CN112679945A - High-glass-fiber-reinforced nylon composite material with good appearance and application thereof - Google Patents
High-glass-fiber-reinforced nylon composite material with good appearance and application thereof Download PDFInfo
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- CN112679945A CN112679945A CN202011469114.2A CN202011469114A CN112679945A CN 112679945 A CN112679945 A CN 112679945A CN 202011469114 A CN202011469114 A CN 202011469114A CN 112679945 A CN112679945 A CN 112679945A
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- 238000000034 method Methods 0.000 claims description 11
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- -1 PA56 Polymers 0.000 claims description 3
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- DQTKCIVHDDGAFK-UHFFFAOYSA-N 2-(5,6-dihydro-4H-cyclopenta[d][1,3]dithiol-2-ylidene)-1,3-dithiole-4,5-dithiol Chemical compound S1C(S)=C(S)SC1=C1SC(CCC2)=C2S1 DQTKCIVHDDGAFK-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003973 paint Substances 0.000 claims 1
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a high-glass-fiber reinforced nylon composite material with good appearance and application thereof. The material comprises the following components in parts by weight: 30-65 parts of glass fiber; 35-70 parts of nylon resin; 3-15 parts of transparent nylon; 0.01-1 part of expanded graphite; 0.1 to 5 portions of other components. The high-glass-fiber-reinforced nylon composite material with good appearance, which is disclosed by the invention, keeps the inherent mechanical properties and thermal properties of the glass-fiber-reinforced nylon material, has excellent apparent quality, low emission and good weather resistance, does not have the problem of surface precipitation when used in a high-temperature and high-humidity environment, can simultaneously meet the application requirements of automotive interior, exterior, engine periphery and the like, and greatly widens the application field of the high-glass-fiber-reinforced nylon composite material.
Description
Technical Field
The invention belongs to the technical field of polyamide, and particularly relates to a high-glass-fiber reinforced nylon composite material with good appearance and application thereof.
Background
The glass fiber reinforced nylon composite material is widely applied to the industries of automobiles, household electrical appliances and electronic and electrical appliances because of excellent mechanical property, creep resistance, fatigue resistance and chemical corrosion resistance. However, when the glass fiber content in the composite material reaches a certain content, the surface of the product is floated, and the appearance is rapidly degraded, so that the application of the material, especially the application of parts with higher appearance requirements, is greatly limited. A great deal of research work is also done by relevant technicians at home and abroad to solve the problems.
Currently, the following methods are generally adopted to improve the problem of floating fibers on the surface of nylon products: 1) the fluidity of the resin matrix is improved, for example, nylon oligomer, low-viscosity nylon, copolymerized nylon, graphene modified high-fluidity nylon and the like are used, the viscosity of the polymer at the injection molding temperature is actually reduced, but the mechanical property and the thermal deformation temperature of the material are sacrificed, the high-temperature thermal storage test cannot be passed, and the glass fiber is easy to get rid of the constraint of the resin matrix due to the excessively low viscosity or the difference of viscosity gradient, so that the exposure is caused. 2) The material fluidity is improved by a common modification means, such as adipic acid, hyperbranched polyester and other fluidity improving additives, but the low molecular weight additives are poor in temperature resistance, can cause material thermal degradation when large-sized products are injection molded, are easy to separate out and influence appearance in the application of heat aging and high-temperature and high-humidity engine periphery, and basically have no effect when the glass fiber content is large. 3) The content of the glass fiber in the material is reduced, for example, part of glass beads, mineral powder or special types of glass fiber such as flat glass fiber, talcum powder, finely ground glass fiber and the like are added, but the cost is increased or the performance of the material is sacrificed, the cost performance of the product is not high, and the effect of improving the floating fiber is not obvious. 4) If the organic dye nigrosine is used, the crystallization temperature of the material is reduced, and the organic dye nigrosine is used, the cost is lower, the obvious improvement effect is achieved, but the addition of the nigrosine can cause the light aging resistance of the material to be deteriorated, the total carbon emission is obviously increased, and the use requirement of the automobile plastic part as an interior and exterior decoration cannot be met. 5) The special polymer is adopted for compounding, such as transparent nylon, the appearance is improved by simultaneously reducing the melting point and the crystallization temperature of polyamide, but in order to achieve the ideal effect of improving floating fiber, the addition amount of the transparent nylon needs to be higher, so that the formula cost of the product is increased, and the thermal deformation temperature of the material is easily reduced too much.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art and provide a high-glass-fiber-reinforced nylon composite material with good appearance, when a blend of the high-glass-fiber-reinforced nylon composite material with good appearance is extruded from an extruder or an injection molding machine, under the dual effects of self-lubricating property of expanded graphite and swelling effect of a high polymer extrudate, the expanded graphite with fluffy volume, light weight and low viscosity flows towards the outer side of a melt along with the expansion direction, and is enriched on the surface layer of the material through delayed solidification of amorphous transparent nylon, so that the aim of improving the fiber floating of a final part is fulfilled while a small amount of transparent nylon is added. The high-glass-fiber-reinforced nylon composite material with good appearance, which is disclosed by the invention, keeps the inherent mechanical properties and thermal properties of the glass-fiber-reinforced nylon material, has excellent apparent quality, low emission and good weather resistance, does not have the problem of surface precipitation when used in a high-temperature and high-humidity environment, can simultaneously meet the application requirements of automotive interior, exterior, engine periphery and the like, and greatly widens the application field of the high-glass-fiber-reinforced nylon composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-glass-fiber reinforced nylon composite material with good appearance comprises the following components in parts by weight:
30-65 parts of glass fiber;
35-70 parts of nylon resin;
2-10 parts of transparent nylon;
0.01-1 part of expanded graphite;
0.1 to 5 portions of other components.
The glass fiber is chopped glass fiber with the fiber diameter of 10 to 20 mu m and the length of 3.0 to 4.5 mm.
The nylon resin is selected from one or a combination of more of PA66, PA56, PA6 and PA 66/6T.
The transparent nylon is (a) an amorphous random copolymer; (b) a block copolymer prepared by melt blending of an amorphous copolymer and a semicrystalline homopolymer or a similar amorphous copolymer; (c) a multipolymer nylon copolymer. The transparent nylon is selected from one or more of PA6I, PA6I/6T, PA6/PACMT, PA6I/6T/6IPD, PA12/MACMI, PA6/TMDT/6T, PA6/PA 12.
The expanded graphite is a loose and porous vermicular substance which is obtained by inserting a non-carbonaceous reactant into the graphite interlayer by using a physical or chemical method through natural graphite flakes, combining with a hexagonal network plane of carbon, simultaneously keeping a crystal compound of a graphite laminated structure and carrying out high-temperature expansion; preferably, the expanded graphite is sulfur-free expanded graphite having a mesh number of 40 to 400, and includes a form of powder, compressed particles, master batch, or the like substantially containing the above components.
The other components are selected from one or more of an antioxidant, a light stabilizer, a heat stabilizer, a mold release agent, a lubricant, a nucleating agent, an antistatic agent, an antibacterial agent, a hydrolysis resistance agent and a color additive according to actual use requirements.
The high-glass-fiber-reinforced nylon composite material with good appearance is applied to the fields of automobile interior and exterior trim, engine periphery, electronics, electrical and mechanical instruments and the like, is suitable for injection molding, extrusion and blow molding, and comprises automobile air outlet blades, a front end frame, a cylinder cover, an intercooler end cover, an elevator guide rail sliding block, a television bracket and other parts.
Compared with the prior art, the invention has the following beneficial effects:
1) when the blend of the high-glass-fiber-reinforced nylon composite material with good appearance is extruded from an extruder or an injection molding machine, under the dual effects of self-lubricity of expanded graphite and swelling effect of a high polymer extrudate, the expanded graphite with fluffy volume, light weight and low viscosity flows towards the outer side of a melt along with the expansion direction, the temperature of the nylon resin with glass-fiber reinforced nucleation is rapidly reduced to be below the crystallization temperature along with the mold filling of the polymer melt, the nylon resin is cooled, crystallized and solidified, the amorphous transparent nylon with high glass transition temperature is cooled more slowly and solidified slowly, and the non-polar expanded graphite is more prone to be enriched towards the transparent nylon with weaker polarity, and finally the non-polar expanded graphite and the amorphous transparent nylon are solidified and shaped together on the surface layer of the material to obtain the polymer with attractive appearance, smoothness and firm inside, so that.
2) The expanded graphite is creatively matched with the transparent nylon to obtain the high-glass-fiber reinforced nylon composite material with good appearance, and a new idea is provided for improving the problem of fiber floating on the surface of a nylon product.
3) The material property of the expanded graphite is creatively utilized, and the expanded graphite is combined with the appearance improvement application of the glass fiber reinforced nylon composite material, so that the application range of the expanded graphite is widened.
Detailed Description
In order to make the technical solution of the present invention clearer and more clear, the present invention is further described below, and any solution obtained by substituting technical features of the technical solution of the present invention with equivalents and performing conventional reasoning falls within the scope of the present invention.
The following materials were used in the examples of the invention:
PA 66: EPR27, Neuma group
PA 56: e-1273, Kaiser Biotechnology
PA 6: MF800, Rimefurt of Jiangsu
PA 66/6T: EP523HT, Huafeng group
Glass fiber: 568H, giant rock group
Transparent nylon PA 6I: TM01, Shandong Chen Ruisen
Transparent nylon PA 6I/6T: PA3426, DuPont
Expanded graphite A: 80 mesh, commercially available
Expanded graphite B: master batch with 20 percent of expanded graphite content and montanic acid wax lubricant serving as carrier, and is prepared by self
Lubricant: OP wax, Kelaien
A stabilizer: h10 Bluggeman
Black masterbatch: n54/1044, Gaolai
Copolymerization nylon: HYG-2500E, Jiangsu Haiyang
Flow improvement aid: refined adipic acid, Huafeng group
Glass beads: 050-20-215, SOVITEC, France
Aniline black masterbatch: n54/1033, Gaolae
Respectively weighing glass fiber, nylon resin, transparent nylon, expanded graphite, a lubricant, a stabilizer and black master according to the formula dosage (parts by weight) of specific examples 1-12 in Table 1 and comparative examples 1-7 in Table 2, and putting the components except the glass fiber into a high-speed mixer for mixing until the components are uniform to obtain a premix; then putting the obtained pre-mixture into a double-screw extruder for melting and mixing, and extruding and granulating the glass fiber filler by adopting a side feeding process to obtain the high-glass-fiber reinforced nylon composite material; wherein the extrusion temperature is 230-270 ℃, and the screw rotating speed is set to be 450-650 rpm.
The product performance testing method comprises the following steps:
drying the particles obtained in the examples and the comparative examples in an oven at 100-120 ℃ for 4-6 h, then performing injection molding at 240-310 ℃ to prepare samples, controlling the mold temperature at 100-120 ℃, and performing related performance tests according to the following test methods, wherein the test results are detailed in tables 1 and 2.
(1) Tensile strength: bars size 170 x 10 x 4mm, test speed 5mm/min according to ISO 527 method;
(2) bending strength: according to ISO 178 method, the sample size is 80 x 10 x 4mm, the test speed is 5 mm/min;
(3) impact strength of the simply supported beam: spline size 80 x 10 x 4mm according to ISO 179/1eA method;
(4) heat distortion temperature: according to ISO 75-2 method, 1.80MPa load, bar size 80X 10X 4 mm;
(5) apparent mass: injection molding a large number of dermatoglyph plaques, 208 × 147 × 2.7mm in size, evaluated visually; the apparent mass of the workpiece is defined by 1-10 values according to the number of floating fibers, and the larger the value is, the fewer the floating fibers are on the surface, and the better the appearance is;
(6) emission property: testing total carbon by a VDA 277 method with test parameters of 120 ℃/5h and a headspace method;
(7) weather resistance: the grey scale of the color plate was evaluated after irradiation with 1240KJ/m2 using the SAE J2412 method;
(8) and (4) precipitation and verification: the prepared sample plate was placed in a high temperature and high humidity aging chamber at 85 ℃/RH 85% and treated for 7 days to observe whether or not a substance was precipitated on the surface.
(9) And (4) hot storage verification: placing the prepared sample plate in a high-temperature aging box at 230 ℃, storing for 1h, and observing experimental phenomena;
table 1 example high glass fiber reinforced nylon composite material composition ratio (parts by weight) and performance test results
Table 2 comparative example the composition ratio (parts by weight) of each component of the high glass fiber reinforced nylon composite material and the results of each performance test
From the examples in table 1 and the comparative examples 6-8 in table 2, the transparent nylon and the expanded graphite are added simultaneously, and the comprehensive performance of the reinforced nylon composite material is obviously superior to that of the transparent nylon or the expanded graphite which is added independently. Even if the use amount of the transparent nylon is doubled under the condition of high glass fiber content, the same apparent mass effect cannot be obtained, and the risk of thermal storage deformation exists. The independent addition of the expanded graphite has little effect on the improvement of the apparent quality of the high-glass-fiber reinforced nylon system.
From comparative examples 1 to 5 in table 2, the conventional methods such as copolymerized nylon, flow improvement aid, mineral, nigrosine and the like have small apparent quality improvement effect in a high glass fiber reinforced nylon system, and have the defects of low mechanical property, poor weather resistance, obvious precipitation and large smoke generation.
Claims (10)
1. The high-glass-fiber-reinforced nylon composite material with good appearance is characterized in that: the paint comprises the following components in parts by weight:
30-65 parts of glass fiber;
35-70 parts of nylon resin;
2-10 parts of transparent nylon;
0.01-1 part of expanded graphite;
0.1 to 5 portions of other components.
2. The high-glass-fiber-reinforced nylon composite material with good appearance as claimed in claim 1, wherein: the glass fiber is chopped glass fiber with the fiber diameter of 10 to 20 mu m and the length of 3.0 to 4.5 mm.
3. The high-glass-fiber-reinforced nylon composite material with good appearance as claimed in claim 1, wherein: the nylon resin is selected from one or a combination of more of PA66, PA56, PA6 and PA 66/6T.
4. The high-glass-fiber-reinforced nylon composite material with good appearance as claimed in claim 1, wherein: the transparent nylon is (a) an amorphous random copolymer; (b) a block copolymer prepared by melt blending of an amorphous copolymer and a semicrystalline homopolymer or a similar amorphous copolymer; (c) a multipolymer nylon copolymer.
5. The high-glass-fiber-reinforced nylon composite material with good appearance as claimed in claim 4, wherein: the transparent nylon is selected from one or more of PA6I, PA6I/6T, PA6/PACMT, PA6I/6T/6IPD, PA12/MACMI, PA6/TMDT/6T, PA6/PA 12.
6. The high-glass-fiber-reinforced nylon composite material with good appearance as claimed in claim 1, wherein: the expanded graphite is a loose and porous vermicular substance which is obtained by inserting non-carbonaceous reactants into graphite layers by using a physical or chemical method through natural graphite flakes, combining with a hexagonal network plane of carbon, simultaneously keeping a graphite laminated structure, and carrying out high-temperature expansion.
7. The high-glass-fiber-reinforced nylon composite material with good appearance of claim 6, wherein the high-glass-fiber-reinforced nylon composite material comprises: the expanded graphite is sulfur-free expanded graphite with the mesh number of 40-400.
8. The high-glass-fiber-reinforced nylon composite material with good appearance as claimed in claim 1, wherein: the other components are selected from one or more of an antioxidant, a light stabilizer, a heat stabilizer, a mold release agent, a lubricant, a nucleating agent, an antistatic agent, an antibacterial agent, a hydrolysis resistance agent and a color additive.
9. The high glass fiber reinforced nylon composite material with good appearance according to any one of claims 1 to 8, wherein: the high-glass-fiber reinforced nylon composite material with good appearance is applied to the fields of automobile interior and exterior decorations, engine peripheries, electronics, electrics and mechanical instruments.
10. The good-appearance high-glass-fiber-reinforced nylon composite material of claim 9, which is characterized in that: the high-glass-fiber-reinforced nylon composite material with good appearance is suitable for injection molding, extrusion and blow molding, and is applied to automobile air outlet blades, front end frames, cylinder cover covers, intercooler end covers, elevator guide rail sliding blocks and television supports.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583440A (en) * | 2021-09-26 | 2021-11-02 | 江苏博云塑业股份有限公司 | Nylon 66 material and preparation method thereof |
| CN114456586A (en) * | 2022-01-26 | 2022-05-10 | 江苏金发科技新材料有限公司 | Floating-fiber-free high-welding-strength reinforced nylon composite material and preparation method and application thereof |
| CN115819967A (en) * | 2022-12-12 | 2023-03-21 | 苏州旭光聚合物有限公司 | Polyamide composite material and preparation method and application thereof |
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