kind of melt blending prepares the method for polyamide-based heat-conductive composite material - Google Patents
A kind of melt blending prepares the method for polyamide-based heat-conductive composite material Download PDFInfo
- Publication number
- CN103862589B CN103862589B CN201210562507.7A CN201210562507A CN103862589B CN 103862589 B CN103862589 B CN 103862589B CN 201210562507 A CN201210562507 A CN 201210562507A CN 103862589 B CN103862589 B CN 103862589B
- Authority
- CN
- China
- Prior art keywords
- polyamide
- heat
- composite material
- conductive composite
- tlcp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a kind of method that melt blending prepares polyamide 6 base heat-conducting plastic, comprise the steps: the first step, do carrier with the elastomer containing polar group, coupling agent treatment heat conduction inorganic filler particle, antioxidant, UV light stabilizing agent etc. are reinstated double screw extruder and prepares multifunctional concentrate；Second step, utilized double screw extruder to prepare heat-conductive composite material together with master batch polyamide 6, TLCP are prepared with the first step.The polyamide 6 based composites that the present invention prepares, there is good heat conductivity, molding processibility and mechanical performance, be suitable to injection mo(u)lding, can be widely applied to electronic apparatus, phone housing and LED lamp goods, improve the product heat dispersion when high temperature, increase the service life.
Description
Technical field
The present invention relates to the preparation method of a kind of polymer matrix composite with high thermal conductance, particularly relating to a kind of being applicable to can be with the preparation method with heat-conducting polymer/inorganic composite materials of injection mo(u)lding.
Background technology
Along with the high speed development of information technology, electronic devices and components and electronic equipment develop to the direction of " thin, light, little ", current densities and load capacity increase sharply, and the local temperature of electronic component can be caused drastically to raise and reduce the life-span.Traditional cooling electronic component main body, radiation cooling plate etc. mainly by metal material, pottery, Machining of Ceramics difficulty, quality weight, are unfavorable for that electronic apparatus develops to the direction of " thin, light, little ".Therefore have heat conductivity, light weight, engineering plastics that specific strength is high are the ideal material of novel electron electric elements.
Macromolecular material because degree of crystallinity is low heat conductivity poor, it is impossible to meet the requirement of electronic devices and components high-cooling property, it is therefore desirable to its heat conductivity is carried out improve modification.Generally improve the method aluminium oxide, boron nitride, carbon fiber or the metal dust such as copper powder, aluminium powder etc. mainly by high heat conduction of plastics heat conductivity, get off to improve its heat conductivity at higher loading (typically at about 80wt%), but, this also reduces the mechanical characteristic that the excellent processing and forming of macromolecule itself is raw and tougher simultaneously.
Existing technology is the heat-conducting plastic using simple melt blending to prepare high filler loading capacity mostly, because filler and resin matrix are difficult to mix homogeneously because of the difference of volume, relatively big to processing and forming and Effect on Mechanical Properties, and heat conductivity improves the most restricted.The present patent application person uses and adds suitable liquid crystal polymer in resin matrix, while obtaining high thermal conductivity, keeps excellent processing characteristics.
Summary of the invention
It is an object of the invention to solve, by the method for melt blending, the problem that macromolecular material heat conductivity is low, it is provided that a kind of preparation method making the excellent polyamide-based heat conduction engineering plastics of high heat conduction, mechanical property and processing characteristics.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of melt blending prepares the method for polyamide-based heat-conductive composite material, comprises the steps:
Step 1. utilizes the elastomer of polar group graft modification to do carrier, the nano heat-conductive filler of coupling agent modified mistake, antioxidant are made multifunctional mother granules together with ultraviolet light stabilizer in double screw extruder, keeping extrusion temperature is 120 DEG C～140 DEG C, extruding pelletization；
Multifunctional mother granules, polyamide 6 and the TLCP mix homogeneously that step 1 is prepared by step 2., 80 DEG C of vacuum is dried 4 hours together, is then added in double screw extruder, and keeping extrusion temperature is 220 DEG C～270 DEG C, extruding pelletization.
Further, in described step 1, described vector resin can be the one in the ethylene-octene copolymer (POE-g-MAH) of the ethylene propylene diene rubber (EPDM-g-MAH) of maleic anhydride grafting, maleic anhydride grafting；Described heat filling is one or more mixture in nano level aluminium oxide, silicon nitride, aluminium powder, carbon fiber, and wherein powder particle size is less than 100nm, and fibre diameter is less than 30nm, and draw ratio is 50: 1～100: 1；Described antioxidant is antioxidant 1010, the one of irgasfos 168 or mixture；Described ultraviolet light stabilizer is the one in UV-531, TINUVIN 770 or mixture,
Further, the mass ratio of the various material vector resin/heat filling/antioxidant/ultraviolet light stabilizers in described step 1 is 10～40: 400～700: 0.5～1.5: 1～5.
Further, the fusing point of the liquid crystal polymer in described step 2 is at about 260 DEG C, and its consumption is the 10%～15% of polyamide quality.
The technology of the present invention optimal case is: the composition of polyamide-based heat-conductive composite material prepared by a kind of melt-mixing method, polyamide 6: liquid crystal polymer: heat filling: vector resin: antioxidant: the quality proportioning of ultraviolet light stabilizer is 100: 15: 600: 40: 1.5: 1, wherein the particle diameter of heat filling is respectively less than 100nm, fibre diameter is less than 30nm, and draw ratio is 50: 1～100: 1；Heat filling coupling agent is titanate esters NDZ-311, and its consumption is the 1% of inorganic nanoparticles protonatomic mass.
Compared with prior art, the present invention has the benefit that TLCP can improve the flow processability of polyamide 6；Meanwhile, liquid crystal forms fento in polyamide 6 matrix resin, advantageously forms complete thermal conductive network chain structure, additionally plays the effect of heterogeneous nucleation, improves polyamide 6 intrinsic thermal conductivity, is conducive to improving composite heat-conductive characteristic.It is also advantageous for improving auxiliary agent dispersibility in polymeric matrix additionally, multifunctional mother granules made by various auxiliary agents by the present invention, heat conductivity and the mechanical property of polyamide 6 based composites can be improved.Because the high comprehensive performances such as the composite heat conductivility that the present invention prepares and mechanics.
Detailed description of the invention:
With specific embodiment, technical scheme is described below, but protection scope of the present invention is not limited to this:
Embodiment 1
First heat filling 400g is carried out surface process with the coupling agent NDZ-311 of 0.5% in homogenizer；Then vector resin/heat filling/antioxidant/ultraviolet light stabilizer one that mass ratio is 10: 400: 0.5: 1 being reinstated double screw extruder pelletize and prepare multifunctional mother granules, extruder barrel temperature controls at 120 DEG C～140 DEG C；Finally prepared multifunctional mother granules is mixed homogeneously with the polyamide 6 of 100g and the TLCP of 10g, 80 DEG C of vacuum is dried 4 hours together, utilizing double screw extruder extrusion preparation polyamide-based heat-conductive composite material, barrel temperature controls at 210 DEG C～280 DEG C, keeps vacuum equipment to open.
Above-mentioned prepared heat-conductive composite material is through injection sample preparation, and the performance test results is as follows: pyroconductivity is 6.5W/m k, hot strength 61.5MPa, bending strength 73.7MPa, notch impact strength 14.6KJ/m2, degree of crystallinity is 35%, and melt index is 135g/10min.
Embodiment 2
First heat filling 400g is carried out surface process with the coupling agent NDZ-311 of 1% in homogenizer；Then vector resin/heat filling/antioxidant/ultraviolet light stabilizer one that mass ratio is 40: 400: 0.5: 1 being reinstated double screw extruder pelletize and prepare multifunctional mother granules, extruder barrel temperature controls at 120 DEG C～140 DEG C；Finally prepared multifunctional mother granules is mixed homogeneously with the polyamide 6 of 100g and the TLCP of 10g, 80 DEG C of vacuum is dried 4 hours together, utilizing double screw extruder extrusion preparation polyamide-based heat-conductive composite material, barrel temperature controls at 210～280 DEG C, keeps vacuum equipment to open.
Above-mentioned prepared heat-conductive composite material is through injection sample preparation, and the performance test results is as follows: pyroconductivity is 5.7W/m k, hot strength 56.3MPa, bending strength 64.7MPa, notch impact strength 19.5KJ/m2, degree of crystallinity is 31%, and melt index is 128g/10min.
Embodiment 3
First heat filling 700g is carried out surface process with the titanate coupling agent NDZ-311 of 1.5% in homogenizer；Then vector resin/heat filling/antioxidant/ultraviolet light stabilizer one that mass ratio is 10: 700: 1: 3 being reinstated double screw extruder pelletize and prepare multifunctional mother granules, extruder barrel temperature controls at 120 DEG C～140 DEG C；Finally prepared multifunctional mother granules is mixed homogeneously with the polyamide 6 of 100g and the TLCP of 10g, 80 DEG C of vacuum is dried 4 hours together, utilizing double screw extruder extrusion preparation polyamide-based heat-conductive composite material, barrel temperature controls at 210～280 DEG C, keeps vacuum equipment to open.
Above-mentioned prepared heat-conductive composite material is through injection sample preparation, and the performance test results is as follows: pyroconductivity is 9.5W/m k, hot strength 69.4MPa, bending strength 64.7MPa, notch impact strength 10.8KJ/m2, degree of crystallinity is 37%, and melt index is 119g/10min.
Embodiment 4
First heat filling 700g is carried out surface process with the coupling agent NDZ-311 of 1.5% in homogenizer；Then vector resin/heat filling/antioxidant/ultraviolet light stabilizer one that mass ratio is 40: 700: 1: 3 being reinstated double screw extruder pelletize and prepare multifunctional mother granules, extruder barrel temperature controls at 120 DEG C～140 DEG C；Finally prepared multifunctional mother granules is mixed homogeneously with the polyamide 6 of 100g and the TLCP of 10g, 80 DEG C of vacuum is dried 4 hours together, utilizing double screw extruder extrusion preparation polyamide-based heat-conductive composite material, barrel temperature controls at 210～280 DEG C, keeps vacuum equipment to open.
Above-mentioned prepared heat-conductive composite material is through injection sample preparation, and the performance test results is as follows: pyroconductivity is 9.0W/m k, hot strength 67.2MPa, bending strength 66.8MPa, notch impact strength 13.5KJ/m2, degree of crystallinity is 36%, and melt index is 126g/10min.
Embodiment 5
First heat filling 700g is carried out surface process with the coupling agent NDZ-311 of 1.5% in homogenizer；Then vector resin/heat filling/antioxidant/ultraviolet light stabilizer one that mass ratio is 10: 700: 1: 3 being reinstated double screw extruder pelletize and prepare multifunctional mother granules, extruder barrel temperature controls at 120 DEG C～140 DEG C；Finally prepared multifunctional mother granules is mixed homogeneously with the polyamide 6 of 100g and the TLCP of 15g, 80 DEG C of vacuum is dried 4 hours together, utilizing double screw extruder extrusion preparation polyamide-based heat-conductive composite material, barrel temperature controls at 210～280 DEG C, keeps vacuum equipment to open.
Above-mentioned prepared heat-conductive composite material is through injection sample preparation, and the performance test results is as follows: pyroconductivity is 12.5W/m k, hot strength 73.7MPa, bending strength 69.6MPa, notch impact strength 9.8KJ/m2, degree of crystallinity is 42%, and melt index is 134g/10min.
Claims (3)
1. the method that the method for melt blending prepares polyamide 6 base heat-conductive composite material, is characterized in that comprising the steps:
Step 1. utilizes the elastomer of polar functionalities to do vector resin, by the nano heat-conductive filler of coupling agent modified mistake, antioxygen
Multifunctional mother granules is made in agent together with ultraviolet light stabilizer in double screw extruder, and keeping extruder temperature is 120 DEG C
～140 DEG C, described vector resin is the ethylene propylene diene rubber (EPDM-g-MAH) of maleic anhydride grafting, maleic anhydride grafting
One in ethylene-octene copolymer (POE-g-MAH)；Described heat filling is two in aluminium oxide, aluminium powder, carbon fiber
Planting or multiple mixing, the particle diameter of wherein said heat filling is respectively less than 100nm, and the diameter of carbon fiber is less than 30nm and length
Footpath ratio is between 50:1～100:1；
Multifunctional mother granules, polyamide 6 and the TLCP mix homogeneously that step 1 is prepared by step 2., the most very
Drying 4 hours, be then added to pelletize in double screw extruder for empty 80 DEG C, keeping extrusion temperature is 220 DEG C～280 DEG C；Described
Liquid crystal polymer be fusing point 260 DEG C backbone chain type TLCP poly-(4-HBA/2-hydroxyl-6-naphthoic acid) tree
Fat (TLCP Vectra A950).
2. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, it is characterised in that described composite
It is made up of, respectively polyamide 6, TLCP, heat filling, vector resin, antioxidant, ultraviolet light stabilizer
The parts by weight of component are as follows:
3. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, it is characterised in that in described step 1
Antioxidant be four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite
The mixture of the one or two kinds of in (2,4-di-tert-butyl-phenyl) (irgasfos 168)；Ultraviolet light stabilizer is 2-hydroxyl
-4-oxy-octyl benzophenone (UV-531), in double (2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN 770)
Plant or the mixture of two kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210562507.7A CN103862589B (en) | 2012-12-18 | 2012-12-18 | A kind of melt blending prepares the method for polyamide-based heat-conductive composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210562507.7A CN103862589B (en) | 2012-12-18 | 2012-12-18 | A kind of melt blending prepares the method for polyamide-based heat-conductive composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103862589A CN103862589A (en) | 2014-06-18 |
| CN103862589B true CN103862589B (en) | 2016-08-24 |
Family
ID=50901905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210562507.7A Expired - Fee Related CN103862589B (en) | 2012-12-18 | 2012-12-18 | A kind of melt blending prepares the method for polyamide-based heat-conductive composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103862589B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448814B (en) * | 2014-11-27 | 2016-05-11 | 湖北洋田塑料制品有限公司 | The high rigidity liquid crystal polymer of a kind of high strength reinforced nylon 66 compounds and preparation method thereof |
| CN105367966B (en) * | 2015-11-10 | 2017-05-17 | 西安科技大学 | Heat-conduction mixed polymer and preparation method thereof |
| CN105255086B (en) * | 2015-11-10 | 2017-03-29 | 西安科技大学 | A kind of heat conduction blended polymer material and its preparation technology |
| CN108587155A (en) * | 2018-05-25 | 2018-09-28 | 郑州智锦电子科技有限公司 | A kind of heat conduction polyamide compoiste material and preparation method thereof |
| CN108727813A (en) * | 2018-05-25 | 2018-11-02 | 郑州智锦电子科技有限公司 | A kind of LED light sheathing material |
| CN111635574B (en) * | 2020-06-19 | 2022-08-09 | 中北大学 | PP/PE/BN/EPDM heat-conducting insulating material and preparation method thereof |
| CN114031934B (en) * | 2021-12-15 | 2023-07-04 | 宁波公牛光电科技有限公司 | Polyamide composite material with high heat conductivity coefficient and preparation method thereof |
| CN114316314B (en) * | 2022-01-12 | 2023-09-05 | 润华(江苏)新材料有限公司 | TLCP-para-aramid pulp composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986639A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院化学研究所 | Thermosetting resin-base composite material and its preparing |
| CN102585488A (en) * | 2011-01-13 | 2012-07-18 | 上海杰事杰新材料(集团)股份有限公司 | High temperature-resistant nylon/thermotropic liquid crystal polymer blend and preparation method for blend |
| CN102702695A (en) * | 2012-06-15 | 2012-10-03 | 昆山聚威工程塑料有限公司 | Heat conducting polyamide (PA)/polybutylene terephthalate (PBT) alloy |
-
2012
- 2012-12-18 CN CN201210562507.7A patent/CN103862589B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986639A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院化学研究所 | Thermosetting resin-base composite material and its preparing |
| CN102585488A (en) * | 2011-01-13 | 2012-07-18 | 上海杰事杰新材料(集团)股份有限公司 | High temperature-resistant nylon/thermotropic liquid crystal polymer blend and preparation method for blend |
| CN102702695A (en) * | 2012-06-15 | 2012-10-03 | 昆山聚威工程塑料有限公司 | Heat conducting polyamide (PA)/polybutylene terephthalate (PBT) alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103862589A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103862589B (en) | A kind of melt blending prepares the method for polyamide-based heat-conductive composite material | |
| CN101914288B (en) | Nylon 6 mineral fiber composite material for automobile engine cover lid and preparation method thereof | |
| CN101831110B (en) | Polypropylene composite material capable of being welded at high frequency and preparation method thereof | |
| CN102585348B (en) | Toughened conducting material and preparation method for toughened conducting material | |
| CN107603211B (en) | High-fluidity high-toughness heat-conducting nylon composite material and preparation method thereof | |
| CN107057339A (en) | A kind of activeness and quietness nylon material and its preparation method and application | |
| US20080293861A1 (en) | Composition of high impact glass fiber reinforced engineering plastic and preparation method thereof | |
| CN105802019A (en) | Graphene/glass fiber reinforcement polypropylene composite material and preparation method thereof | |
| CN108250747B (en) | Thermoplastic polyetherimide insulating and heat-conducting composite material and preparation method thereof | |
| CN102174254A (en) | Highly heat-conducting insulation engineering plastic and preparation method thereof | |
| CN105504803B (en) | A kind of high fluidity fiber reinforced nylon composite material and preparation method thereof | |
| CN102675738A (en) | Heat-resistant conductive polypropylene composite material and preparation method thereof | |
| CN107523049B (en) | Graphene polymer composite heat-conducting plastic and preparation method thereof | |
| CN107541049B (en) | Graphene-continuous glass fiber reinforced halogen-free flame-retardant weather-resistant PPO/HIPS alloy material and preparation method thereof | |
| CN102643480A (en) | Anti-static alloy composite material and preparation method thereof | |
| WO2022105149A1 (en) | Toughened cyclic polyolefin material with high transparency and low dielectric loss and preparation method therefor | |
| CN110437540B (en) | Polypropylene material with low dielectric constant, high strength and good weather resistance and preparation method thereof | |
| CN107418197B (en) | Heat-conducting nylon engineering plastic and preparation method thereof | |
| CN105017765A (en) | Basic magnesium sulfate whisker/PA610T composite material and preparation method thereof | |
| CN104262965A (en) | PPS (polyphenylene sulfide) composite material and preparation method thereof | |
| CN1944513A (en) | Melt flowable polyethylene/thermosetting resin composite material | |
| CN104629335A (en) | Aging-resistant reinforced PC/ABS alloy, and preparation method thereof | |
| CN113321866A (en) | Laser direct forming polypropylene material and preparation method thereof | |
| CN115433458A (en) | Graphene/carbon fiber reinforced nylon 66 composition and preparation method thereof | |
| CN101781455B (en) | Super-tough nylon alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Hangzhou Qianshi Technology Co., Ltd. Document name: Notification of Publication of the Application for Invention |
|
| DD01 | Delivery of document by public notice |
Addressee: Hangzhou Qianshi Technology Co., Ltd. Document name: Approval notice for cost mitigation |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20161218 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |