CN114350140A - Low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 and preparation method thereof - Google Patents
Low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-deformation easy-forming reinforced nitrogen flame-retardant PA6/PA66 and a preparation method thereof. A low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following raw materials in parts by weight: 45-63 parts of PA6 resin, 10-15 parts of PA66 resin, 10-20 parts of nitrogen flame retardant MCA, 15-30 parts of calcium sulfate whisker, 0.5-1 part of high-temperature antioxidant, 0.5-1 part of lubricant, 0-0.5 part of nucleating agent, 0.5-1 part of flowing agent and 0.5-1 part of coupling agent. The PA6 material adopts calcium sulfate whiskers to replace glass fibers, reduces the warping degree of an injection molding product, improves the dimensional stability and reduces the assembly clearance.
Description
Technical Field
The invention relates to a low-deformation easy-forming reinforced nitrogen flame-retardant PA6/PA66 and a preparation method thereof, belonging to the technical field of plastics.
Background
Along with the improvement of the life quality of people and the increase of market competition of enterprises, various low-voltage electrical appliance manufacturers put forward the requirements of miniaturization, thinning and high efficiency on low-voltage electrical appliance shells and put forward higher requirements on the injection molding performance and the assembly performance of modified plastics.
The glass fiber is widely applied as a reinforcing agent of the low-voltage apparatus shell modified plastic, but the glass fiber is difficult to be uniformly distributed in a complex mould, and a poor glue area is easy to appear, so that the surface smoothness of the material is poor, the performance is unstable, and the fluidity of the material is greatly reduced due to the structure of the glass fiber, so that high yield in one cavity is difficult to realize, and the production efficiency is influenced. In addition, the processing has serious abrasion to the die, particularly to thin-wall parts, the phenomenon of glue shortage is obvious, the appearance and the performance of the injection molding product are influenced, particularly the deformation amount after molding is larger, and larger clearance tolerance exists after assembly.
The existing glass fiber reinforced nitrogen-based flame-retardant PA6 material has low production efficiency and large gaps in the assembly process, and cannot meet the increasingly mature market requirements.
In order to solve the problem of assembly tolerance of the existing glass fiber reinforced nitrogen-based flame-retardant PA6 material, the glass fiber is ground for use in the prior art, namely the length of the glass fiber in the composite material is reduced, and the glass fiber with small length-diameter ratio is used for reinforcing the nitrogen-based flame-retardant PA6 composite material, so that the warping degree of the composite material is reduced, but the ground glass fiber is difficult to process, and the price is about one time higher than that of the common glass fiber, so that the material cost is increased; the purpose of shearing and crushing the general glass fibers added with the composite material is achieved by adjusting the screw combination of a double-screw extruder of a composite material processing machine, namely enhancing the clipping of the screw, so that the warping degree of the composite material is finally reduced, but high shearing seriously abrades the screw, the equipment is quickly worn, and the material cost is finally improved; besides, the traditional mineral fillers such as talcum powder, calcium carbonate, mica powder and the like are used for replacing glass fiber, so that the warping degree of the composite material can be reduced, but the mechanical property of the whole composite material also has large loss, and the product performance requirement cannot be well met.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the reinforced nitrogen flame-retardant PA6/PA66 with low deformation and easy forming and the preparation method thereof, and the calcium sulfate whisker is adopted to replace glass fiber, so that the warping degree of an injection molding product is reduced, the dimensional stability is improved, and the assembly clearance is reduced.
The invention is realized by the following technical scheme:
a low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following raw materials:
the low-deformation easy-forming reinforced nitrogen-based flame-retardant PA6/PA66 has the viscosity of the PA6 resin of 2.2-2.6 Pa.S.
The low-deformation easy-forming reinforced nitrogen-based flame-retardant PA6/PA66 has the viscosity of the PA66 resin of 2.4-2.8 Pa.S.
The low-deformation easy-forming reinforced nitrogen flame-retardant PA6/PA66 is a mixture of an antioxidant 245 and an antioxidant 168.
The low-deformation easy-forming reinforced nitrogen flame-retardant PA6/PA66 is characterized in that the weight ratio of the antioxidant 245 to the antioxidant 168 is 1: 1.
The low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 is prepared from N, N' -ethylene bis stearamide.
The low-deformation easy-forming reinforced nitrogen flame-retardant PA6/PA66 comprises a coupling agent and a crosslinking agent, wherein the coupling agent is gamma-aminopropyltriethoxysilane.
The preparation method of the low-deformation easy-forming reinforced nitrogen-based flame-retardant PA6/PA66 comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) mixing the weighed raw materials in a medium-speed mixer for 3-7min to obtain a mixed material;
(3) and (3) adding the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt reaction, and carrying out extrusion granulation.
The preparation method of the low-deformation easy-forming reinforced nitrogen flame-retardant PA6/PA66 comprises the following process conditions of a double-screw extruder: temperature in the first zone: 260 ℃, zone two temperature: 260 ℃, three-zone temperature: 260 ℃, four zone temperature: 250 ℃, five zone temperature: 230 ℃, six zone temperature: 220 ℃, temperature in seven zones: 210 ℃, eight zone temperature: 210 ℃, head temperature: 250 ℃; screw rotation speed: 300-500 r/min.
The invention achieves the following beneficial effects:
the PA6 material adopts calcium sulfate whiskers to replace glass fibers, reduces the warping degree of an injection molding product, improves the dimensional stability and reduces the assembly clearance.
By compounding and using the raw materials according to a specific proportion, the product is ensured to have ultrahigh flowing property under the condition of not reducing the mechanical property, and the mold filling rate can be greatly improved.
The size of the whisker is fine, and the whisker as a reinforcing agent of the modified plastic does not influence the molding fluidity of the composite material and is close to that of the unfilled resin. The whiskers can be uniformly distributed in the polymer matrix, so that extremely thin, extremely narrow and even corner parts can be uniformly filled, and obvious anisotropy does not occur, thereby reducing the deformation of the product and ensuring the precision.
The calcium sulfate whisker has a certain length-diameter ratio (10-300), has a fine structure (the diameter is 0.1-10 microns), has the characteristics of high strength and high modulus, and can be uniformly dispersed in plastic composite materials such as PP, PA, PBT, PE, ABS, PVC, POM and the like, so that the cohesive strength of a polymer is increased, weak links are reduced, and the mechanical strength of the composite material is obviously improved.
The calcium sulfate crystal whisker is derived from natural gypsum ore, and has wide source, large yield and moderate price.
The calcium sulfate whisker reinforced nitrogen flame-retardant PA6/PA66 composite material has the advantages that the size stability is good on the premise that the mechanical property of the composite material is not remarkably reduced, the crystallization speed can be more efficiently improved by the PA66 and the nucleating agent, the injection molding period is shortened, the ultrahigh fluidity realizes that more products are produced by one mold, the deformation quantity of the products can be effectively reduced by adding the whisker, the cost of the existing material is not increased, and the requirements of miniaturization, thin wall and high efficiency on a low-voltage apparatus shell of an existing low-voltage apparatus manufacturer can be met.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following raw materials:
wherein, the viscosity of the PA6 resin is 2.2-2.6 Pa.S. The viscosity of the PA66 resin is 2.4-2.8 Pa.S. The antioxidant is a mixture of the antioxidant 245 and the antioxidant 168 according to the weight ratio of 1: 1. The lubricant is N, N' -ethylene bis stearamide. The coupling agent is gamma-aminopropyl triethoxysilane. The nucleating agent is Bruggemann Bruggolen P22. The flowable agent is Bruggemann Bruggolen M1420.
A preparation method of low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) mixing the weighed raw materials in a medium-speed mixer for 3-7min to obtain a mixed material;
(3) adding the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt reaction, and extruding and granulating, wherein the process conditions of the double-screw extruder are as follows: temperature in the first zone: 260 ℃, zone two temperature: 260 ℃, three-zone temperature: 260 ℃, four zone temperature: 250 ℃, five zone temperature: 230 ℃, six zone temperature: 220 ℃, temperature in seven zones: 210 ℃, eight zone temperature: 210 ℃, head temperature: 250 ℃; screw rotation speed: 300-500 r/min.
Example 2
A low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following raw materials:
wherein, the viscosity of the PA6 resin is 2.2-2.6 Pa.S. The viscosity of the PA66 resin is 2.4-2.8 Pa.S. The antioxidant is a mixture of the antioxidant 245 and the antioxidant 168 according to the weight ratio of 1: 1. The lubricant is N, N' -ethylene bis stearamide. The coupling agent is gamma-aminopropyl triethoxysilane. The nucleating agent is Bruggemann Bruggolen P22. The flowable agent is Bruggemann Bruggolen M1420.
A preparation method of low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) mixing the weighed raw materials in a medium-speed mixer for 3-7min to obtain a mixed material;
(3) adding the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt reaction, and extruding and granulating, wherein the process conditions of the double-screw extruder are as follows: temperature in the first zone: 260 ℃, zone two temperature: 260 ℃, three-zone temperature: 260 ℃, four zone temperature: 250 ℃, five zone temperature: 230 ℃, six zone temperature: 220 ℃, temperature in seven zones: 210 ℃, eight zone temperature: 210 ℃, head temperature: 250 ℃; screw rotation speed: 300-500 r/min.
Example 3
A low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following raw materials:
wherein, the viscosity of the PA6 resin is 2.2-2.6 Pa.S. The viscosity of the PA66 resin is 2.4-2.8 Pa.S. The antioxidant is a mixture of the antioxidant 245 and the antioxidant 168 according to the weight ratio of 1: 1. The lubricant is N, N' -ethylene bis stearamide. The coupling agent is gamma-aminopropyl triethoxysilane. The nucleating agent is Bruggemann Bruggolen P22. The flowable agent is Bruggemann Bruggolen M1420.
A preparation method of low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) mixing the weighed raw materials in a medium-speed mixer for 3-7min to obtain a mixed material;
(3) adding the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt reaction, and extruding and granulating, wherein the process conditions of the double-screw extruder are as follows: temperature in the first zone: 260 ℃, zone two temperature: 260 ℃, three-zone temperature: 260 ℃, four zone temperature: 250 ℃, five zone temperature: 230 ℃, six zone temperature: 220 ℃, temperature in seven zones: 210 ℃, eight zone temperature: 210 ℃, head temperature: 250 ℃; screw rotation speed: 300-500 r/min.
Comparative example 1
A low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following raw materials:
the rest is the same as in example 3.
Comparative example 2
A low-deformation easy-forming reinforced nitrogen-series flame-retardant PA6/PA66 comprises the following raw materials:
the rest is the same as in example 3.
The plastic materials prepared in the examples and comparative examples were subjected to property measurement, and the results are shown in Table 1.
Table 1 results of performance test of each example and comparative example.
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Maximum deformation amount% | 0.6 | 0.8 | 0.5 | 1.6 | 5.3 |
| Molding cycle s | 14 | 14.5 | 13.5 | 18 | 21 |
| Flow rate g/10min | 56 | 56 | 55 | 28 | 3.0 |
| Impact Strength (KJ/M2) | 27 | 32 | 30 | 24 | 93 |
As can be seen from table 1, compared with comparative example 1, examples 1, 2 and 3 have removed the use of calcium sulfate whiskers for glass fibers, and in terms of impact strength, examples 1, 2 and 3 have not increased much, but have better improvement in flow rate and maximum deformation amount, and at the same time, have shortened the forming cycle, thus has improved the processing efficiency, because the whiskers can be distributed in the polymeric matrix evenly, can make extremely thin, extremely narrow and even corner position can get the homogeneous filling, apparent anisotropy does not appear, thus reduce the deformation amount of the product, guarantee the precision.
Compared with the comparative example 2, the nucleating agents are added in the examples 1, 2 and 3, and the PA66 and the nucleating agents can more effectively improve the crystallization speed and shorten the injection molding period.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A low-deformation easy-forming reinforced nitrogen flame-retardant PA6/PA66 is characterized by comprising the following raw materials in parts by weight:
2. the PA6/PA66 with low deformation and easy forming and reinforced nitrogen flame retardance as claimed in claim 1, wherein the viscosity of the PA6 resin is 2.2-2.6 Pa.S.
3. The PA6/PA66 with low deformation and easy forming and reinforced nitrogen flame retardance as claimed in claim 1, wherein the viscosity of the PA66 resin is 2.4-2.8 Pa.S.
4. The PA6/PA66 with low deformation and easy forming and reinforced nitrogen flame retardance as claimed in claim 1, wherein the antioxidant is a mixture of an antioxidant 245 and an antioxidant 168.
5. The low deformation amount easy-forming reinforced nitrogen-based flame retardant PA6/PA66 as claimed in claim 4, wherein the weight ratio of the antioxidant 245 to the antioxidant 168 is 1: 1.
6. The PA6/PA66 with low deformation and easy forming and reinforced nitrogen flame retardance as claimed in claim 1, wherein the lubricant is N, N' -ethylene bis stearamide.
7. The PA6/PA66 with low deformation and easy forming and reinforced nitrogen flame retardance as claimed in claim 1, wherein the coupling agent is gamma-aminopropyltriethoxysilane.
8. The method for preparing the low-deformation easy-forming reinforced nitrogen-based flame-retardant PA6/PA66 as claimed in any one of claims 1-7, wherein the method comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) mixing the weighed raw materials in a medium-speed mixer for 3-7min to obtain a mixed material;
(3) and (3) adding the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt reaction, and carrying out extrusion granulation.
9. The preparation method of the low-deformation easy-forming reinforced nitrogen-based flame retardant PA6/PA66 as claimed in claim 8, wherein the process conditions of the twin-screw extruder are as follows: temperature in the first zone: 260 ℃, zone two temperature: 260 ℃, three-zone temperature: 260 ℃, four zone temperature: 250 ℃, five zone temperature: 230 ℃, six zone temperature: 220 ℃, temperature in seven zones: 210 ℃, eight zone temperature: 210 ℃, head temperature: 250 ℃; screw rotation speed: 300-500 r/min.
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- 2021-12-29 CN CN202111633837.6A patent/CN114350140A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408926A (en) * | 2013-06-26 | 2013-11-27 | 安徽科聚新材料有限公司 | Polyamide composite material and preparation method thereof |
| CN105542446A (en) * | 2015-11-12 | 2016-05-04 | 浙江铧淳塑料有限公司 | High-fluidity and easy-injection molding PA6-PA66 composite material and preparation method thereof |
| CN106243702A (en) * | 2016-07-29 | 2016-12-21 | 浙江铧淳塑料有限公司 | A kind of nitrogen system flame-proof PA 6 composite and its preparation method and application |
| CN106280428A (en) * | 2016-08-10 | 2017-01-04 | 浙江铧淳塑料有限公司 | A kind of anti-yellowing step-down warpage flame-retardant reinforced nylon and preparation method thereof |
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