A kind of hydrolysis aluminium nitride fills polyamide-based heat-conducting plastic and preparation method thereof
Technical field
The present invention relates to polyamide heat-conducting field of compound material, be specifically related to a kind of hydrolysis aluminium nitride and fill polyamide-based heat-conducting plastic and preparation method thereof.
Background technology
Polymer materials is as the widely used material of one, there is the advantages such as light weight, easily machine-shaping, price are lower, corrosion-resistant, there is very important using value in fields such as chemical industry, the energy, electron device, electronic information, aerospace, and start the potential application foreground showing alternative metals material.And compared with metallic substance, polymer materials is all the poor conductor of heat.The filling-modified important channel having become research heat-conducting plastic is both at home and abroad carried out to polymer materials, and prepares high heat conduction and the heat-conducting plastic with excellent mechanical performances has become research emphasis in recent years.
Polymeric amide (PA) is commonly called as nylon, and it has good mechanical property, thermotolerance, wearability and chemical resistant properties, and easily processing, frictional coefficient are low, are applicable to carrying out the research of Inorganic Fillers Filled enhancing modified.Its good heat conductivility can be given by adding aluminium nitride filler in polyamide resin.
Aluminium nitride is as the efficient heat conductive filler of one, and it compares with other Nitride Phases the favor that reasonable price are subject to heat conductive filler field, has wide market outlook.The deliquescence but the character due to himself easily absorbs water, easily generates aluminium hydroxide in the process preparing heat-conducting plastic, thermal conducting path is produced and interrupts, affect the transmission of phonon, finished product thermal conductivity is declined.
At present conventional filling surface treatment process mostly is and adds coupling agent in the pre-compounding process of starting material and filler, this treatment process is fairly simple, but poor to the treatment effect of filler, effective decorative layer can not be formed well between interface, improve filler water resistance.
It is a kind of containing diatomaceous thermally conductive polyamides that application publication number is that the Chinese invention patent application of CN 102076751A (application number is 200980124627.5) discloses, and comprises: A) polyamide thermoplastic of 19.9% ~ 69.99 % by weight; B) aluminum oxide of 30% ~ 80 % by weight; C) diatomite of 0.01% ~ 30 % by weight; D) other additives of 0% ~ 30 % by weight.This thermoplastic compounds has good mobility together with good mechanical property, and the thermal conductivity significantly improved.Said composition can be used for the heat radiation of CPU, resistor, IC, battery, store battery, electric motor, coil, rly., diode, lead channels etc., can contact most effectively thus heat can be discharged in environment by moulding compound by thermal source.
Application publication number is that the Chinese invention patent application of CN 102796369A (application number is 201210260919.5) discloses a kind of heat conduction polyamide compoiste material and its preparation method and application, this heat conduction polyamide compoiste material comprises the component of following weight per-cent: polymeric amide 18.2% ~ 58.6%, lubricant 0.1% ~ 1%, oxidation inhibitor 0.1% ~ 0.5%, surface-modifying agent 1.0% ~ 1.5% and enhanced thermal conduction properties-correcting agent 40% ~ 81%, described enhanced thermal conduction properties-correcting agent is carbon fiber, carbon dust, silicon carbide, aluminum oxide, one in boron nitride and aluminium nitride, two or three.Described surface-modifying agent is the conventional various surface-modifying agents that can be used for polyamide compoiste material used in this area, is preferably ethylene-vinyl acetate copolymer and/or silicone master batch.The content of the vinyl acetate segment in described ethylene-vinyl acetate copolymer is preferably 58 ~ 68wt%.This technical scheme increases the thermal conductivity of matrix material by adding enhanced thermal conduction properties-correcting agent, surface-modifying agent, for changing the interfacial characteristics of polymeric amide, improves its mechanical property, but as aluminium nitride is easily hydrolyzed in enhanced thermal conduction properties-correcting agent, environment weathering resistance is poor.
Summary of the invention
The object of the invention is to solve existing aluminium nitride powder facile hydrolysis, infiltrate undesirable with polyamide resin matrix, prepared aluminium nitride fills the not good technical problem of polyamide heat-conducting material conducts heat performance, and proposes a kind of hydrolysis aluminium nitride filling polyamide-based heat-conducting plastic and preparation method thereof.
Hydrolysis aluminium nitride of the present invention fills polyamide-based heat-conducting plastic preparation method simply, and cost is low.By carrying out tensio-active agent pre-treatment to aluminum nitride powder surface, making it obtain good anti-hydrolytic performance, having prepared that a kind of heat conductivility is good on this basis and the hydrolysis aluminium nitride with stronger environment weathering resistance fills polyamide-based heat-conducting plastic.
A kind of hydrolysis aluminium nitride fills polyamide-based heat-conducting plastic, is made up of the raw material of following weight part:
The aluminium nitride of the surfactant modified 60-120 part after described surfactant-modified aluminium nitride is atomized process by 2-15 part obtains.
The present invention adopts tensio-active agent as surface treatment agent, carry out mixing with aluminium nitride powder after utilizing FTG type continuous powdery surface modification machine Surfactant to carry out atomization process and modify, be beneficial to decorative layer fully coated at aln surface, aluminium nitride filler modified in pre-compounding process is fully contacted with polyamide substrate, then set up effective interface, improve mechanics and the processing characteristics of strongthener entirety while thermal conductivity.
As preferably, described tensio-active agent is one or more in Sodium dodecylbenzene sulfonate, sodium oleate, sodium lauryl sulphate, tween 80, polysorbate85, class of department 60, class 80 of department, TX-10, oleic acid, stearic acid.Above-mentioned tensio-active agent has fixing hydrophilic and oleophilic end, aligns in the surface energy of solution.One end of its molecule is carboxyl, ether or metal-salt isopolarity group, with inorganic filler surface, chemistry or physical adsorption can occur, reach the object of stuffing surface modification; Its molecule the other end is chain alkyl, and has good consistency between polyamide substrate, obtains good dispersion effect in the base.
The above-mentioned tensio-active agent selected of the present invention is aniorfic surfactant or nonionic surface active agent, after being directly atomized in powder modifying machine, modifying and decorating is carried out to aln surface, simple and fast more, has stopped the pollution of use to environment of organic solvent.Define chain alkyl decorative layer at aln surface after modifying simultaneously, this hydrophobic modification layer significantly can not only improve the water resistance of aluminum nitride powder surface, there is good consistency between chain alkyl and polyamide resin simultaneously, make the interface cohesion of resin and filler more tight.
Described surfactant-modified aluminium nitride be in preprocessing process with atomization after tensio-active agent in FTG type continuous powdery surface modification machine, complete surface coating decoration.、
Described polymeric amide is polyamide 6 or polyamide 66.
Described oxidation inhibitor be Hinered phenols antioxidant and phosphite ester kind antioxidant is composite or antioxidant 1010 and irgasfos 168 composite.
Described processing aid is the mixture of one or more in calcium stearate, ethylene bis stearic acid amide, silicone powder.
As preferably, described hydrolysis aluminium nitride fills polyamide-based heat-conducting plastic, is made up of the raw material of following weight part:
Described surfactant-modified aluminium nitride is obtained by the aluminium nitride of surfactant modified 100 ~ 120 parts after 5 ~ 15 parts of atomization process.
Further preferably, described hydrolysis aluminium nitride fills polyamide-based heat-conducting plastic, is made up of the raw material of following weight part:
Described surfactant-modified aluminium nitride is obtained by the aluminium nitride of surfactant modified 110 parts after 8 parts of atomization process.
Further preferably, described hydrolysis aluminium nitride fills polyamide-based heat-conducting plastic, is made up of the raw material of following weight part:
Described surfactant-modified aluminium nitride is obtained by the aluminium nitride of surfactant modified 110 parts after 8 parts of atomization process;
Described tensio-active agent is sodium oleate.
Adopt sodium oleate and aluminium nitride under specific weight ratio, both have stronger synergy, can improve thermal conductivity and hydrolysis preferably, improve the weather resistance of material.
Present invention also offers the preparation method that a kind of hydrolysis aluminium nitride fills polyamide-based heat-conducting plastic, it is easy to industrialization scale operation, and significantly can reduce production cost, further, the hydrolysis aluminium nitride obtained is filled polyamide-based heat-conducting plastic and is had good thermal conductivity and good weathering resistance.
Hydrolysis aluminium nitride fills a preparation method for polyamide-based heat-conducting plastic, comprises the following steps:
1) join in the modification cylinder in powder surface modifier after aluminium nitride being heated, by in the cartridge case that joins after tensio-active agent heating atomization in powder surface modifier, tensio-active agent through nozzle atomization in modification cylinder, fully contact with the powder of aluminium nitride, after drying, obtain surfactant-modified aluminium nitride;
2) by polymeric amide, oxidation inhibitor, processing aid and step 1) surfactant-modified aluminium nitride mixing after, join in twin screw extruder and melt extrude, obtain hydrolysis aluminium nitride and fill polyamide-based heat-conducting plastic.
Step 1) in, aluminium nitride is heated to 70 ~ 100 DEG C.
Step 1) in, the drying conditions obtaining surfactant-modified aluminium nitride after drying is: drying 1 ~ 6 hour in the baking oven of 70 DEG C ~ 150 DEG C.
Step 2) in, base polyamide need use after 3 ~ 5 hours 110 DEG C ~ 130 DEG C dryings.
Step 2) in, the temperature melt extruded in described twin screw extruder is 230 ~ 280 DEG C.
Hydrolysis aluminium nitride of the present invention fills polyamide-based heat-conducting plastic, can be used for the heat radiation of CPU, resistor, battery, store battery, electric motor, coil, rly., diode etc.
Compared with prior art, usefulness of the present invention is:
The present invention adopts tensio-active agent as surface treatment agent, carry out mixing with aluminium nitride powder after utilizing FTG type continuous powdery surface modification machine Surfactant to carry out atomization process and modify, be beneficial to decorative layer fully coated at aln surface, aluminium nitride filler modified in pre-compounding process is fully contacted with polyamide substrate, then set up effective interface, improve mechanics and the processing characteristics of strongthener entirety while thermal conductivity.Further, the hydrolysis aluminium nitride obtained is filled polyamide-based heat-conducting plastic and is had good thermal conductivity and good weathering resistance.
Hydrolysis aluminium nitride of the present invention fills the preparation method of polyamide-based heat-conducting plastic, existing processing unit powder surface modifier and twin screw extruder is adopted to realize, it is easy to industrialization scale operation, and significantly can reduce production cost, has broad application prospects.
Embodiment
Below by several embodiment, the present invention is specifically described, but technical scope of the present invention is not limited to these embodiments.In the present invention, when not specified, part all refers to weight part.
Embodiment 1:
Starting material preparation raw material by weight part in table 1:
Table 1
Starting material title |
Producer and the trade mark |
Weight ratio |
PA6 |
New meeting U.S.A reach 2500I |
100 parts |
Aluminium nitride |
/ |
110 parts |
Sodium oleate |
/ |
8 parts |
Antioxidant 1010/168 are composite |
Weight ratio 1:1, BASF |
5 parts |
Silicone powder |
/ |
5 parts |
Its preparation process is as follows:
1) preparation of surfactant-modified aluminium nitride:
Taking modification cylinder and cartridge case that aluminium nitride and sodium oleate add FTG type continuous powdery surface modification machine respectively in proportion, the aluminium nitride of preheating venting moisture being heated rapidly to preset temperature (85 DEG C), by entering modification cylinder after measuring fixed amount; By the sodium oleate of heating, utilize high-pressure air to be atomised to modification indoor by special nozzle, fully contact with aluminium nitride powder, powder, in the indoor collision mutually of modification, makes each particle all obtain fully coated.Enter accelerate cooling system after completing, the aluminium nitride of obtained surface modification, the product of acquisition is placed in dry 5 hours of the baking oven of 110 DEG C, after drying completes, obtains surfactant-modified aluminium nitride.
2) hydrolysis aluminium nitride fills the preparation of polyamide-based heat-conducting plastic:
Dried by base polyamide, drying plant position blowing-type drying machine, drying conditions is at 120 DEG C of temperature dry 4 hours; Use after base polyamide drying, then in proportion raw material is added in stirrer of preparing burden at a high speed (1000 revs/min), mix 4 minutes, mixed Preblend is placed in twin screw and melt extrudes granulation, the processing temperature of twin screw 230 ~ 280 DEG C, feeding frequency 10Hz, engine speed 300r/min, finally obtain hydrolysis aluminium nitride and fill polyamide-based heat-conducting plastic.
Embodiment 2:
Starting material preparation raw material by weight part in table 2:
Table 2
Starting material title |
Producer and the trade mark |
Weight part |
PA6 |
New meeting U.S.A reach 2500I |
100 parts |
Aluminium nitride |
/ |
110 parts |
Sodium dodecylbenzene sulfonate |
/ |
8 parts |
Antioxidant 1010/168 are composite |
Weight ratio 1:1, BASF |
5 parts |
Silicone powder |
/ |
5 parts |
Its preparation process is with embodiment 1.
Embodiment 3:
Starting material preparation raw material by weight part in table 3:
Table 3
Starting material title |
Producer and the trade mark |
Weight part |
PA6 |
New meeting U.S.A reach 2500I |
100 parts |
Aluminium nitride |
/ |
110 parts |
TX-10 |
/ |
8 parts |
Antioxidant 1010/168 are composite |
Weight ratio 1:1, BASF |
5 parts |
Silicone powder |
/ |
5 parts |
Its preparation process is with embodiment 1.
Embodiment 4:
Starting material preparation raw material by weight part in table 4:
Table 4
Starting material title |
Producer and the trade mark |
Weight ratio |
PA6 |
New meeting U.S.A reach 2500I |
100 parts |
Aluminium nitride |
/ |
100 parts |
Sodium oleate |
/ |
18 parts |
Antioxidant 1010/168 are composite |
Weight ratio 1:1, BASF |
5 parts |
Silicone powder |
/ |
5 parts |
Its preparation process is with embodiment 1.
Comparative example 1:
Press the starting material preparation raw material of weight part in table 1 in embodiment 4, wherein do not adopt sodium oleate, namely aluminium nitride does not select tensio-active agent process, and all the other are with embodiment 1.
The test result of embodiment 1 ~ 4 and comparative example 1
Hydrolysis aluminium nitride embodiment 1 prepared is filled polyamide-based heat-conducting plastic and is obtained standard batten, carries out first time test, and standard batten, temperature 25 DEG C, carries out second time test under humidity 90% condition after placing 72h;
Hydrolysis aluminium nitride embodiment 2 prepared is filled polyamide-based heat-conducting plastic and is obtained standard batten, carries out first time test, and standard batten, temperature 25 DEG C, carries out second time test under humidity 90% condition after placing 72h;
Hydrolysis aluminium nitride embodiment 3 prepared is filled polyamide-based heat-conducting plastic and is obtained standard batten, carries out first time test, and standard batten, temperature 25 DEG C, carries out second time test under humidity 90% condition after placing 72h;
Hydrolysis aluminium nitride embodiment 4 prepared is filled polyamide-based heat-conducting plastic and is obtained standard batten, carries out first time test, and standard batten, temperature 25 DEG C, carries out second time test under humidity 90% condition after placing 72h;
Hydrolysis aluminium nitride comparative example 1 prepared is filled polyamide-based heat-conducting plastic and is obtained standard batten, carries out first time test, and standard batten, temperature 25 DEG C, carries out second time test under humidity 90% condition after placing 72h;
Table 5 is polyamide-based heat-conducting plastic embodiment 1 ~ 4 of the present invention and the performance synopsis of comparative example 1 before and after wet environment.
Table 5
As known from Table 5, each composition of raw materials best performance of embodiment 1, embodiment 4 is compared with embodiment 1, its total weight part is the same, and difference is, the weight ratio of aluminium nitride and sodium oleate, visible, embodiment 1 be combined as ideal weight proportion, effect is ideal.Comparative example 1 is for adopting surface-modifying agent, and temperature 25 DEG C, after placing 72h under humidity 90% condition, its thermal conductivity declines rapidly, and its heat conductivility declines rapidly, and its major cause is this aluminium nitride powder facile hydrolysis, causes its heat conductivility sharply to decline.Visible, hydrolysis aluminium nitride of the present invention is filled polyamide-based heat-conducting plastic and is had good heat conductivility, and the not facile hydrolysis in wet condition of the aluminium nitride filler after surface modification, still can keep original thermal conductivity level after test.