CN114213840A - Ultra-high strength, low warpage and low floating fiber PA (polyamide) reinforced material and preparation process thereof - Google Patents

Ultra-high strength, low warpage and low floating fiber PA (polyamide) reinforced material and preparation process thereof Download PDF

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CN114213840A
CN114213840A CN202111592045.9A CN202111592045A CN114213840A CN 114213840 A CN114213840 A CN 114213840A CN 202111592045 A CN202111592045 A CN 202111592045A CN 114213840 A CN114213840 A CN 114213840A
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glass fiber
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CN114213840B (en
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何子超
倪世茂
王志鹏
陶鹏
李敬玉
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Guangzhou Shitian Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The invention provides a PA (polyamide) reinforced material with ultrahigh strength, low warpage and low floating fiber, which comprises the following components in percentage by weight: 620-40 parts of PA, 55-80 parts of glass fiber, 2-8 parts of mineral powder, 2-8 parts of functional compatilizer, 0.2-0.6 part of lubricant and 0.2-1.5 parts of antioxidant; the functional compatilizer is maleic anhydride grafted ethylene-octylene copolymer, maleic anhydride grafted ethylene-propylene copolymer or maleic anhydride grafted ethylene-propylene-diene monomer rubber; the PA6 comprises a high-melting-index PA6 and a low-melting-index PA6, wherein the melting indexes are respectively 70-100 g/10min and 30-50 g/10min, the high-melting-index PA6 accounts for 40-50%, and the low-melting-index PA6 accounts for 40-60%. In the invention, the ultra-high glass fiber content (more than 60 percent) provides excellent performances such as higher mechanical strength, heat resistance, dimensional stability and the like for the PA reinforced material, and simultaneously overcomes the defects of high warpage, high fiber floating, low gloss and the like generated by high-content fibers.

Description

Ultra-high strength, low warpage and low floating fiber PA (polyamide) reinforced material and preparation process thereof
Technical Field
The invention belongs to the field of PA (polyamide) reinforced materials, and particularly relates to a PA reinforced material with ultrahigh strength, low warpage and low floating fiber and a preparation process thereof.
Background
Nylon (PA) resins typically require the addition of glass fibers to improve the strength of the material. After the PA is reinforced by the glass fiber, the strength of the PA can reach more than several times of the original strength. The glass fiber content is higher, the strength is higher, the heat resistance is higher, and the glass fiber content can be even compared with metal materials. Therefore, PA reinforcement materials can be used in various mechanical parts instead of metals. The glass fiber reinforced nylon has the advantages of high strength, good toughness, good fatigue resistance, good self-lubricating property, high wear resistance, high heat resistance, easy processing and the like, and is widely applied to peripheral parts of automobile engines and other products with high strength and certain heat resistance requirements needed in other fields. With the increase of the content of the glass fiber, although the mechanical strength and the heat resistance of the glass fiber are gradually improved, the glass fiber is easy to warp due to uneven heat conduction, so that the injection molding part is deformed, and the use of the injection molding part is influenced. Meanwhile, the content of the glass fiber is increased, so that the surface of the plastic part is more prone to fiber floating, and the appearance of the plastic part is affected.
CN201510873933.6 discloses a glass fiber reinforced PA6 composition with improved floating fiber and a preparation method thereof, and the composition is prepared by mixing, extruding and granulating 30-60 parts of PA6, 1-10 parts of PA66, 25-45 parts of glass fiber, 5-15 parts of mica, 0-5 parts of toughening agent, 5-10 parts of nucleating agent and 5-10 parts of silicone powder. After the mica and the silicone powder are mixed, the compatibility between the PA6 and the glass fiber is enhanced, and similar anchoring nodes, namely cross-linking points, are formed between the glass fiber and the nylon resin, so that the bonding state of the glass fiber and the resin is improved, and the separation of the glass fiber and the resin is reduced; meanwhile, the nylon 66 also improves the mechanical strength of the composition. CN201610425990.2 discloses a glass fiber reinforced PA6 composition for improving fiber floating phenomenon and a preparation method thereof, wherein the composition is prepared from the following components in parts by weight: PA6, PA66, glass fiber, magnesium sulfate whisker, toughening agent, nucleating agent and silicone oil. The magnesium sulfate whisker and the silicone oil are mixed to enhance the compatibility with the glass fiber, similar anchoring nodes, namely cross-linking points, are formed between the glass fiber and the nylon resin, the bonding state of the glass fiber and the resin is improved, the separation of the glass fiber and the resin is reduced, the glass fiber and the resin flow synchronously in the processing process, the glass fiber is not easy to tear, the exposure of the glass fiber is greatly reduced, and the mechanical strength of the PA6 composition is improved by adding the PA 66. According to the technical scheme, the strength is increased through the PA66, the processing temperature is increased, and the production cost is obviously increased; in addition, the compatibility of the glass fiber and nylon is improved by adding other additives, but actually, the combination of mica and silicone powder or the combination of magnesium sulfate whisker and silicone oil has a general effect of improving the compatibility of the glass fiber and nylon, and the phenomenon of fiber floating is easy to occur in the processing process.
In conclusion, the research on the glass fiber reinforced PA material with ultrahigh strength, low warpage and low floating fiber and the preparation process thereof have wide application prospects.
Disclosure of Invention
The invention aims to provide a PA reinforcing material with ultrahigh strength, low warpage and low floating fiber. The ultra-high glass fiber content (more than 60 percent) provides excellent performances such as higher mechanical strength, heat resistance, dimensional stability and the like for the PA reinforced material, and simultaneously overcomes the defects of high warpage, high fiber floating, low gloss and the like generated by high-content fibers.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the PA reinforcing material with ultrahigh strength, low warpage and low floating fiber comprises the following raw materials in parts by weight:
PA 620-40 parts
55-80 parts of glass fiber
2-8 parts of mineral powder
2-8 parts of functional compatilizer
0.2 to 0.6 portion of lubricant
0.2-1.5 parts of an antioxidant;
the functional compatilizer is maleic anhydride grafted ethylene-octylene copolymer, maleic anhydride grafted ethylene-propylene copolymer or maleic anhydride grafted ethylene-propylene-diene monomer rubber;
the PA6 comprises a high-melting-index PA6 and a low-melting-index PA6, wherein the melting index of the high-melting-index PA6 is 70-100 g/10min, and the melting index of the low-melting-index PA6 is 30-50 g/10 min; in the PA6, the high-melting-index PA6 accounts for 40-50%, and the low-melting-index PA6 accounts for 40-60%. The melt index indicates the melt flow rate, and a high value of the melt index indicates good melt flowability, whereas poor flowability.
The glass fiber is subjected to alkali treatment or acid treatment, and the glass fiber with the length of 3mm and the diameter of 15-17 mu m is selected as the glass fiber.
According to the molecular structure characteristics and the similar compatibility principle, the invention adopts the functional compatilizer (maleic anhydride grafted ethylene-octylene copolymer, maleic anhydride grafted ethylene-propylene copolymer or maleic anhydride grafted ethylene propylene diene monomer) which is both PA and glass fiber compatible, and the glass fiber is wound or wrapped under the coordination of the lubricant to form a high-strength reinforced concrete structure, thereby forming the PA reinforced composite material with ultrahigh strength, low warpage and low fiber floating. Taking maleic anhydride grafted ethylene-octylene block copolymer as an example, the ethylene-octylene block copolymer has amphiphilic characteristics similar to a surfactant, maleic acid groups (carbonyl and carboxyl) are easy to be compatible with glass fiber (-O-Si-O-) and are also easy to be compatible with PA groups (amide group), and ethylene-octylene groups are easy to be compatible with PA molecular chains, so that the glass fiber can be tightly wound or wrapped to form a wrapped rubber bundle structure, the strength of the material is greatly improved, warping is prevented, and few fibers are floated.
Meanwhile, the PA6 is combined by using the high-melt-index PA6 and the low-melt-index PA6, and a great deal of research shows that the PA6 can be used by combining the PA6 with the melt index of 70-100 g/10min and 30-50 g/10min, so that advantages and disadvantages can be brought forward, and better processing performance, mechanical strength and aging resistance can be obtained. The PA6 resin melt with low melting point has low flow rate, and forms a central main fluid layer with glass fibers (difficult to flow); the high-melt-index PA6 resin melt has relatively high flow velocity, and the mobile phase forms turbulent flow in advance of the main fluid, so that glass fibers can be wound or wrapped, rubber bundles wrapping the glass fibers can be arranged radially, the strength of the material is enhanced, and floating fibers cannot be generated. Furthermore, according to the turbulent effect of the fluid, the plastic with low melt index is easy to be in the front of the turbulent flow when flowing, thereby contacting the mold wall with low temperature firstly and forming a surface solidification layer rapidly (see fig. 1). Through the control of the pressure maintaining time process, the PA6 resin with high melt index wound or coated by the PA6 resin is finally formed, and simultaneously forms a multilayer grid structure with the glass fibers arranged in the radial direction, so that the strength of the material is enhanced, and the effect of preventing the glass fibers from being exposed is also generated.
In the present invention, preferably, the glass fiber is treated in one of the following two ways:
alkaline treatment: a. soaking the glass fiber in a sodium hydroxide solution for 8-12 h at the temperature of 30-65 ℃; b. naturally airing the soaked glass fibers, and placing the glass fibers into a drying oven at 150 ℃ for drying;
acid treatment: a. soaking the glass fiber in an acrylic acid or acrylate solution for 8-12 h at the temperature of 30-65 ℃; b. naturally airing the soaked glass fiber, and drying in a drying oven at 150 ℃.
The preferable treatment method is soaking treatment in sodium hydroxide solution, wherein the soaking time is 10h, and the soaking temperature is 45 ℃. After alkaline pretreatment, a hydrated layer or silicon hydroxyl (-Si-OH) appears on the glass fiber, so that the binding capacity of the glass fiber and anhydride or carboxylic acid groups in functional compatilizer molecules is improved, and better comprehensive mechanical properties can be obtained.
In the invention, the lubricant is preferably one or a mixture of more of lubricant EBS, lubricant PETS and lubricant paraffin, and is preferably lubricant EBS. The lubricant can be dissociated in the functional compatilizer and the glass fiber and serves as an auxiliary medium, so that the extrusion processing of the material is facilitated, the floating fiber is reduced, and the gloss is formed.
In the present invention, preferably, the mineral powder is at least one of talc powder, kaolin powder and mica powder. 1250 mesh talc is preferred.
Microscopically, the PA6 and the glass fiber form a three-dimensional framework structure through amphipathy by the functional compatilizer, and a reinforced concrete structure is formed with the aid of the lubricant and the talcum powder. Of these, PA6, the functional compatibilizer and the lubricant are similar to cement (lubricant is similar to water), glass fiber is similar to steel bar, and talc is similar to sand. PA6 and functional compatilizer molecules are wrapped or wound with glass fibers under the assistance of a lubricant to form rubber bundles, and the glass fibers are radially staggered and directionally arranged under the action of an extrusion external force, so that the probability of transverse arrangement (stand-off) is reduced, and the degree of fiber floating is greatly reduced. Due to the criss-cross arrangement of the glass fibers (arrangement of the reinforcing steel bars), when the glass fibers are subjected to external load, the structural synergistic effect in the matrix resin can mutually disperse and absorb external energy, so that a good synergistic enhancement effect is generated, and deformation (warping) is not easy to occur.
In the invention, preferably, the antioxidant is one or a mixture of several of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 1098. An equal ratio mixture of antioxidants 1098 and 168 is preferred.
In the invention, preferably, the functional compatilizer is maleic anhydride grafted ethylene-octylene copolymer, and in the maleic anhydride grafted ethylene-octylene copolymer, the mass fraction of maleic anhydride is 2-3%, and the grafting rate is more than or equal to 1%.
In the present invention, preferably, the high melting index PA6 has a melting index of 80g/10min, and the low melting index PA6 has a melting index of 40g/10 min; in PA6, the high melting index PA6 accounts for 50%, and the low melting index PA6 accounts for 50%.
In the invention, preferably, the ultra-high strength, low warpage and low floating fiber PA reinforcing material is prepared from the following raw materials in parts by weight:
PA 620-22 parts
65-70 parts of glass fiber
2-3 parts of mineral powder
5-8 parts of functional compatilizer
0.4 portion of lubricant
1.0 part of antioxidant.
The proportion of the raw materials, the high glass fiber content can obviously improve the mechanical strength, heat resistance and dimensional stability of the PA6, and simultaneously, the dosage of the compatilizer is increased, and the high-melting-index PA6 and the low-melting-index PA6 are combined, so that the warping is prevented, and the floating fiber is reduced.
The invention also provides a preparation process of the PA reinforcing material with ultrahigh strength, low warpage and low floating fiber, which comprises the following steps:
s1, drying PA6 at 100-120 ℃ for 2-4 h;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant in proportion, stirring in a high-speed stirrer for 1-3 minutes, and uniformly mixing;
s3, adding the uniformly mixed materials in the step S2 into an internal mixer, mixing, and granulating to obtain a glass fiber compatilizer mixture;
s4, weighing the glass fiber compatilizer mixture obtained in the step S3, mineral powder and PA6 in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
and S5, finally, extruding the material through a double-screw extruder, cooling, drying and granulating to obtain the PA reinforced material.
Preferably, the process conditions of the extrusion are: the extrusion temperature is 220-250 ℃, and the rotation speed of a main machine is 400-550 rpm.
The preparation process of the invention mixes and granulates the glass fiber with the compatilizer, the lubricant and the antioxidant, and then mixes the glass fiber with the PA6, so that the compatibility of the glass fiber and the PA6 is greatly improved, the glass fiber is uniformly dispersed in the PA6, and the phenomena of warping, fiber floating and the like are reduced.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the existing glass fiber modified PA reinforced material, the reinforced material provided by the invention not only maintains excellent mechanical properties, but also improves the defects of warping, fiber floating and the like, and the glossiness of a plastic part is better.
2. The PA6 of the invention adopts the combination use of the high-melt-index PA6 and the low-melt-index PA6, the high-melt-index PA6 resin melt forms turbulent flow in advance of the main fluid (the low-melt-index PA6 and the glass fibers) due to the relatively fast flow rate, so that the glass fibers can be wound or wrapped, the rubber beams wrapping the glass fibers are radially arranged, the high-melt-index PA6 resin is finally wound or wrapped on the low-melt-index PA6 resin, and the radial arranged glass fibers form a multi-layer grid structure, thereby enhancing the strength of the material and generating the effect of preventing the glass fibers from being exposed.
3. According to the molecular structure characteristics and the similar compatibility principle, the invention adopts the functional compatilizer which is compatible with PA and glass fiber, and the glass fiber is wound or wrapped under the coordination of the lubricant to form a high-strength reinforced concrete structure, thereby forming the PA reinforced composite material with ultrahigh strength, low warpage and low floating fiber.
Drawings
FIG. 1 is a schematic illustration of the turbulence generated by the melt at different flow rates according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, but the scope of the present invention is not limited to the embodiments.
In the following embodiments, the raw materials are commercially available unless otherwise specified.
Wherein, the functional compatilizer is maleic anhydride grafted ethylene-octylene copolymer, and in the maleic anhydride grafted ethylene-octylene copolymer, the mass fraction of maleic anhydride is 2-3%, and the grafting rate is more than or equal to 1%. The antioxidant is selected from the mixture of antioxidants 1098 and 168 in equal ratio. The adopted glass fiber is subjected to alkaline treatment, the length is 3mm, the diameter is 15-17 mu m, and the alkaline treatment steps are as follows: a. soaking the glass fiber in a sodium hydroxide solution for 10 hours at the soaking temperature of 45 ℃; b. naturally airing the soaked glass fiber, and drying in a drying oven at 150 ℃.
Example 1
The PA reinforced material with ultrahigh strength, low warpage and low floating fiber is prepared from the following raw materials:
PA 622 Kg (high melt index PA 612 Kg, melt index 80g/10 min; low melt index PA 610 Kg, melt index 40g/10min)
65Kg of glass fiber
1250-mesh talcum powder 3Kg
5Kg of functional compatilizer
Lubricant EBS 0.4Kg
1.0Kg of antioxidant.
The preparation method of the PA reinforcing material with ultrahigh strength, low warpage and low floating fiber comprises the following steps:
s1, drying PA6 at 110 ℃ for 3 h;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant in proportion, stirring for 1 minute in a high-speed stirrer, and uniformly mixing;
s3, adding the uniformly mixed materials in the step S2 into an internal mixer, mixing, and granulating to obtain a glass fiber compatilizer mixture;
s4, weighing the glass fiber compatilizer mixture obtained in the step S3, talcum powder and PA6 in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
and S5, finally, extruding the material by a double-screw extruder (the extrusion temperature is 240 ℃, and the rotating speed of a main machine is 500rpm), cooling, drying and granulating to obtain the PA reinforcing material.
The PA reinforcing material of this example was tested using ISO standards and the results are given in table 1 below.
TABLE 1
Figure BDA0003430155090000061
Example 2
The PA reinforced material with ultrahigh strength, low warpage and low floating fiber is prepared from the following raw materials:
PA620 Kg (high melt index PA66 Kg, melt index 80g/10 min; low melt index PA 614 Kg, melt index 40g/10min)
Glass fiber 70Kg
1250-mesh talcum powder 2Kg
8Kg of functional compatilizer
Lubricant EBS 0.4Kg
1.0Kg of antioxidant.
The preparation method of the PA reinforcing material with ultrahigh strength, low warpage and low floating fiber comprises the following steps:
s1, drying PA6 at 110 ℃ for 3 h;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant in proportion, stirring for 1 minute in a high-speed stirrer, and uniformly mixing;
s3, adding the uniformly mixed materials in the step S2 into an internal mixer, mixing, and granulating to obtain a glass fiber compatilizer mixture;
s4, weighing the glass fiber compatilizer mixture obtained in the step S3, talcum powder and PA6 in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
and S5, finally, extruding the material by a double-screw extruder (the extrusion temperature is 230 ℃, and the rotation speed of a main machine is 450rpm), cooling, drying and granulating to obtain the PA reinforcing material.
The PA composite of this example was tested using ISO standards and the results are given in table 2 below.
TABLE 2
Figure BDA0003430155090000071
Example 3
The PA reinforced material with ultrahigh strength, low warpage and low floating fiber is prepared from the following raw materials:
PA630 Kg (high melt index PA 613 Kg, melt index 90g/10 min; low melt index PA 617 Kg, melt index 50g/10min)
75Kg of glass fiber
1250-mesh talcum powder 5Kg
6Kg of functional compatilizer
Lubricant EBS 0.5Kg
1.2Kg of antioxidant.
The preparation method of the PA reinforcing material with ultrahigh strength, low warpage and low floating fiber comprises the following steps:
s1, drying PA6 at 100 ℃ for 4 h;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant in proportion, stirring for 3 minutes in a high-speed stirrer, and uniformly mixing;
s3, adding the uniformly mixed materials in the step S2 into an internal mixer, mixing, and granulating to obtain a glass fiber compatilizer mixture;
s4, weighing the glass fiber compatilizer mixture obtained in the step S3, talcum powder and PA6 in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
and S5, finally, extruding the material by a double-screw extruder (the extrusion temperature is 230 ℃, and the rotation speed of a main machine is 550rpm), cooling, drying and granulating to obtain the PA reinforcing material.
The PA composite of this example was tested using ISO standards and the results are given in table 3 below.
TABLE 3
Figure BDA0003430155090000081
Example 4
The PA reinforced material with ultrahigh strength, low warpage and low floating fiber is prepared from the following raw materials:
PA635 Kg (high melt index PA 618 Kg, melt index 100g/10 min; low melt index PA 617 Kg, melt index 45g/10min)
Glass fiber 80Kg
1250-mesh talcum powder 6Kg
8Kg of functional compatilizer
Lubricant EBS 0.6Kg
1.5Kg of antioxidant.
The preparation method of the PA reinforcing material with ultrahigh strength, low warpage and low floating fiber comprises the following steps:
s1, drying PA6 at 120 ℃ for 2 h;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant in proportion, stirring for 3 minutes in a high-speed stirrer, and uniformly mixing;
s3, adding the uniformly mixed materials in the step S2 into an internal mixer, mixing, and granulating to obtain a glass fiber compatilizer mixture;
s4, weighing the glass fiber compatilizer mixture obtained in the step S3, talcum powder and PA6 in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
and S5, finally, extruding the material by a double-screw extruder (the extrusion temperature is 250 ℃, and the rotating speed of a main machine is 500rpm), cooling, drying and granulating to obtain the PA reinforcing material.
The PA composite of this example was tested using ISO standards and the results are given in table 4 below.
TABLE 4
Figure BDA0003430155090000091
Comparative example 1
Different from the example 1, the glass fiber is not subjected to alkaline treatment, and other conditions and preparation processes are not changed.
The PA reinforcement of this comparative example was tested using ISO standards and the results are given in table 5 below.
TABLE 5
Figure BDA0003430155090000101
The glass fiber used in the comparative example is not subjected to alkaline treatment, the compatilizer cannot be effectively combined with the glass fiber, and the material performance is reduced.
Comparative example 2
In contrast to example 1, comparative example 2 was prepared as follows:
(1) drying PA6 at 110 ℃ for 3 h;
(2) weighing the PA6, the glass fiber, the talcum powder, the functional compatilizer, the lubricant and the antioxidant in proportion, and stirring for 10 minutes in a high-speed stirrer;
(3) the PA reinforced material is obtained by melt extrusion (extrusion temperature 230 ℃, main machine rotation speed 450rpm) of the materials through a double-screw extruder, cooling, drying and granulation.
The PP composite of this comparative example was tested using ISO standards and the results are given in table 6 below.
TABLE 6
Figure BDA0003430155090000102
Figure BDA0003430155090000111
Unlike example 1, the glass fiber and the compatibilizer of this comparative example were extruded and pelletized in a twin-screw extrusion without being mixed in an internal mixer. Because the residence time of the plastic melt and the glass fiber in the double-screw extruder is short, the dispersion and distribution effect is poor, the mutual contact chance among the resin, the compatilizer and the glass fiber is less, the compatibility effect is poor, and the performance of the material is reduced. In example 1, the glass fiber and the compatilizer are mixed in an internal mixer to be fully contacted, and then the mixture is extruded together with other components in a double screw, so that the plastic and the glass fiber have good combination effect and excellent material performance.
Comparative example 3
The preparation raw materials are as follows:
the low melt index is PA 622 Kg, and the melt index is 40g/10min
Glass fiber 70Kg
1250-mesh talcum powder 2Kg
8Kg of functional compatilizer
Lubricant EBS 0.4Kg
1.0Kg of antioxidant.
The preparation process is the same as in example 1.
The PA reinforcement of this comparative example was tested using ISO standards and the results are given in table 7 below.
TABLE 7
Figure BDA0003430155090000112
Unlike example 1, example 1 was formulated using two different melt index PA 6. In the injection molding process, because of the difference of the melt indexes of two PA6 resin melts, the PA6 resin melt with the low melt index has low flow rate and forms a central main fluid layer with glass fibers (difficult to flow); the high-melt-index PA6 resin melt has relatively high flow velocity, and the mobile phase forms turbulent flow in advance of the main fluid, so that glass fibers can be wound or wrapped, rubber bundles wrapping the glass fibers can be arranged radially, the strength of the material is enhanced, and floating fibers cannot be generated. Furthermore, according to the turbulent effect of the fluid, the plastic with low melt index is easy to be in the front of the turbulent flow when flowing, thereby contacting the mold wall with low temperature firstly and forming a surface solidification layer rapidly (see fig. 1). Through the control of the pressure maintaining time process, the PA6 resin with high melt index wound or coated by the PA6 resin is finally formed, and simultaneously forms a multilayer grid structure with the glass fibers arranged in the radial direction, so that the strength of the material is enhanced, and the effect of preventing the glass fibers from being exposed is also generated.
Comparative example 4
Different from the embodiment 1, the functional compatilizer is not added, and other conditions and preparation processes are not changed.
The PA reinforcement of this comparative example was tested using ISO standards and the results are given in table 8 below.
TABLE 8
Figure BDA0003430155090000121
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. The PA reinforcing material with ultrahigh strength, low warpage and low floating fiber is characterized by comprising the following raw materials in parts by weight:
PA 620-40 parts
55-80 parts of glass fiber
2-8 parts of mineral powder
2-8 parts of functional compatilizer
0.2 to 0.6 portion of lubricant
0.2-1.5 parts of an antioxidant;
the functional compatilizer is maleic anhydride grafted ethylene-octylene copolymer, maleic anhydride grafted ethylene-propylene copolymer or maleic anhydride grafted ethylene-propylene-diene monomer rubber;
the PA6 comprises a high-melting-index PA6 and a low-melting-index PA6, wherein the melting index of the high-melting-index PA6 is 70-100 g/10min, and the melting index of the low-melting-index PA6 is 30-50 g/10 min; in the PA6, the high-melting-index PA6 accounts for 40-50%, and the low-melting-index PA6 accounts for 40-60%;
the glass fiber is subjected to alkali treatment or acid treatment, and the glass fiber with the length of 3mm and the diameter of 15-17 mu m is selected as the glass fiber.
2. The ultra-high strength, low warpage, low floating fiber PA reinforcement material of claim 1, wherein said glass fibers are processed in one of two ways:
alkaline treatment: a. soaking the glass fiber in a sodium hydroxide solution for 8-12 h at the temperature of 30-65 ℃; b. naturally airing the soaked glass fibers, and placing the glass fibers into a drying oven at 150 ℃ for drying;
acid treatment: a. soaking the glass fiber in an acrylic acid or acrylate solution for 8-12 h at the temperature of 30-65 ℃; b. naturally airing the soaked glass fiber, and drying in a drying oven at 150 ℃.
3. The ultra-high strength, low warpage, low floating fiber PA reinforcement material of claim 1, wherein said mineral powder is at least one of talc, kaolin, mica powder.
4. The ultra-high strength, low warpage, low floating fiber PA reinforced material of claim 1, wherein the antioxidant is one or a mixture of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 1098.
5. The ultra-high strength, low warpage, low floating fiber PA reinforcing material of claim 1, wherein the lubricant is one or a mixture of more of lubricant EBS, lubricant PETS and lubricant paraffin wax.
6. The ultra-high strength, low warpage and low floating fiber PA reinforced material of claim 1, wherein the functional compatibilizer is maleic anhydride grafted ethylene-octene copolymer, the mass fraction of maleic anhydride in the maleic anhydride grafted ethylene-octene copolymer is 2% -3%, and the grafting ratio is greater than or equal to 1%.
7. The ultra-high strength, low warpage, low floating fiber PA reinforcement material of claim 1, wherein the high melt index PA6 has a melt index of 80g/10min, and the low melt index PA6 has a melt index of 40g/10 min; in PA6, the high melting index PA6 accounts for 50%, and the low melting index PA6 accounts for 50%.
8. The ultra-high strength, low warpage, low floating fiber PA reinforcement material of claim 1, characterized in that it is prepared from the following raw materials in parts by weight:
PA 620-22 parts
65-70 parts of glass fiber
2-3 parts of mineral powder
5-8 parts of functional compatilizer
0.4 portion of lubricant
1.0 part of antioxidant.
9. A process for preparing the ultra-high strength, low warpage, low floating fiber PA reinforcement material of any of claims 1-8, comprising the steps of:
s1, drying PA6 at 100-120 ℃ for 2-4 h;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant in proportion, stirring in a high-speed stirrer for 1-3 minutes, and uniformly mixing;
s3, adding the uniformly mixed materials in the step S2 into an internal mixer, mixing, and granulating to obtain a glass fiber compatilizer mixture;
s4, weighing the glass fiber compatilizer mixture obtained in the step S3, mineral powder and PA6 in proportion, and stirring in a high-speed stirrer for 5-10 minutes;
and S5, finally, extruding the material through a double-screw extruder, cooling, drying and granulating to obtain the PA reinforced material.
10. The process for preparing an ultra-high strength, low warpage, low floating fiber PA reinforcement material according to claim 9, wherein said extrusion process conditions are: the extrusion temperature is 220-250 ℃, and the rotation speed of a main machine is 400-550 rpm.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114921092A (en) * 2022-03-23 2022-08-19 金发科技股份有限公司 Nylon composition and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114921092A (en) * 2022-03-23 2022-08-19 金发科技股份有限公司 Nylon composition and preparation method and application thereof
CN114921092B (en) * 2022-03-23 2023-09-19 金发科技股份有限公司 Nylon composition and preparation method and application thereof

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