CN109280374A - A kind of high glass fibre reinforced nylon material and preparation method thereof - Google Patents
A kind of high glass fibre reinforced nylon material and preparation method thereof Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C08K5/00—Use of organic ingredients
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- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention discloses a kind of high glass fibre reinforced nylon materials and preparation method thereof.High glass fibre reinforced nylon material includes following components and content: PA6,30-70wt%；GF, 30-60wt%；Compatilizer, 1-5wt%；Coupling agent, 0.5-1wt%；Antioxidant, 0.2-0.4wt%；Anti-floating fibre auxiliary agent, 0.5-1%.Preparation method: raw material is weighed by above-mentioned weight proportion, it is put into high-speed mixer and mixing 2-5min, mixed raw material is placed in extruding pelletization in double screw extruder and side feed material by discharging, and the main feeding revolving speed of screw machine is 200-500r/min, side feed material is 5-10r/min, and temperature is 230-250 DEG C.High fiber nylon of the invention has intensity height, good stability of the dimension, high fluidity, scratch-resistant and excellent heat resistance；High fiber nylon has good comprehensive performance, is widely used in the industries such as electric, automobile, building, office equipment, machinery, aerospace.
Description
Technical field
The present invention relates to a kind of high glass fibre reinforced nylon materials and preparation method thereof.
Background technique
PA6 has the characteristics such as thermoplasticity, lightweight, good toughness, chemicals-resistant and durability be good, is generally used for zero, automobile
The products such as part, mechanical part, electric equipment products, engineering accessory.In order to improve the mechanical property of PA6, it is frequently added various each
The modifying agent of sample, glass fibre are exactly the most common additive.For the product of not additive, the contraction 1% to 1.5% of PA6
Between, glass fiber additives, which are added, can make that shrinking percentage is reduced to 0.3%(and the perpendicular direction of process also wants slightly higher one
A bit).Polyamide glass fiber reinforced materials can add range of the glass fiber content in 5-60%, this kind of material according to the characteristic requirements of product
With good intensity, heat resistance, excellent shock resistance, good dimensional stability and low warpage properties etc., but it is added
Floating fine phenomenon is easily caused after glass fiber reinforcement.
" floating fibre " phenomenon is caused by glass emergence on the surface, and white glass is floated during plastic melt filling flow and is exposed to outside
Table just forms radial white trace on plastic surface after molding to be condensed, can be because of the difference of color when plastic is black
Increase and it is more obvious.The main reason for causing floating fibre is glass fibre and the difference of flowability and incompatibility of PA6.It is being molded
When, the two has isolated trend, and the small glass of density is floated to surface, and the big resin of density sinks to lining, then forms glass
Fine exposing phenomenon.Floating fibre phenomenon seriously will affect plastic appearance, this be in some plastics it is not received, so will be to glass
The nylon material of enhancing carries out structure optimization and surface is modified.
Summary of the invention
It is injection-molded finished the purpose of the present invention is to provide a kind of high glass fibre reinforced nylon material and preparation method thereof
Appearance floats fibre or less without floating fibre, and keeps excellent mechanical property and good mobility.
To achieve the goals above, the technical scheme is to design a kind of high glass fibre reinforced nylon material, packets
Include following components and content:
PA6 30-70wt%；
GF 30-60wt%；
Antioxidant 0.2-0.4wt%；
Coupling agent 0.5-1wt%；
Compatilizer 1-5wt%；
Anti-floating fibre auxiliary agent 0.5-1wt%；
The PA6 be viscosity 2.4 nylon raw material, 215 DEG C -225 DEG C of fusing point；
The GF is thermoplastic chopped strand, and diameter is 10 μm；
The antioxidant is the antioxidant and phosphite ester antioxidant of Hinered phenols；
The coupling agent is silane coupling agent, density 1.069g/cm3；
The compatilizer is containing the group that can be carried out with PA6 and glass physically or chemically；
The anti-floating fibre auxiliary agent be novel dendritic polymers, 135 DEG C of fusing point.
The compatilizer be maleic anhydride MAH type, carboxylic acid compatilizer it is one or more.
The maleic anhydride MAH type is ethylene and octene and maleic anhydride graft copolymer POE-g-MAH or EP rubbers
It is one or more with the graft copolymer EPDM-g-MAH or maleic anhydride EVA of maleic anhydride.
The maleic anhydride content of the maleic anhydride grafting POE-g-MAH is 8-15%.
The carboxylic acid type compatilizer is the graft copolymer PS-g- of acrylic acid and styrene PS, styrene-acrylonitrile AS
Graft copolymer PA-g-MAA, AS-g-MAA of AA, AS-g-AA or methacrylic acid and styrene PS, styrene-acrylonitrile AS
One of or it is a variety of.
The silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
The Hinered phenols antioxidant is N, N- hexamethylene bis (3,5- di-t-butyl -4- hydroxyl hydrocinnamamide) (antioxygen
Agent 1098), phosphite ester antioxidant is phosphorous acid three (2.4- di-tert-butyl-phenyl) ester (irgasfos 168).
The anti-floating fibre auxiliary agent is dendritic, is different from conventional adjuvants, surface is contained a large amount of functional groups and possessed
Nanoscale molecule has good dispersibility.
A kind of preparation method of high glass fibre reinforced nylon material, comprising the following steps:
(1) raw material is weighed by weight ratio；
(2) glass fibre is rendered into black with carbon black；
(3) remaining raw material is put into high-speed mixer and mixing 2-5 minutes；
(4) it discharges；
(5) mixed raw material is put into extruding pelletization in dual-screw-stem machine, glass is uniformly exported in side feed material, and the revolving speed of screw machine is
180-300 revs/min, temperature is 260-280 DEG C.
Wherein, PA6 selects viscosity for 2.4 raw material, and lower viscosity can reduce PA6 and glass fibre in plastic
Difference of flowability, and reduce the phenomenon that glass is separated with nylon.
Glass fibre selects 568H, and 10 μm of diameter, chopped length 3mm is rendered to black with carbon black in advance, can reduce floating
Appearance effects of the fibre to black plastic.
Compatilizer can improve filler surface property by functional group reactions, improve phase of the glass fibre with nylon
Capacitive.
Anti-floating fibre auxiliary agent is different from traditional polymer molecule, and dendritic structure is more advantageous to the reaction between functional group,
Inter-molecular binding force is increased, the mobility of compatibility and the material entirety of glass and nylon is improved.
PA6 has good comprehensive performance, and fusing point is lower, and Process temperature ranges are wide, and density is low, is easy molding, design is certainly
Big, the partiting thermal insulation by spending, and also have apparent advantage on mold and assembling cost.Not only tensile strength is high by PA6, impact
The excellent and heat distortion temperature of energy is high, heat-resisting, coefficient of friction is low, and wear-resistant, self-lubricating, oil resistant, chemical-resistance are excellent, and especially
It is adapted for using glass or other materials filling enhancing modified, promotes material property and class, meet final component and customer demand.
Since PA6 and glass fibre are incompatible material, the addition of coupling agent improves filler in the dispersibility of material, mentions
The high compatibility and binding force of material.The silane coupling agent of selection has the reactivity base for having affinity with polymer molecule
Group can be such that the bonding force between PA6 and glass fibre increases with containing polymer reactions such as carboxyl, epoxy group, isocyanate groups,
Interfacial tension is reduced, dispersibility is increased, ultimately forms the structure of thermodynamically stable even macroscopic microsegregation, and material has
There are good elongation at break, impact strength and weatherability.
Hinered phenols antioxidant 1098 and phosphite ester antioxidant 168 in antioxidant, are mainly used for preventing various originals
The oxidation of material.
The advantages and beneficial effects of the present invention are: a kind of high glass fibre reinforced nylon material of the present invention and its preparation side
Method, appearance of the high glass fibre reinforced nylon material with excellent mechanical property and beautification, dimensionally stable, good fluidity,
Easy to process, excellent weather resistance, chemical resistance, scratch resistance etc. solve the problems, such as the floating fibre that high-content glass easily causes.It can be wide
It is general to be applied to auto parts and components, mechanical part, electric equipment products, engineering accessory etc..
Specific embodiment
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical solution of the present invention, and not intended to limit the protection scope of the present invention.
1 ~ 4 concrete condition of embodiment is shown in Table one
Table one: formula and appearance detail
The nylon material that can be seen that the formula enhances for different glass fiber content from above-described embodiment 1-4 can all be done out
Excellent product is seen, plastic surface does not influence appearance without floating fine or a small amount of unobvious floating fibre.It can with the increase of content of glass fiber
Fine-tuning recipes are floating fine to reduce.We increase by 5 groups of embodiments on this basis and one group of comparative example studies formula situation in detail.
Table two: formula detail
The PA6 material that will be prepared above according to embodiment 1 ~ 5 and comparative example 1 is prepared according to same injecting condition and is tested
Batten and colour table.Specific injecting condition is injection temperature: 230 ~ 260 DEG C, injection pressure: and 40 ~ 70Mpa, injection moulding speed: 30 ~
60%.Mold temperature: 100 DEG C, specific physical property detection project is as follows, and performance test results are shown in Table three:,
Tensile strength: according to ISO 527(50mm/min) standard detection.
Bending strength/bending modulus: according to ISO 178(2mm/min) standard detection.
Izod notched impact strength: according to ISO 180/1A(room temperature, notch is milled) standard detection.
Heat distortion temperature: according to ISO 75(1.8Mpa) standard detection.
Appearance comparison, with in-company grade assessment method, content and result see the table below four.
Table three: mechanical property comparison
| Project/unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Tensile strength/MPa | 215 | 200 | 195 | 185 | 218 | 180 |
| Bending strength/MPa | 280 | 265 | 260 | 250 | 290 | 245 |
| Bending modulus/MPa | 11593 | 10261 | 9890 | 9680 | 12500 | 9340 |
| Impact strength/(J/m) | 13.5 | 12.5 | 11.7 | 11.2 | 14.2 | 10.5 |
| Heat distortion temperature/DEG C | 205.8 | 203.2 | 201.7 | 200.5 | 206.2 | 200.1 |
| Melt index/(g/10min) | 20.1 | 18.9 | 16.4 | 17.7 | 15.8 | 17.2 |
Table four: appearance comparison
From the comparing result (table three and table four) of above embodiments it can be found that in terms of mechanical property (table three), in appearance
Comparison (table four) in it can be found that: the addition of coupling agent so that the binding force between PA6 and glass fibre is reinforced so that it
Mechanical property and appearance are all improved；The addition of compatilizer is so that the compatibility of PA6 and glass improves, mechanical property and outer
Sight is more excellent, and the addition of anti-floating fibre auxiliary agent is effectively reduced surface floating fiber, but has minimal effect to mechanical property.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of high glass fibre reinforced nylon material, which is characterized in that including following components and content:
PA6 30-70wt%；
GF 30-60wt%；
Antioxidant 0.2-0.4wt%；
Coupling agent 0.5-1wt%；
Compatilizer 1-5wt%；
Anti-floating fibre auxiliary agent 0.5-1wt%；
The PA6 be viscosity 2.4 nylon raw material, 215 DEG C -225 DEG C of fusing point；
The GF is thermoplastic chopped strand, and diameter is 10 μm；
The antioxidant is the antioxidant and phosphite ester antioxidant of Hinered phenols；
The coupling agent is silane coupling agent, density 1.069g/cm3；
The compatilizer is containing the group that can be carried out with PA6 and glass physically or chemically；
The anti-floating fibre auxiliary agent be novel dendritic polymers, 135 DEG C of fusing point.
2. according to claim 1 a kind of high glass fibre reinforced nylon material, which is characterized in that the compatilizer be horse
Come acid anhydrides MAH type, carboxylic acid compatilizer it is one or more.
3. according to claim 2 a kind of high glass fibre reinforced nylon material, which is characterized in that the maleic anhydride
MAH type is the graft copolymerization of ethylene and octene and maleic anhydride graft copolymer POE-g-MAH or EP rubbers and maleic anhydride
Object EPDM-g-MAH's or maleic anhydride EVA is one or more.
4. according to claim 3 a kind of high glass fibre reinforced nylon material, which is characterized in that the maleic anhydride connects
The maleic anhydride content of branch POE-g-MAH is 8-15%.
5. according to claim 2 a kind of high glass fibre reinforced nylon material, which is characterized in that the carboxylic acid type is compatible
Agent be acrylic acid and styrene PS, graft copolymer PS-g-AA, AS-g-AA of styrene-acrylonitrile AS or methacrylic acid with
One of graft copolymer PA-g-MAA, AS-g-MAA of styrene PS, styrene-acrylonitrile AS or a variety of.
6. according to claim 1 a kind of high glass fibre reinforced nylon material, which is characterized in that silanes coupling
Agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
7. according to claim 1 a kind of high glass fibre reinforced nylon material, which is characterized in that the Hinered phenols are anti-
Oxygen agent is N, N- hexamethylene bis (3,5- di-t-butyl -4- hydroxyl hydrocinnamamide), and phosphite ester antioxidant is phosphorous acid three
(2.4- di-tert-butyl-phenyl) ester.
8. a kind of preparation method for preparing high glass fibre reinforced nylon material as described in claim 1, which is characterized in that packet
Include following steps:
(1) raw material is weighed by weight ratio；
(2) glass fibre is rendered into black with carbon black；
(3) remaining raw material is put into high-speed mixer and mixing 2-5 minutes；
(4) it discharges；
(5) mixed raw material is put into extruding pelletization in dual-screw-stem machine, glass is uniformly exported in side feed material, and the revolving speed of screw machine is
180-300 revs/min, temperature is 260-280 DEG C.
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| CN114230775A (en) * | 2021-12-27 | 2022-03-25 | 厦门德丰行塑胶工业有限公司 | Hyperbranched ester compound and nylon fiber-adding composite material and preparation method thereof |
| CN116023783A (en) * | 2023-02-17 | 2023-04-28 | 潮州明园新材料有限公司 | Scratch-resistant PA6 glass fiber reinforced material and preparation method thereof |
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| CN110594496A (en) * | 2019-03-30 | 2019-12-20 | 河北汇锐管业有限公司 | High-pressure-resistant anti-seepage heat-insulation composite pipeline and preparation method thereof |
| CN110594496B (en) * | 2019-03-30 | 2021-03-09 | 河北汇锐管业有限公司 | High-pressure-resistant anti-seepage heat-insulation composite pipeline and preparation method thereof |
| CN114230775A (en) * | 2021-12-27 | 2022-03-25 | 厦门德丰行塑胶工业有限公司 | Hyperbranched ester compound and nylon fiber-adding composite material and preparation method thereof |
| CN114230775B (en) * | 2021-12-27 | 2023-08-04 | 厦门德丰行塑胶工业有限公司 | Hyperbranched ester compound and nylon fiber composite material and preparation method thereof |
| CN116023783A (en) * | 2023-02-17 | 2023-04-28 | 潮州明园新材料有限公司 | Scratch-resistant PA6 glass fiber reinforced material and preparation method thereof |
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Application publication date: 20190129 |