CN110591344A - Efficient flame-retardant heat-conducting nylon composite material and preparation method thereof - Google Patents
Efficient flame-retardant heat-conducting nylon composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-efficiency flame-retardant heat-conducting nylon composite material and a preparation method thereof, wherein the preparation method comprises the following steps: mixing the components according to the formula proportion (in parts by weight, 20-60 parts of nylon matrix, 40-70 parts of heat-conducting filler, 3-10 parts of flame retardant, 0.5-3 parts of dipentaerythritol and 0.1-0.5 part of phosphite antioxidant), and then carrying out melt extrusion to prepare the high-efficiency flame-retardant heat-conducting nylon composite material; the finally prepared high-efficiency flame-retardant heat-conducting nylon composite material comprises a nylon matrix, heat-conducting filler, a flame retardant, dipentaerythritol and a phosphite antioxidant. The preparation method of the high-efficiency flame-retardant heat-conducting nylon composite material is simple and high-efficiency, and has low cost; the finally prepared high-efficiency flame-retardant heat-conducting nylon composite material has the advantages of high mechanical strength, excellent flame-retardant property, high heat-conducting efficiency and high thermal stability after long-term use, and is particularly suitable for thermal contact structural components with high requirements on heat conduction and heat dissipation.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a high-efficiency flame-retardant heat-conducting nylon composite material and a preparation method thereof.
Background
At present, in the field of polymer materials, the application of replacing metal with plastic is expanding, but the heat conductivity of metal is not possessed by common plastic. At present, in many fields such as civil electronic appliances, toys, communication, cables, military industry and the like, parts with certain heat conduction or heat dissipation functions are required, and meanwhile, the parts need to have higher mechanical strength and certain temperature resistance. Nylon is one of the most used engineering plastics, and nylon 6 generally has a thermal conductivity of 0.25W/(m · K), which limits its application in the fields of heat dissipation, heat conduction, etc.
In the prior art, the heat conductivity of the material is generally improved by adding a filler with high heat conductivity into a resin matrix, and common heat-conducting fillers comprise aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, carbon fibers, metal fibers and the like; the composite material is mainly composed of micron-sized alumina and silica powder, nano-sized alumina, graphene and nitride are used as filling powder in the field of high heat conduction, and zinc oxide is mostly used as heat-conducting silicone grease filler, which is expensive in cost and has a large addition amount in some flame-retardant application scenes.
Chinese patent 201610632928.0 discloses a nylon-based heat-conducting composite material and a preparation method thereof, wherein the nylon-based heat-conducting composite material comprises the following components: the nylon-based heat-conducting composite material has good heat-conducting, antistatic and flame-retardant functions, and good mechanical properties and processability, but the invention uses graphite as the heat-conducting filler, is not insulated per se, is limited in use in some power environments, and simultaneously uses a bromine flame-retardant system, has large addition amount of the flame retardant, is easy to remain free small-molecule bromine, and is easy to accelerate degradation of a resin matrix in a long-term thermal contact environment, so that the service life of the product is influenced.
Therefore, the research on the high-efficiency flame-retardant heat-conducting nylon composite material with good thermal stability and the preparation method thereof have very important significance.
Disclosure of Invention
The invention aims to solve the problem of poor thermal stability of a nylon-based flame-retardant heat-conducting composite material in the prior art, and provides a high-efficiency flame-retardant heat-conducting nylon composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
the efficient flame-retardant heat-conducting nylon composite material comprises the following components in parts by weight: 20-60 parts of a nylon matrix, 40-70 parts of a heat-conducting filler, 3-10 parts of a flame retardant, 0.5-3 parts of dipentaerythritol and 0.1-0.5 part of a phosphite antioxidant.
The invention selects dipentaerythritol as a char forming agent, has excellent char forming capability, can be compounded with a flame retardant so as to be beneficial to reducing the using amount of the flame retardant, has particularly excellent thermal stability after being compounded with a phosphite antioxidant, can ensure that a composite material has higher mechanical property and color retention property under long-term thermal environment contact, prolongs the service life of the composite material, and has the following specific mechanism: the dipentaerythritol and the phosphite antioxidant have good compatibility, after being mixed in a screw extruder, a thermal-oxidation-resistant protective group with uniform phase quality can be obtained, one end of the thermal-oxidation-resistant protective group is a charring agent, the charring agent is easy to dehydrate and carbonize under a high-temperature environment to form a compact carbonized layer, so that most of oxygen invasion can be isolated (the aging effect is actually that materials react with oxygen at high temperature), and the other end of the thermal-oxidation-resistant protective group is a free radical trapping agent which is used for blocking free radicals (part of oxygen enters the interior of molecules and oxidation reaction generates free radicals at high temperature) formed by oxygen invasion reaction, stopping and continuing degradation, so that the dipentaerythritol and the phosphite antioxidant are compounded according to a certain proportion, the dipentaerythritol and the phosphite antioxidant play a synergistic role in protecting resin from being oxidized finally.
The content of each component in the raw material of the high-efficiency flame-retardant heat-conducting nylon composite material is preferably in the above range, but the content is not limited to the above range, and can be properly adjusted, but the adjusted content of each component is not too high or too low, and the too high or too low content has different adverse effects on the nylon composite material, for example, the content of dipentaerythritol is too high and is easy to precipitate, so that the mechanical property of the nylon composite material is poor; if the temperature is too low, a compact carbon layer structure cannot be formed, and the aging can not be slowed down well.
As a preferable scheme:
according to the efficient flame-retardant heat-conducting nylon composite material, the nylon matrix is polyamide 6, and the carboxyl end group content of the polyamide 6 is 30-100 mu mol/g, preferably 60-80 mu mol/g; the effect of controlling the content of the terminal carboxyl groups in the range is good, when the content of the terminal carboxyl groups is too low, the reactive groups in nylon are reduced, the heat conducting performance of the product is reduced (the main reason is that the heat conducting filler contains groups capable of reacting with the terminal carboxyl groups of polyamide 6, the polyamide 6 is connected with the heat conducting filler in a chemical bond mode, the chemical bond is stronger than that of physical blending, and meanwhile, the problem of re-agglomeration after dispersion caused by physical blending can be effectively avoided, the heat conducting filler is ensured to be uniformly and stably dispersed, and further, the heat conducting performance of the composite material is ensured, when the content of the terminal carboxyl groups of the polyamide 6 is lower, the polyamide cannot be sufficiently connected with the heat conducting filler through the chemical bond, and further, the heat conducting performance of the product is reduced), when the content of the terminal carboxyl groups is too high, the phenomenon that the small molecules.
According to the efficient flame-retardant heat-conducting nylon composite material, the heat-conducting filler is aminosilane modified gamma crystalline phase boehmite with the particle size of D50 being 0.7-1.5 mu m, the heat-conducting filler is prepared by a method of mixing raw material aminosilane and gamma crystalline phase boehmite at a low speed, and the specific steps are as follows: 1) weighing aminosilane and gamma crystalline phase boehmite in a mass ratio of 0.5: 95.5; 2) proportionally introducing into a mixer, wherein the mixing process comprises the following steps: rotating for 1min and stopping for 2min at 50-80 rpm (avoiding destroying the gamma crystal phase boehmite at a high speed), and repeating for four to six times (avoiding continuous rotation so as to cause overhigh shearing heat and destroy the gamma crystal phase boehmite).
The boehmite is used as the heat-conducting filler, which not only has excellent and certain flame retardant effect, but also has better thermal stability than the general boehmite material, meanwhile, the gamma-crystalline phase boehmite is subjected to polar surface treatment by using aminosilane, the particle size is controlled within a certain range, the shearing resistance in the processing process is effectively improved (the specific mechanism is that the gamma-crystalline phase boehmite coated by the aminosilane is equivalent to a layer of flexible layer for a hard crystalline phase, and the amino silane absorbs shearing energy in the processing process to protect the gamma-crystalline phase boehmite and further improve the shearing resistance of the gamma-crystalline phase boehmite), and meanwhile, the gamma-crystalline phase boehmite can be better dispersed in resin to form the heat-conducting effect, has rich sources and low cost, in addition, the molecular structure contains water, and the heat can be greatly reduced by decomposition at high temperature, form better heat conduction network chain, heat conductivility and flame retardant efficiency promote greatly.
According to the high-efficiency flame-retardant heat-conducting nylon composite material, the flame retardant is melamine or a salt compound thereof; besides excellent flame retardant effect, the melamine flame retardant also has excellent self-lubricating effect, thereby reducing the shearing heat in the processing process, having high whiteness and being made into products with various colors.
According to the high-efficiency flame-retardant heat-conducting nylon composite material, the purity of dipentaerythritol is more than or equal to 95%, namely the mass content of reaction byproducts is less than or equal to 5%, wherein the mass content of reaction byproducts, namely monopentaerythritol is less than 1%.
According to the high-efficiency flame-retardant heat-conducting nylon composite material, the phosphite antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite or antioxidant 168.
According to the efficient flame-retardant heat-conducting nylon composite material, the tensile strength of the efficient flame-retardant heat-conducting nylon composite material is 38-56 MPa, the retention rate of the tensile strength after aging is 68-86%, the heat conductivity coefficient is 0.51-1.25, and the GWIT is 850-875 ℃.
The invention also provides a method for preparing the high-efficiency flame-retardant heat-conducting nylon composite material, which is characterized in that the high-efficiency flame-retardant heat-conducting nylon composite material is prepared by mixing the components according to the formula proportion and then carrying out melt extrusion.
As a preferable scheme:
in the method, the mixing refers to mixing in a high-speed mixer for 3-5 min, a double-screw extruder is adopted for melt extrusion, the processing temperature of the double-screw extruder is 180-250 ℃, and the rotating speed of the screws is 180-600 rpm.
Has the advantages that:
(1) the preparation method of the high-efficiency flame-retardant heat-conducting nylon composite material is simple, high-efficiency, low in cost and suitable for large-scale production;
(2) the high-efficiency flame-retardant heat-conducting nylon composite material disclosed by the invention has the advantages of good mechanical strength, excellent flame-retardant property, high heat-conducting efficiency and good thermal stability after long-term use, and is particularly suitable for thermal contact structural components with high requirements on heat conduction and heat dissipation.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The preparation method of the aminosilane modified gamma crystalline phase boehmite comprises the following steps: 1) weighing aminosilane and gamma crystalline phase boehmite in a mass ratio of 0.5: 95.5; 2) introducing aminosilane and gamma crystalline phase boehmite into a mixer according to a formula, wherein the mixing process comprises the following steps: the preparation method is characterized in that the steps of rotating at 60 revolutions per minute (avoiding high-speed destruction of the gamma crystal phase boehmite), rotating at 1 minute, stopping for 2 minutes, and repeating for five times to prepare the aminosilane modified gamma crystal phase boehmite.
Examples 2 to 9
The efficient flame-retardant heat-conducting nylon composite material comprises the following components in parts by weight: 20-60 parts of a nylon matrix, 40-70 parts of a heat-conducting filler, 3-10 parts of a flame retardant, 0.5-3 parts of dipentaerythritol and 0.1-0.5 part of a phosphite antioxidant, wherein the nylon matrix is polyamide 6 with the terminal carboxyl group content of 30-100 mu mol/g; the heat-conducting filler is aminosilane modified gamma crystalline phase boehmite with the particle size of D50 being 0.7-1.5 mu m, and the preparation method is the same as that of example 1; the flame retardant is melamine or salt compound thereof; the purity of the dipentaerythritol is more than or equal to 95 percent, and the mass content of the reaction by-product monopentaerythritol is less than 1 percent; the phosphite antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite or antioxidant 168.
The preparation method comprises the following steps: mixing the components in a high-speed mixer for 3-5 min according to the formula proportion, and then carrying out melt extrusion by using a double-screw extruder, wherein the processing temperature of the double-screw extruder is 180-250 ℃, and the rotating speed of a screw is 180-600 revolutions per minute.
Specific parameters and performance indexes of the high-efficiency flame-retardant heat-conducting nylon composite material are shown in table 1, wherein an aging test is carried out in a heat aging oven at 140 ℃ for 1500h, the heat conductivity coefficient is tested according to an ISO 22007-longitudinal test standard, the flame-retardant grade is tested according to an UL-941.6 mm standard, GWIT is tested according to an IEC 60965-2 standard, in the classes of flame retardants, the first represents melamine, the second represents melamine cyanurate, in the classes of antioxidants, the first represents bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and the second represents antioxidant 168.
TABLE 1 preparation parameters in examples 2 to 9
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Without departing from the method of the invention, several improvements and additions may be made, which shall also be considered as the scope of protection of the invention.
Comparative example 1
The preparation process of the flame-retardant heat-conducting nylon composite material is basically the same as that in example 2, except that the weight parts of dipentaerythritol and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite in the raw materials are 1.5 parts and 2 parts respectively. The performance indexes of the finally obtained flame-retardant heat-conducting nylon composite material are shown in table 2.
Comparative example 2
A flame-retardant heat-conducting nylon composite material is prepared by the same process as in example 2, except that the raw materials comprise 3.4 parts by weight of dipentaerythritol and 0.1 part by weight of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite. The performance indexes of the finally obtained flame-retardant heat-conducting nylon composite material are shown in table 2.
Comparative example 3
The preparation process of the flame-retardant heat-conducting nylon composite material is basically the same as that in example 2, except that dipentaerythritol is not added into the raw materials, and the weight part of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite is 3.5 parts. The performance indexes of the finally obtained flame-retardant heat-conducting nylon composite material are shown in table 2.
Comparative example 4
The preparation process of the flame-retardant heat-conducting nylon composite material is basically the same as that in example 2, except that bis (2, 4-dicumylphenyl) pentaerythritol diphosphite is not added to the raw materials, and the weight part of dipentaerythritol is 3.5 parts. The performance indexes of the finally obtained flame-retardant heat-conducting nylon composite material are shown in table 2.
Comparative example 5
The preparation process of the flame-retardant heat-conducting nylon composite material is basically the same as that in the example 2, except that dipentaerythritol in the raw materials is replaced by monopentaerythritol. The performance indexes of the finally obtained flame-retardant heat-conducting nylon composite material are shown in table 2.
Comparative example 6
The preparation process of the flame-retardant heat-conducting nylon composite material is basically the same as that in example 2, except that the raw material, the aminosilane-modified gamma-crystalline phase boehmite, is replaced by graphite, and the performance index of the finally obtained flame-retardant heat-conducting nylon composite material is shown in table 2.
Comparative example 7
A flame-retardant heat-conductive nylon composite material, whose preparation process is substantially the same as that in example 2, except that the gamma-crystalline phase boehmite modified with the amino silane in the raw material was replaced with the gamma-crystalline phase boehmite, and the performance index of the finally obtained flame-retardant heat-conductive nylon composite material is shown in table 2.
Comparative example 8
The preparation process of the flame-retardant heat-conducting nylon composite material is basically the same as that in the embodiment 2, except that the polyamide 6 with the carboxyl end group content of 30-100 mu mol/g serving as a nylon matrix in the raw materials is replaced by the polyamide 6 with the carboxyl end group content of 150 mu mol/g, and the performance index of the finally obtained flame-retardant heat-conducting nylon composite material is shown in the table 2.
Comparative example 9
The preparation process of the flame-retardant heat-conducting nylon composite material is basically the same as that in the embodiment 2, except that the polyamide 6 with the carboxyl end group content of 30-100 mu mol/g is replaced by the polyamide 6 with the carboxyl end group content of 10 mu mol/g in the nylon matrix in the raw materials, and the performance index of the finally obtained flame-retardant heat-conducting nylon composite material is shown in the table 2.
TABLE 2
Comparing example 2 with comparative example 1, it can be seen that the thermal stability of the product of example 2 is better, because the char-forming agent and the antioxidant in example 2 can well form the thermal-oxidation-resistant protecting group with char-forming agent at one end and radical scavenger at the other end, which can be used to prevent oxygen invasion, and simultaneously capture the radicals formed by the oxygen invasion reaction, and terminate the degradation, while the amount of dipentaerythritol in comparative example 1 is too low compared with bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and dipentaerythritol cannot form a compact carbon layer structure, which does not have a good effect of isolating oxygen, so that the thermal stability of the prepared composite material is relatively poor.
Comparing example 2 with comparative example 2, it can be seen that the thermal stability of the product of example 2 is better, because the char-forming agent and the antioxidant in example 2 can well form the thermal-oxygen-resistant protecting group with char-forming agent at one end and radical scavenger at the other end, which can be used to prevent oxygen invasion and end the radical scavenger formed by oxygen invasion reaction to stop its continued degradation, while the amount of dipentaerythritol in comparative example 2 is too high compared with bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and the dipentaerythritol itself has a low melting point, is easy to precipitate to affect the processing and product appearance, and cannot function efficiently, so that the thermal stability of the composite material is relatively poor.
Comparing example 2 with comparative example 3, it can be seen that the thermal stability of the product of example 2 is better, because the comparative example 3 does not contain dipentaerythritol, a compact carbon layer structure cannot be formed, and a good oxygen isolation effect cannot be achieved, so that the flame retardant property and the thermal stability of the prepared composite material are relatively poor.
Comparing example 2 with comparative example 4, it can be seen that the thermal stability of the product of example 2 is much better, because the comparative example 4 does not contain bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, can not capture the free radicals formed by the oxygen invasion reaction, and can not terminate the continuous degradation, so that the thermal stability of the composite material is relatively poor.
Comparing example 2 with comparative example 5, it can be seen that the heat stability of the product of example 2 is more excellent because monopentaerythritol is added instead of dipentaerythritol in comparative example 5 and not all char-forming agents can act synergistically with bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and thus the heat stability of the composite material in comparative example 5 is relatively poor.
Comparing example 2 with comparative example 6, it can be seen that the product of example 2 has better thermal stability, because graphite is added in comparative example 6 instead of aminosilane modified gamma crystalline phase boehmite, and the graphite has good conductivity and cannot play the role of insulation, so the application in some electric environments is limited.
As can be seen from comparison between example 2 and comparative example 7, the gamma-crystalline boehmite of example 2 was subjected to polar surface treatment with aminosilane, and the modification treatment improved the shear resistance of the gamma-crystalline boehmite, i.e., the particle size thereof could be controlled within a certain range, thereby preventing deterioration and non-uniformity of heat conduction due to random particle size breakage.
Comparing example 2 with comparative example 8, it can be seen that the product of example 2 has better performance, because the nylon matrix adopted in comparative example 8 has too high carboxyl end group content, which indicates that too many small molecules in the nylon matrix remain, and the thermal stability and flame retardant performance of the product are affected by too many small molecules.
Comparing the example 2 with the comparative example 9, it can be seen that the performance of the product in the example 2 is better, because the content of the terminal carboxyl group in the nylon matrix adopted in the comparative example 9 is too low, and the nylon matrix lacks a group capable of reacting with the heat-conducting filler, so that the combination of the nylon matrix and the heat-conducting filler is weakened, and the problem of re-agglomeration after dispersion caused by physical blending cannot be effectively avoided, so that the heat-conducting filler cannot be uniformly and stably dispersed, and further the heat-conducting performance of the composite material is weakened.
Claims (9)
1. The efficient flame-retardant heat-conducting nylon composite material is characterized by comprising the following components in parts by weight: 20-60 parts of a nylon matrix, 40-70 parts of a heat-conducting filler, 3-10 parts of a flame retardant, 0.5-3 parts of dipentaerythritol and 0.1-0.5 part of a phosphite antioxidant.
2. The efficient flame-retardant heat-conducting nylon composite material as claimed in claim 1, wherein the nylon matrix is polyamide 6, and the carboxyl end group content of the polyamide 6 is 30-100 μmol/g.
3. The efficient flame-retardant heat-conducting nylon composite material as claimed in claim 1, wherein the heat-conducting filler is aminosilane-modified gamma crystalline phase boehmite with a D50 particle size of 0.7-1.5 μm.
4. The nylon composite material as claimed in claim 1, wherein the flame retardant is melamine or its salt compound.
5. The efficient flame-retardant heat-conducting nylon composite material as claimed in claim 1, wherein the purity of dipentaerythritol is greater than or equal to 95%, and the mass content of reaction by-product monopentaerythritol is less than 1%.
6. The nylon composite material of claim 1, wherein the phosphite antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite or antioxidant 168.
7. The efficient flame-retardant heat-conducting nylon composite material as claimed in any one of claims 1 to 6, wherein the tensile strength of the efficient flame-retardant heat-conducting nylon composite material is 38-56 MPa, the retention rate of the tensile strength after aging is 68-86%, the heat conductivity coefficient is 0.51-1.25, and the GWIT is 850-875 ℃.
8. The preparation method of the high-efficiency flame-retardant heat-conducting nylon composite material as claimed in any one of claims 1 to 7, is characterized by comprising the following steps: the components are mixed according to the formula proportion and then are melted and extruded to prepare the high-efficiency flame-retardant heat-conducting nylon composite material.
9. The method according to claim 8, wherein the mixing is carried out in a high-speed mixer for 3-5 min, the melt extrusion is carried out by using a double-screw extruder, the processing temperature of the double-screw extruder is 180-250 ℃, and the screw rotating speed is 180-600 rpm.
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