CN103862589A - Method for preparing polyamide-based heat conduction composite material through melt blending - Google Patents
Method for preparing polyamide-based heat conduction composite material through melt blending Download PDFInfo
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- CN103862589A CN103862589A CN201210562507.7A CN201210562507A CN103862589A CN 103862589 A CN103862589 A CN 103862589A CN 201210562507 A CN201210562507 A CN 201210562507A CN 103862589 A CN103862589 A CN 103862589A
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Abstract
The invention relates to a method for preparing polyamide 6-based heat conduction plastic through melt blending. The method comprises the following steps: 1, preparing a multifunctional master batch from an elastomer which contains a polar group and is used as a carrier and coupling agent treated heat conduction inorganic filler particles, an antioxidant, an ultraviolet stabilizing agent and the like through a double-screw extruder; and 2, preparing the heat conduction composite material from polyamide 6, a thermotropic liquid crystal polymer and the master batch prepared in the first step through the double-screw extruder. The polyamide 6-based composite material prepared by the method disclosed by the invention is high in heat conduction performance, high in forming processing property and high in mechanical property, is suitable for injection molding, and can be widely applied to electronic appliances, mobile phone shells and LED (light emitting diode) lamp products; the heat dissipation performance of a product at high temperature is improved, and the service life of the product is prolonged.
Description
Technical field
The present invention relates to a kind of preparation method of the polymer matrix composite with high thermal conductance, relate in particular to a kind of be applicable to can injection mo(u)lding the preparation method with heat-conducting polymer/inorganic composite materials.
Background technology
Along with the high speed development of information technology, electronic devices and components and electronic equipment are to the future development of " thin, light, little ", and current densities and load capacity increase sharply, and can cause that the local temperature of electronic component sharply raises and reduces the life-span.Traditional cooling electronic component main body, radiation cooling plate etc. are mainly by metal material, pottery, Machining of Ceramics difficulty, and quality weight, is unfavorable for the future development of electronic apparatus to " thin, light, little ".Therefore there is thermal conductivity, quality is light, specific strength is high engineering plastics are ideal materials of novel electron electric elements.
Macromolecular material is poor because of the low thermal conductivity of degree of crystallinity, can not meet the requirement of electronic devices and components high-cooling property, therefore needs its heat conductivity to improve modification.Conventionally the method that improves plastics thermal conductivity is mainly to utilize the metal dusts such as the aluminium oxide of high heat conduction, boron nitride, carbon fiber or copper powder, aluminium powder etc., get off to improve its thermal conductivity at higher loading (generally in 80wt% left and right), but this has also reduced excellent processing and forming life and the more tough mechanical characteristic of macromolecule itself simultaneously.
Existing technology is to adopt simple melt blending to prepare the heat-conducting plastic of high filler loading capacity mostly, because filler and resin matrix are difficult to mix because of the difference of volume, larger to processing and forming and Effect on Mechanical Properties, and thermal conductivity improves also restricted.The present patent application person adopts and in resin matrix, adds suitable liquid crystal polymer, when obtaining high thermal conductivity, keeps excellent processing characteristics.
Summary of the invention
The object of the invention is to solve the low problem of macromolecular material heat conductivity by the method for melt blending, a kind of preparation method who makes the polyamide-based heat conduction engineering plastics that high heat conduction, mechanical property and processing characteristics are good is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of melt blending is prepared 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 to multifunctional mother granules together with ultraviolet light stabilizing agent in double screw extruder, keeping extrusion temperature is 120 ℃～140 ℃, extruding pelletization;
Multifunctional mother granules, polyamide 6 and TLCP that step 2. makes step 1 mix, and 80 ℃ of oven dry of vacuum 4 hours, then join in double screw extruder together, and keeping extrusion temperature is 220 ℃～270 ℃, extruding pelletization.
Further, in described step 1, described vector resin can be the one in the ethylene-octene copolymer (POE-g-MAH) of ethylene propylene diene rubber (EPDM-g-MAH), maleic anhydride graft of maleic anhydride graft; Described heat filling is one or more mixtures 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 one or the mixture of antioxidant 1010, irgasfos 168; Described ultraviolet light stabilizing agent is one or the mixture in UV-531, TINUVIN 770,
Further, the mass ratio of the various material vector resin/heat filling/antioxidant/ultraviolet light stabilizing agents 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 260 ℃ of left and right, and its consumption is 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 stabilizing agent is 100: 15: 600: 40: 1.5: 1, wherein the particle diameter of heat filling is all 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 1% of inorganic nanoparticles protonatomic mass.
Compared with prior art, the present invention has following benefit: TLCP can improve the flow processability of polyamide 6; Meanwhile, liquid crystal forms fento in polyamide 6 matrix resin, is conducive to form complete thermal conductive network chain structure, plays in addition the effect of heterogeneous nucleation, improves polyamide 6 intrinsic thermal conductivity, is conducive to improve composite heat-conductive characteristic.In addition, multifunctional mother granules made by various auxiliary agents by the present invention is also of value to the dispersiveness of raising auxiliary agent in polymeric matrix, can improve heat conductivity and the mechanical property of polyamide 6 based composites.Because the high comprehensive performance such as composite heat conductivility and mechanics that the present invention makes.
The specific embodiment:
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
Embodiment 1
First heat filling 400g is carried out to surface treatment with 0.5% coupling agent NDZ-311 in homogenizer; Then be 10: 400: 0.5 mass ratio: vector resin/heat filling/antioxidant/ultraviolet light stabilizing agent one of 1 is reinstated double screw extruder granulation and made multifunctional mother granules, extruder barrel temperature is controlled at 120 ℃～140 ℃; Finally the multifunctional mother granules making is mixed with the polyamide 6 of 100g and the TLCP of 10g, 80 ℃ of oven dry of vacuum 4 hours together, utilize double screw extruder to extrude preparation polyamide-based heat-conductive composite material, barrel temperature is controlled at 210 ℃～280 ℃, keeps vacuum plant to open.
The above-mentioned heat-conductive composite material making is through injection moulding sample preparation, and the performance test results is as follows: pyroconductivity is 6.5W/mk, hot strength 61.5MPa, bending strength 73.7MPa, notched Izod impact strength 14.6KJ/m
2, degree of crystallinity is 35%, melt index is 135g/10min.
Embodiment 2
First heat filling 400g is carried out to surface treatment with 1% coupling agent NDZ-311 in homogenizer; Then be 40: 400: 0.5 mass ratio: vector resin/heat filling/antioxidant/ultraviolet light stabilizing agent one of 1 is reinstated double screw extruder granulation and made multifunctional mother granules, extruder barrel temperature is controlled at 120 ℃～140 ℃; Finally the multifunctional mother granules making is mixed with the polyamide 6 of 100g and the TLCP of 10g, 80 ℃ of oven dry of vacuum 4 hours together, utilize double screw extruder to extrude preparation polyamide-based heat-conductive composite material, barrel temperature is controlled at 210～280 ℃, keeps vacuum plant to open.
The above-mentioned heat-conductive composite material making is through injection moulding sample preparation, and the performance test results is as follows: pyroconductivity is 5.7W/mk, hot strength 56.3MPa, bending strength 64.7MPa, notched Izod impact strength 19.5KJ/m
2, degree of crystallinity is 31%, melt index is 128g/10min.
Embodiment 3
First heat filling 700g is carried out to surface treatment with 1.5% titanate coupling agent NDZ-311 in homogenizer; Then be 10: 700: 1 mass ratio: vector resin/heat filling/antioxidant/ultraviolet light stabilizing agent one of 3 is reinstated double screw extruder granulation and made multifunctional mother granules, extruder barrel temperature is controlled at 120 ℃～140 ℃; Finally the multifunctional mother granules making is mixed with the polyamide 6 of 100g and the TLCP of 10g, 80 ℃ of oven dry of vacuum 4 hours together, utilize double screw extruder to extrude preparation polyamide-based heat-conductive composite material, barrel temperature is controlled at 210～280 ℃, keeps vacuum plant to open.
The above-mentioned heat-conductive composite material making is through injection moulding sample preparation, and the performance test results is as follows: pyroconductivity is 9.5W/mk, hot strength 69.4MPa, bending strength 64.7MPa, notched Izod impact strength 10.8KJ/m
2, degree of crystallinity is 37%, melt index is 119g/10min.
Embodiment 4
First heat filling 700g is carried out to surface treatment with 1.5% coupling agent NDZ-311 in homogenizer; Then be 40: 700: 1 mass ratio: vector resin/heat filling/antioxidant/ultraviolet light stabilizing agent one of 3 is reinstated double screw extruder granulation and made multifunctional mother granules, extruder barrel temperature is controlled at 120 ℃～140 ℃; Finally the multifunctional mother granules making is mixed with the polyamide 6 of 100g and the TLCP of 10g, 80 ℃ of oven dry of vacuum 4 hours together, utilize double screw extruder to extrude preparation polyamide-based heat-conductive composite material, barrel temperature is controlled at 210～280 ℃, keeps vacuum plant to open.
The above-mentioned heat-conductive composite material making is through injection moulding sample preparation, and the performance test results is as follows: pyroconductivity is 9.0W/mk, hot strength 67.2MPa, bending strength 66.8MPa, notched Izod impact strength 13.5KJ/m
2, degree of crystallinity is 36%, melt index is 126g/10min.
Embodiment 5
First heat filling 700g is carried out to surface treatment with 1.5% coupling agent NDZ-311 in homogenizer; Then be 10: 700: 1 mass ratio: vector resin/heat filling/antioxidant/ultraviolet light stabilizing agent one of 3 is reinstated double screw extruder granulation and made multifunctional mother granules, extruder barrel temperature is controlled at 120 ℃～140 ℃; Finally the multifunctional mother granules making is mixed with the polyamide 6 of 100g and the TLCP of 15g, 80 ℃ of oven dry of vacuum 4 hours together, utilize double screw extruder to extrude preparation polyamide-based heat-conductive composite material, barrel temperature is controlled at 210～280 ℃, keeps vacuum plant to open.
The above-mentioned heat-conductive composite material making is through injection moulding sample preparation, and the performance test results is as follows: pyroconductivity is 12.5W/mk, hot strength 73.7MPa, bending strength 69.6MPa, notched Izod impact strength 9.8KJ/m
2, degree of crystallinity is 42%, melt index is 134g/10min.
Claims (8)
1. the method for melt blending is prepared a method for polyamide 6 base heat-conductive composite material, it is characterized in that comprising the steps:
Step 1. utilizes the elastomer of polar functionalities to do carrier, and the nano heat-conductive filler of coupling agent modified mistake, antioxidant are made to multifunctional mother granules together with ultraviolet light stabilizing agent in double screw extruder, and keeping extruder temperature is 120 ℃～140 ℃;
Multifunctional mother granules, polyamide 6 and TLCP that step 2. makes step 1 mix, and 80 ℃ of oven dry of vacuum 4 hours, then join granulation in double screw extruder together, and keeping extrusion temperature is 220 ℃～280 ℃.
2. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, it is characterized in that the vector resin consumption in described step 1 is 10%～40% of polyamide substrate resin demand, described vector resin can be the one in the ethylene-octene copolymer (POE-g-MAH) of ethylene propylene diene rubber (EPDM-g-MAH), maleic anhydride graft of maleic anhydride graft.
3. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, it is characterized in that in described step 1, heat filling used is two or more mixing in aluminium oxide, aluminium powder, carbon fiber etc., in homogenizer, carry out surface treatment with coupling agent.The particle diameter of described heat filling is all less than 100nm, and wherein the diameter of carbon fiber is less than 30nm, and draw ratio is between 50: 1～100: 1; The consumption of described heat filling is 400%～700% of polyamide consumption; Described coupling agent is titanate coupling agent NDZ-311, and consumption is 0.5%～1.5% of heat filling gross mass.
4. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, it is characterized in that its consumption of antioxidant in described step 1 is 0.5%～1.5% of polyamide consumption, described antioxidant can be four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] a kind of or two kinds of mixtures in pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl-phenyl) (irgasfos 168).
5. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, the consumption that it is characterized in that the ultraviolet light stabilizing agent in described step 1 is 1%～5% of polyamide consumption, ultraviolet light stabilizing agent is UV-531 (UV-531), two (2,2,6,6-tetramethyl-4-piperidyl) one or both mixtures in sebacate (TINUVIN 770).
6. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, it is characterized in that the liquid crystal polymer in described step 2 is that fusing point is 260 ℃ of left and right, backbone chain type TLCP, is preferably poly-(4-HBA/2-hydroxyl-6-naphthoic acid) resin (TLCP Vectra A950).
7. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, it is characterized in that described composite is made up of polyamide 6, TLCP, heat filling, vector resin, antioxidant, ultraviolet light stabilizing agent, the parts by weight of each component are as follows:
8. the preparation method of polyamide 6 base heat-conductive composite material as claimed in claim 1, is characterized in that, concrete steps are as follows:
(1) in homogenizer, heat filling is processed with titanate coupling agent NDZ-311 according to 1% mass fraction; According to the formula described in claim 7, vector resin, heat filling, antioxidant and ultraviolet light stabilizing agent one are reinstated to double screw extruder granulation, control extruder temperature at 120 ℃～140 ℃;
(2) finally polyamide 6, TLCP and multifunctional mother granules are mixed, 80 ℃ of oven dry of vacuum 4 hours, add extruding pelletization in double screw extruder together together, control extruder temperature at 210 ℃～280 ℃.
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Cited By (9)
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| CN104448814A (en) * | 2014-11-27 | 2015-03-25 | 湖北洋田塑料制品有限公司 | High-strength and high-rigidity liquid crystal polymer reinforced nylon 66 composite and preparation method thereof |
| CN105255086A (en) * | 2015-11-10 | 2016-01-20 | 西安科技大学 | Thermal conductive blended polymer material and preparation process thereof |
| CN105367966A (en) * | 2015-11-10 | 2016-03-02 | 西安科技大学 | Heat-conduction mixed polymer and preparation method thereof |
| 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 |
| CN111635574A (en) * | 2020-06-19 | 2020-09-08 | 中北大学 | PP/PE/BN/EPDM heat-conducting insulating material and preparation method thereof |
| CN114031934A (en) * | 2021-12-15 | 2022-02-11 | 宁波公牛光电科技有限公司 | Polyamide composite material with high thermal conductivity coefficient and preparation method thereof |
| CN114316314A (en) * | 2022-01-12 | 2022-04-12 | 润华(江苏)新材料有限公司 | TLCP (thermotropic liquid Crystal Polymer) -para-aramid pulp composite material and preparation method thereof |
| CN116496621A (en) * | 2023-04-11 | 2023-07-28 | 华南理工大学 | Three-phase double-percolation high-heat-conductivity composite material and preparation method and application thereof |
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| CN104448814A (en) * | 2014-11-27 | 2015-03-25 | 湖北洋田塑料制品有限公司 | High-strength and high-rigidity liquid crystal polymer reinforced nylon 66 composite and preparation method thereof |
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| CN105255086A (en) * | 2015-11-10 | 2016-01-20 | 西安科技大学 | Thermal conductive blended polymer material and preparation process thereof |
| CN105367966A (en) * | 2015-11-10 | 2016-03-02 | 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 |
| CN105367966B (en) * | 2015-11-10 | 2017-05-17 | 西安科技大学 | Heat-conduction mixed polymer and preparation method thereof |
| 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 |
| CN111635574A (en) * | 2020-06-19 | 2020-09-08 | 中北大学 | PP/PE/BN/EPDM heat-conducting insulating material and preparation method thereof |
| CN114031934A (en) * | 2021-12-15 | 2022-02-11 | 宁波公牛光电科技有限公司 | Polyamide composite material with high thermal conductivity coefficient 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 |
| CN114316314A (en) * | 2022-01-12 | 2022-04-12 | 润华(江苏)新材料有限公司 | TLCP (thermotropic liquid Crystal Polymer) -para-aramid pulp composite material 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 |
| CN116496621A (en) * | 2023-04-11 | 2023-07-28 | 华南理工大学 | Three-phase double-percolation high-heat-conductivity composite material and preparation method and application thereof |
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