CN105199191A - High-tenacity heat-conducting inflaming retarding plastic and preparation method thereof - Google Patents
High-tenacity heat-conducting inflaming retarding plastic and preparation method thereof Download PDFInfo
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- CN105199191A CN105199191A CN201510591406.6A CN201510591406A CN105199191A CN 105199191 A CN105199191 A CN 105199191A CN 201510591406 A CN201510591406 A CN 201510591406A CN 105199191 A CN105199191 A CN 105199191A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The invention provides high-tenacity heat-conducting inflaming retarding plastic and a preparation method thereof. The high-tenacity heat-conducting inflaming retarding plastic is prepared from, by weight, 22%-49% of HDPE, 35%-55% of self-manufactured compound heat-conducting filler, 5%-7% of flexibilizer, 10%-14% of fire retardant, 0.2-0.5% of antioxygen, 0.5%-0.7% of dispersing agent and 0.3%-0.8% of coupling agent. The tenacity, flame retardant property and heat conductivity of the material can be greatly improved, the plastic can be prepared through weighing, mixing, melt extrusion and prilling, operation is easy, conditions are easy to control, cost is low, the requirement for equipment is low, and the plastic is suitable for industrial production.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of high tenacity heat conductive flame-retarding plastics and preparation method thereof.
Background technology
High density polyethylene(HDPE) (HDPE) is high, the nonpolar thermoplastic resin of a kind of degree of crystallinity.The milky appearance of ortho states HDPE, translucent in meagre cross section in a certain degree, have good thermotolerance and winter hardiness, chemical stability is good, also has higher rigidity and toughness, and physical strength is good, dielectric properties, and environmental stress crack resistance is also better.But its ventilative difference, yielding, easily aging, easy embrittlement, makes it apply and is greatly limited.Simultaneously its thermal conductivity is lower, only have 0.33W/m.k, and itself does not have flame retardant effect, does not meet and is needing good heat dissipation effect and the high product of flame-retardancy requirements use.
Current investigator both domestic and external has carried out large quantifier elimination for thermally conductive material, mainly carries out modification and research and development for PA6, PA66, makes some progress.But due to the problem that cost is high or material is partially crisp, be not widely used.We consideration HDPE replaces PA6, PA66, add the toughness that appropriate toughner POE improves heat conduction HDPE again, simultaneously because HDPE loading level greatly, also has higher rigidity and toughness, make material while wananty costs is low, keep the toughness that material is higher.
Now, the geometrical dimension of electronics and computer aspect product constantly reduces, and the heat that will bear is increasing, makes the research of thermally conductive material more and more important.HDPE material quality is light, and molding processibility is good, cheap and good insulating, but thermal conductivity is low.By adding heat conductive filler magnesium oxide, aluminum oxide, silicon carbide, aluminium nitride, boron nitride etc., heat conductivility can be improved significantly.
At present, have a lot of patent to be all research about PA6, PA66 heat-conducting plastic both at home and abroad, but the heat-conducting plastic studied as matrix with HDPE is fewer.Therefore, the present invention is great for heat-conducting plastic Research Significance, has a extensive future.
Summary of the invention
The object of the invention is to the defect overcoming prior art, provide a kind of high tenacity heat conductive flame-retarding plastics, it has high tenacity, fire-retardant characteristic.
In addition, the present invention also provides a kind of preparation method of high tenacity heat conductive flame-retarding plastics, and it has simple to operate, is applicable to the characteristic of suitability for industrialized production.
The present invention is achieved in that a kind of high tenacity heat conductive flame-retarding plastics, comprises the formula composition of following weight percent:
Further, described HDPE is other high density polyethylene(HDPE) of high flow stage, and wherein melt flow mass rate (MFR) is 7-9 (unit: g/10min; Test condition: 190 DEG C/2.16kg), density is 0.95-0.96g/cm3.
Further, the composite heat conductive filler of described self-control is magnesium oxide, aluminum oxide, zinc oxide, silicon nitride, one or more in aluminium carbide, composite again after special surface activation treatment according to certain ratio, finally mix according to a certain percentage with crystal whisker materials and obtain.
Further, described toughner is be the copolymer p OE of ethene and octene.
Further, described fire retardant is that antimonous oxide and bromide fire retardant (as tetrabromo-bisphenol, TDE, brominated Polystyrene, brominated epoxy, brominated triazine etc.) are composite with the ratio of 1:3.
Further, to be that four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidants and tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) auxiliary anti-oxidant two kinds press 1:1 composite for described oxidation inhibitor.
Further, described dispersion agent is N, N'-ethylene bis stearamide dispersion agent.
Further, described coupling agent is one or more in organic complex, silicane, titanate ester and aluminate coupling agent.
A preparation method for high tenacity heat conductive flame-retarding plastics, comprises the following steps:
(1) each component starting material corresponding are taken by above-mentioned weight percent;
(2) by each component starting material taken in step (1) at high-speed mixer and mixing 6-10 minute;
(3) mixing material mixed in step (2) is put into the loading hopper of twin screw extruder, through melt extruding, granulation; Wherein twin screw extruder one district temperature 160-175 DEG C, two district temperature 165-180 DEG C, three district temperature 170-190 DEG C, four district temperature 170-190 DEG C, head 180-200 DEG C, the residence time 2 ~ 3min, pressure is 12-18MPa, screw speed 130-150 rev/min.
The present invention adopts the copolymer p OE of ethene and octene as toughner, and this toughner and material have good consistency, and can increase substantially the toughness of material.Adopt fire retardant can give the flame retardant properties of material excellence.The composite heat conductive filler of self-control adopted for the whiteness of material and Effect on Mechanical Properties less, can make, between particle, bridge joint effect occurs containing whisker composition in the composite heat conductive filler system of self-control, make the thermal conducting path that is made up of heat conductive filler further perfect, thus the thermal conductivity of matrix material can be made to improve rapidly.
Another the present invention also provides a kind of preparation method of high tenacity heat conductive flame-retarding plastics, and by taking, mixing, melt extrudes, granulation, and simple to operate, condition is easily controlled, with low cost, low for equipment requirements, is suitable for suitability for industrialized production.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
The schema that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
As Fig. 1, the embodiment of the present invention provides a kind of high tenacity heat conductive flame-retarding plastics and preparation method thereof, and particularly, described high tenacity heat conductive flame-retarding plastics, comprise the formula composition of following weight percent:
Further, described HDPE is other high density polyethylene(HDPE) of high flow stage, and wherein melt flow mass rate (MFR) is 7-9 (unit: g/10min; Test condition: 190 DEG C/2.16kg), density is 0.95-0.96g/cm3, selects the FHC7260 of Jilin Petrochemical.
The composite heat conductive filler of described self-control is magnesium oxide, aluminum oxide, zinc oxide, silicon nitride, one or more in aluminium carbide, composite again after special surface activation treatment according to certain ratio, mixes according to a certain percentage and obtain with crystal whisker materials.Concrete operations are as follows: take that particle diameter is 1600 object magnesium oxide 30%, particle diameter is 300 object magnesium oxide 20%, particle diameter is 300 object aluminum oxide 15%, particle diameter is 300 object zinc oxide 28%, particle diameter is 300 object aluminium carbides 15% by weight percentage, add the silane coupling agent of 2% again, stir, then put into baking oven and dry fully drying in 4 hours with 80 DEG C.Then the mixture getting oven dry selects 3000 object calcium sulfate crystal whiskers 15% to mix by weight 85% with whisker, so just can obtain making composite heat conductive filler by oneself.
Described toughner is be the copolymer p OE of ethene and octene.Select Tao Shi 8150.
Described fire retardant is that antimonous oxide and bromide fire retardant (as tetrabromo-bisphenol, TDE, brominated Polystyrene, brominated epoxy, brominated triazine etc.) are composite with the ratio of 1:3, selects the antimonous oxide of occasion state antimony industry and the TDE of extra large Wang Huagong.
Described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidant and tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) to press 1:1 composite for auxiliary anti-oxidant two kinds, Ciba company is selected to produce, trade names are respectively Irganox1010, and Irganox168.
Described dispersion agent is N, N'-ethylene bis stearamide dispersion agent.Select the safe chemical industry EBS120D of Guangzhou swallow.
Described coupling agent is one or more in organic complex, silicane, titanate ester and aluminate coupling agent.Select the KH-550 of Hangzhou boiling point Chemical Manufacture.
The preparation method of described high tenacity heat conductive flame-retarding plastics, comprises the following steps:
(1) each component starting material corresponding are taken by above-mentioned weight percent;
(2) by each component starting material taken in step (1) at high-speed mixer and mixing 6-10 minute;
(3) mixing material mixed in step (2) is put into the loading hopper of twin screw extruder, through melt extruding, granulation; Complete processing is as follows: twin screw extruder one district temperature 160-175 DEG C, two district temperature 165-180 DEG C, three district temperature 170-190 DEG C, four district temperature 170-190 DEG C, head 180-200 DEG C, the residence time 2 ~ 3min, pressure is 12-18MPa, screw speed 130-150 rev/min.
Below in conjunction with specific embodiment, the present invention is described in detail:
Embodiment 1
Be HDPE45.6% by weight percent, make composite heat conductive filler 35%, toughner 6%, fire retardant 12%, oxidation inhibitor 0.3%, dispersion agent 0.6%, coupling agent 0.5% by oneself mix 8 minutes in high speed mixer, the loading hopper of twin screw extruder is put into after fully mixing, through melt extruding, granulation; Complete processing is as follows: twin screw extruder one district temperature 165 DEG C, two district's temperature 175 DEG C, three district's temperature 180 DEG C, four district's temperature 180 DEG C, head 190 DEG C, residence time 2min, and pressure is 16MPa, screw speed 150 revs/min.
Embodiment 2
Be HDPE35.6% by weight percent, make composite heat conductive filler 45%, toughner 6%, fire retardant 12%, oxidation inhibitor 0.3%, dispersion agent 0.6%, coupling agent 0.5% by oneself mix 8 minutes in high speed mixer, the loading hopper of twin screw extruder is put into after fully mixing, through melt extruding, granulation; Complete processing is as follows: twin screw extruder one district temperature 165 DEG C, two district's temperature 175 DEG C, three district's temperature 180 DEG C, four district's temperature 180 DEG C, head 190 DEG C, residence time 2min, and pressure is 16MPa, screw speed 150 revs/min.
Embodiment 3
Be HDPE25.6% by weight percent, make composite heat conductive filler 55%, toughner 6%, fire retardant 12%, oxidation inhibitor 0.3%, dispersion agent 0.6%, coupling agent 0.5% by oneself mix 8 minutes in high speed mixer, the loading hopper of twin screw extruder is put into after fully mixing, through melt extruding, granulation; Complete processing is as follows: twin screw extruder one district temperature 165 DEG C, two district's temperature 175 DEG C, three district's temperature 180 DEG C, four district's temperature 180 DEG C, head 190 DEG C, residence time 2min, and pressure is 16MPa, screw speed 150 revs/min.
Comparative example 1
Be HDPE80.6% by weight percent, make composite heat conductive filler 0%, toughner 6%, fire retardant 12%, oxidation inhibitor 0.3%, dispersion agent 0.6%, coupling agent 0.5% by oneself mix 8 minutes in high speed mixer, the loading hopper of twin screw extruder is put into after fully mixing, through melt extruding, granulation; Complete processing is as follows: twin screw extruder one district temperature 165 DEG C, two district's temperature 175 DEG C, three district's temperature 180 DEG C, four district's temperature 180 DEG C, head 190 DEG C, residence time 2min, and pressure is 16MPa, screw speed 150 revs/min.
Comparative example 2
Be HDPE31.6% by weight percent, make composite heat conductive filler 55%, toughner 0%, fire retardant 12%, oxidation inhibitor 0.3%, dispersion agent 0.6%, coupling agent 0.5% by oneself mix 8 minutes in high speed mixer, the loading hopper of twin screw extruder is put into after fully mixing, through melt extruding, granulation; Complete processing is as follows: twin screw extruder one district temperature 165 DEG C, two district's temperature 175 DEG C, three district's temperature 180 DEG C, four district's temperature 180 DEG C, head 190 DEG C, residence time 2min, and pressure is 16MPa, screw speed 150 revs/min.
Comparative example 3
Be HDPE37.6% by weight percent, make composite heat conductive filler 55%, toughner 6%, fire retardant 0%, oxidation inhibitor 0.3%, dispersion agent 0.6%, coupling agent 0.5% by oneself mix 8 minutes in high speed mixer, the loading hopper of twin screw extruder is put into after fully mixing, through melt extruding, granulation; Complete processing is as follows: twin screw extruder one district temperature 165 DEG C, two district's temperature 175 DEG C, three district's temperature 180 DEG C, four district's temperature 180 DEG C, head 190 DEG C, residence time 2min, and pressure is 16MPa, screw speed 150 revs/min.
[performance evaluation carries out standard and test data]
By the particle in the convection oven of 70 ~ 80 DEG C dry 4 ~ 6 hours completing granulation in above-described embodiment 1 ~ 3, comparative example 1 ~ 3, then by the injection moulding sample preparation on 80T injection moulding machine of the particle of drying; That tests the results are shown in following table:
As can be seen from upper table embodiment 1 ~ 3 and comparative example 1, with simple HDPE resin-phase ratio, that makes composite heat conductive filler by oneself adds the heat-conduction coefficient that membership obviously increases matrix material, and when the content making composite heat conductive filler by oneself is 55%, thermal conductivity reaches 1.4W/ (mK).When can find out interpolation toughner by upper table embodiment 1 ~ 3 and comparative example 2, the impact property of matrix material increases significantly.Show material toughness be improved significantly.When can find out interpolation fire retardant by upper table embodiment 1 ~ 3 and comparative example 3, the flame retardant properties of matrix material can increase significantly.Material prepared by the present invention has high thermal conductivity, flame retardant resistance and mechanical property simultaneously, avoid the shortcoming that market like product cannot obtain high thermal conductivity, flame retardant resistance and high mechanical property simultaneously, extend the Application Areas of high-density polyethylene composite material.
Above a kind of high tenacity heat conductive flame-retarding plastics provided by the present invention and preparation method thereof are described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of an above enforcement example just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (9)
1. high tenacity heat conductive flame-retarding plastics, is characterized in that, comprise the formula composition of following weight percent:
2. a kind of high tenacity heat conductive flame-retarding plastics as claimed in claim 1, is characterized in that: described HDPE is other high density polyethylene(HDPE) of high flow stage, wherein melt flow mass rate (MFR) is 7-9 (unit: g/10min; Test condition: 190 DEG C/2.16kg), density is 0.95-0.96g/cm3.
3. a kind of high tenacity heat conductive flame-retarding plastics as claimed in claim 1, it is characterized in that: the composite heat conductive filler of described self-control is magnesium oxide, aluminum oxide, zinc oxide, silicon nitride, one or more in aluminium carbide, composite again after special surface activation treatment according to certain ratio, finally mix according to a certain percentage with crystal whisker materials and obtain.
4. a kind of high tenacity heat conductive flame-retarding plastics as claimed in claim 1, is characterized in that: described toughner is be the copolymer p OE of ethene and octene.
5. a kind of high tenacity heat conductive flame-retarding plastics as claimed in claim 1, is characterized in that: described fire retardant is that antimonous oxide and bromide fire retardant (as tetrabromo-bisphenol, TDE, brominated Polystyrene, brominated epoxy, brominated triazine etc.) are composite with the ratio of 1:3.
6. a kind of high tenacity heat conductive flame-retarding plastics as claimed in claim 1, it is characterized in that: described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] to press 1:1 composite for pentaerythritol ester primary antioxidant and tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) auxiliary anti-oxidant two kinds.
7. a kind of high tenacity heat conductive flame-retarding plastics as claimed in claim 1, is characterized in that: described dispersion agent is N, N'-ethylene bis stearamide dispersion agent.
8. a kind of high tenacity heat conductive flame-retarding plastics as claimed in claim 1, is characterized in that: described coupling agent is one or more in organic complex, silicane, titanate ester and aluminate coupling agent.
9. a preparation method for high tenacity heat conductive flame-retarding plastics as claimed in claim 1, is characterized in that, comprise the following steps:
(1) each component starting material corresponding are taken by above-mentioned weight percent;
(2) by each component starting material taken in step (1) at high-speed mixer and mixing 6-10 minute;
(3) mixing material mixed in step (2) is put into the loading hopper of twin screw extruder, through melt extruding, granulation; Wherein twin screw extruder one district temperature 160-175 DEG C, two district temperature 165-180 DEG C, three district temperature 170-190 DEG C, four district temperature 170-190 DEG C, head 180-200 DEG C, the residence time 2 ~ 3min, pressure is 12-18MPa, screw speed 130-150 rev/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105694186A (en) * | 2016-04-22 | 2016-06-22 | 杭州富阳飞博科技有限公司 | Flame-retardant heat-conducting plastic cement and application thereof |
| CN105837911A (en) * | 2016-05-27 | 2016-08-10 | 国网河南社旗县供电公司 | Insulating heat conducting cable material and preparation method thereof |
| CN105957735A (en) * | 2016-05-11 | 2016-09-21 | 杭州日月电子有限公司 | Fast-connection high-flexibility waterproof and fireproof safety switch |
| CN109705434A (en) * | 2018-12-28 | 2019-05-03 | 郑州贝欧科儿童用品股份有限公司 | A kind of car duct and preparation method thereof |
| CN110092964A (en) * | 2019-03-27 | 2019-08-06 | 广州市白云区钟落潭家立美塑料制品厂 | A kind of preparation method of polyvinyl high thermal conductivity composite plastic |
| CN112143074A (en) * | 2020-09-15 | 2020-12-29 | 浙江大丰体育设备有限公司 | High-density polyethylene composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105694186A (en) * | 2016-04-22 | 2016-06-22 | 杭州富阳飞博科技有限公司 | Flame-retardant heat-conducting plastic cement and application thereof |
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| CN110092964A (en) * | 2019-03-27 | 2019-08-06 | 广州市白云区钟落潭家立美塑料制品厂 | A kind of preparation method of polyvinyl high thermal conductivity composite plastic |
| CN112143074A (en) * | 2020-09-15 | 2020-12-29 | 浙江大丰体育设备有限公司 | High-density polyethylene composition and preparation method thereof |
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| CN105199191B (en) | 2018-01-26 |
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