CN114213840B - Ultra-high strength, low warpage and low floating fiber PA reinforced material and preparation process thereof - Google Patents

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

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CN114213840B
CN114213840B CN202111592045.9A CN202111592045A CN114213840B CN 114213840 B CN114213840 B CN 114213840B CN 202111592045 A CN202111592045 A CN 202111592045A CN 114213840 B CN114213840 B CN 114213840B
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glass fiber
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CN114213840A (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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    • 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
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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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    • 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
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    • 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
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    • C08K3/34—Silicon-containing compounds
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    • 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
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Abstract

The invention provides an ultra-high strength, low warpage and low floating fiber PA reinforced material, which comprises the following components: 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-octyl copolymer, maleic anhydride grafted ethylene-propylene copolymer or maleic anhydride grafted ethylene propylene diene monomer rubber; the PA6 comprises high melt index PA6 and low melt index PA6, the melt indexes are respectively 70-100 g/10min and 30-50 g/10min, the high melt index PA6 accounts for 40-50%, and the low melt index PA6 accounts for 40-60%. In the invention, the ultra-high glass fiber content (more than 60%) provides excellent performances such as higher mechanical strength, heat resistance, dimensional stability and the like for the PA reinforcing material, and simultaneously overcomes the defects of high warpage, high fiber floating, low gloss and the like generated by high-content fiber.

Description

Ultra-high strength, low warpage and low floating fiber PA reinforced material and preparation process thereof
Technical Field
The invention belongs to the field of PA reinforced materials, and particularly relates to an ultra-high strength, low warpage and low fiber floating PA reinforced material and a preparation process thereof.
Background
Nylon (PA) resins generally require the addition of glass fibers to increase the strength of the material. The strength of the PA can reach more than several times of the original strength after the PA is reinforced by glass fibers. The higher the glass fiber content, the higher the strength, the higher the heat resistance, and even the glass fiber can be compared with metal materials. PA reinforcement can therefore be used in place of metals for various mechanical components. 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 the peripheral parts of automobile engines and other products with high strength and certain heat resistance requirements in the fields. With the improvement of the glass fiber content, the mechanical strength and the heat resistance of the glass fiber are gradually improved, but the glass fiber is easier to warp due to uneven heat conduction, so that the injection molding piece is deformed, and the use of the injection molding piece is affected. Meanwhile, as the glass fiber content is improved, the surface of the plastic part is more likely to generate floating fiber, 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, which 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 points, namely crosslinking 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; at the same time nylon 66 also increases the mechanical strength of the composition. CN201610425990.2 discloses a glass fiber reinforced PA6 composition for improving the 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 glass fibers, and similar anchoring nodes, namely crosslinking points, are formed between the glass fibers and nylon resin, so that the bonding state of the glass fibers and the resin is improved, the separation of the glass fibers and the resin is reduced, the glass fibers and the resin synchronously flow in the processing process, are not easy to tear, the exposure of the glass fibers 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 glass fiber and nylon is improved by adding other auxiliary agents, but in practice, 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 glass fiber and nylon, and the phenomenon of floating fiber is easy to occur in the processing process.
In summary, research on a glass fiber reinforced PA material with ultra-high strength, low warpage and low fiber floating and a preparation process thereof has wide application prospect.
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%) provides excellent performances such as higher mechanical strength, heat resistance, dimensional stability and the like for the PA reinforced material, and overcomes the defects of high warpage, high fiber floating, low gloss and the like generated by high-content fiber.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the ultra-high strength, low-warpage and low-floating fiber PA reinforcing material comprises the following raw materials in parts by weight:
20 to 40 parts of PA6
55-80 parts of glass fiber
2-8 parts of mineral powder
2-8 parts of functional compatilizer
0.2 to 0.6 part of lubricant
0.2 to 1.5 portions of antioxidant;
the functional compatilizer is maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted ethylene-propylene copolymer or maleic anhydride grafted ethylene propylene diene monomer;
the PA6 comprises a high melt index PA6 and a low melt index PA6, wherein the melt index of the high melt index PA6 is 70-100 g/10min, and the melt index of the low melt index PA6 is 30-50 g/10min; in the PA6, the high melt index PA6 accounts for 40-50%, and the low melt index PA6 accounts for 40-60%. The melt index represents the melt flow rate, and a high melt index value indicates good melt flow, whereas poor flow.
The glass fiber is subjected to alkali treatment or acid treatment, and the glass fiber is selected from glass fibers with the length of 3mm and the diameter of 15-17 mu m.
According to the molecular structure characteristics and the similar compatibility principle, the invention adopts the functional compatilizer (maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted ethylene-propylene copolymer or maleic anhydride grafted ethylene propylene diene monomer) with both the affinity for PA and glass fiber, and the glass fiber is wound or wrapped under the cooperation 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-octene block copolymer as an example, the maleic anhydride grafted ethylene-octene block copolymer has amphiphilic property similar to a surfactant, groups (carbonyl and carboxyl) of maleic acid are easy to be affine with glass fiber (-O-Si-O-) and groups (amide groups) of PA, and ethylene-octene groups of the maleic anhydride grafted ethylene-octene block copolymer are easier to be affine with molecular chains of PA, so that 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 floating fiber is less.
Meanwhile, the PA6 is combined with the PA6 with high melt index and the PA6 with low melt index, and through a great deal of researches, the invention discovers that the combination of the PA6 with the melt index of 70-100 g/10min and the PA6 with the melt index of 30-50 g/10min can be used for the best and the best of the processing performance, the mechanical strength and the ageing resistance. The PA6 resin with low melt index has low melt flow rate and forms a central main fluid layer with glass fiber (difficult to flow); the high-melting-point PA6 resin melt is relatively fast in flow velocity, and the mobile phase forms turbulence before the main flow, 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 can not be generated. Moreover, according to the turbulent flow effect of the fluid, the plastic with low melt index is easy to be in front of turbulent flow when flowing, thus contacting with the mold wall with low temperature at first, 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 is finally formed to be wound or coated with the PA6 resin with low melt index, and meanwhile, the PA6 resin and the glass fibers which are radially arranged form a multi-layer grid structure, 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. immersing the glass fiber into sodium hydroxide solution for 8-12 h at 30-65 ℃; b. naturally airing the soaked glass fiber, and putting the glass fiber into a baking oven at 150 ℃ for baking;
acid treatment: a. immersing the glass fiber into an acrylic acid or acrylic ester solution for 8-12 h at the temperature of 30-65 ℃; b. naturally airing the soaked glass fiber, and putting the glass fiber into a baking oven at 150 ℃ for baking.
The preferred treatment method is a sodium hydroxide solution soaking treatment, wherein the soaking time is 10 hours, and the soaking temperature is 45 ℃. Through alkaline pretreatment, a hydration layer or a silicon hydroxyl (-Si-OH) appears on the glass fiber, so that the combination capability 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 present invention, preferably, the lubricant is one or a mixture of several of lubricant EBS, lubricant PETS and lubricant paraffin, preferably lubricant EBS. The lubricant can be dissociated in the functional compatilizer and the glass fiber to serve as an auxiliary medium, is beneficial to extrusion processing of materials, reduces floating fiber and forms luster.
In the present invention, preferably, the mineral powder is at least one of talc, kaolin and mica powder. Preferably 1250 mesh talc.
And (3) microscopically analyzing, wherein the functional compatilizer forms a three-dimensional framework structure by amphipathic property of PA6 and glass fiber, and forms a reinforced concrete structure with the assistance of a lubricant and talcum powder. Among these, PA6, functional compatibiliser and lubricant are cement-like (lubricant is water-like), glass fiber is rebar-like, and talc is sand-like. The PA6 and the functional compatilizer molecules are wrapped or wound with the glass fibers under the assistance of the lubricant to form rubber micelles, and the glass fibers are arranged in a radial staggered orientation under the action of extrusion external force, so that the probability of transverse arrangement (stand out) is reduced, and the degree of fiber floating is greatly reduced. Because the glass fibers are crisscrossed (arranged by steel bars), when the glass fibers are subjected to external load, the structural synergism in the matrix resin can disperse each other and absorb external energy, so that good synergism is generated, and deformation (warping) is not generated.
In the present invention, preferably, the antioxidant is one or a mixture of several of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 1098. An equal ratio of the mixture of antioxidants 1098 and 168 is preferred.
In the invention, preferably, the functional compatilizer is a maleic anhydride grafted ethylene-octene copolymer, wherein the mass fraction of maleic anhydride in the maleic anhydride grafted ethylene-octene copolymer is 2% -3%, and the grafting rate is more than or equal to 1%.
In the present invention, preferably, the melt index of the high melt index PA6 is 80g/10min, and the melt index of the low melt index PA6 is 40g/10min; in PA6, the high melt index PA6 accounts for 50 percent, and the low melt index PA6 accounts for 50 percent.
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:
20 to 22 parts of PA6
65-70 parts of glass fiber
2-3 parts of mineral powder
5-8 parts of functional compatilizer
0.4 part of lubricant
1.0 part of antioxidant.
The ratio of the raw materials is high, the mechanical strength, the heat resistance and the dimensional stability of the PA6 can be obviously improved due to high glass fiber content, and meanwhile, the consumption of the compatilizer is increased, and the high melt index PA6 and the low melt 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 ultra-high strength, low warpage and low floating fiber PA reinforced material, which comprises the following steps:
s1, drying PA6 at 100-120 ℃ for 2-4 hours;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant according to a proportion, stirring for 1-3 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, the mineral powder and the PA6 according to the proportion, and stirring for 5-10 minutes in a high-speed stirrer;
s5, finally, extruding the materials through a double-screw extruder, cooling, drying and granulating to obtain the PA reinforcing material.
Preferably, the process conditions of the extrusion: the extrusion temperature is 220-250 ℃, and the host rotation speed is 400-550 rpm.
The preparation process of the invention firstly mixes and granulates the glass fiber with the compatilizer, the lubricant and the antioxidant, and then mixes with the PA6, thus 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 reinforcing material, the reinforcing material provided by the invention not only maintains excellent mechanical properties, but also improves defects such as warping, fiber floating and the like, and the glossiness of a plastic part is good.
2. The PA6 is formed by combining the high-melt-index PA6 and the low-melt-index PA6, the flow speed of the high-melt-index PA6 resin melt is relatively high, the mobile phase forms turbulence before the main fluid (the low-melt-index PA6 and the glass fiber), the glass fiber can be wound or wrapped, the rubber bundles wrapping the glass fiber can be arranged in a radial direction, the PA6 resin with the high-melt-index PA6 resin wound or wrapped with the low-melt-index PA6 resin is finally formed, and meanwhile, the high-melt-index PA6 resin and the glass fiber arranged in the radial direction form a multi-layer grid structure, so that the strength of the material is enhanced, and the effect of preventing the glass fiber from being exposed is also generated.
3. According to the molecular structure characteristics and the similar compatibility principle, the invention adopts the functional compatilizer with both the affinity for PA and the affinity for glass fiber, and the glass fiber is wound or wrapped under the cooperation 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.
Drawings
FIG. 1 is a schematic view of turbulence generated by different flow rates of a melt according to the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but the scope of the present invention is not limited to the examples.
In the following specific examples, all the raw materials used are commercially available unless otherwise specified.
Wherein the functional compatilizer is maleic anhydride grafted ethylene-octyl copolymer, the mass fraction of maleic anhydride in the maleic anhydride grafted ethylene-octyl copolymer is 2% -3%, and the grafting rate is more than or equal to 1%. The antioxidant is an equal proportion of mixture of antioxidants 1098 and 168. 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. immersing the glass fiber in sodium hydroxide solution for 10 hours at the temperature of 45 ℃; b. naturally airing the soaked glass fiber, and putting the glass fiber into a baking oven at 150 ℃ for baking.
Example 1
The ultra-high strength, low warpage and low floating fiber PA reinforced material is prepared from the following raw materials:
PA6 22Kg (high melt index PA6 12Kg, melt index 80g/10min; low melt index PA 610 Kg, melt index 40g/10 min)
65Kg of glass fiber
1250 mesh talcum powder 3Kg
5Kg of functional compatilizer
Lubricant EBS 0.4Kg
Antioxidant 1.0Kg.
The preparation method of the ultra-high strength, low-warpage and low-floating fiber PA reinforced material comprises the following steps:
s1, drying PA6 at 110 ℃ for 3 hours;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant according to a 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 in the S3, talcum powder and PA6 according to a proportion, and stirring in a high-speed stirrer for 5-10 minutes;
s5, finally, extruding the materials by a double-screw extruder (the extrusion temperature is 240 ℃ and the host rotation speed is 500 rpm), cooling, drying and granulating to obtain the PA reinforced material.
The PA reinforcements of this example were tested using ISO standards and the results are given in table 1 below.
TABLE 1
Example 2
The ultra-high strength, low warpage and low floating fiber PA reinforced material is prepared from the following raw materials:
PA620 Kg (high melt index PA66 Kg, melt index 80g/10min; low melt index PA6 14Kg, melt index 40g/10 min)
70Kg of glass fiber
1250 mesh talcum powder 2Kg
8Kg of functional compatilizer
Lubricant EBS 0.4Kg
Antioxidant 1.0Kg.
The preparation method of the ultra-high strength, low-warpage and low-floating fiber PA reinforced material comprises the following steps:
s1, drying PA6 at 110 ℃ for 3 hours;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant according to a 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 in the S3, talcum powder and PA6 according to a proportion, and stirring in a high-speed stirrer for 5-10 minutes;
s5, finally, extruding the materials by a double-screw extruder (the extrusion temperature is 230 ℃ and the host rotation speed is 450 rpm), cooling, drying and granulating to obtain the PA reinforced material.
The PA composites of this example were tested using ISO standards and the results are given in table 2 below.
TABLE 2
Example 3
The ultra-high strength, low warpage and low floating fiber PA reinforced material is prepared from the following raw materials:
PA630 Kg (high melt index PA6 13Kg, melt index 90g/10min; low melt index PA6 17Kg, melt index 50g/10 min)
75Kg of glass fiber
1250 mesh talcum powder 5Kg
6Kg of functional compatilizer
Lubricant EBS 0.5Kg
Antioxidant 1.2Kg.
The preparation method of the ultra-high strength, low-warpage and low-floating fiber PA reinforced material comprises the following steps:
s1, drying PA6 at the temperature of 100 ℃ for 4 hours;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant according to a 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 in the S3, talcum powder and PA6 according to a proportion, and stirring in a high-speed stirrer for 5-10 minutes;
s5, finally, extruding the materials by a double-screw extruder (the extrusion temperature is 230 ℃ and the main machine rotating speed is 550 rpm), cooling, drying and granulating to obtain the PA reinforced material.
The PA composites of this example were tested using ISO standards and the results are given in table 3 below.
TABLE 3 Table 3
Example 4
The ultra-high strength, low warpage and low floating fiber PA reinforced material is prepared from the following raw materials:
PA635 Kg (high melt index PA6 18Kg, melt index 100g/10min; low melt index PA6 17Kg, melt index 45g/10 min)
80Kg of glass fiber
1250 mesh talcum powder 6Kg
8Kg of functional compatilizer
Lubricant EBS 0.6Kg
Antioxidant 1.5Kg.
The preparation method of the ultra-high strength, low-warpage and low-floating fiber PA reinforced material comprises the following steps:
s1, drying PA6 at 120 ℃ for 2 hours;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant according to a 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 in the S3, talcum powder and PA6 according to a proportion, and stirring in a high-speed stirrer for 5-10 minutes;
s5, finally, extruding the materials by a double-screw extruder (the extrusion temperature is 250 ℃ and the host rotation speed is 500 rpm), cooling, drying and granulating to obtain the PA reinforced material.
The PA composites of this example were tested using ISO standards and the results are given in table 4 below.
TABLE 4 Table 4
Comparative example 1
Unlike example 1, the glass fiber was not subjected to alkaline treatment, and other conditions and preparation process were unchanged.
The PA reinforcements of this comparative example were tested using ISO standards and the results are given in table 5 below.
TABLE 5
The glass fiber used in this comparative example was not subjected to alkaline treatment, and the compatibilizer could not be effectively combined with the glass fiber, and the material properties were lowered.
Comparative example 2
In contrast to the comparison of example 1, the preparation process of comparative example 2 is as follows:
(1) Drying PA6 at 110 ℃ for 3 hours;
(2) Weighing the PA6, the glass fiber, the talcum powder, the functional compatilizer, the lubricant and the antioxidant according to the proportion, and stirring for 10 minutes in a high-speed stirrer;
(3) And (3) carrying out melt extrusion (the extrusion temperature is 230 ℃ and the host rotation speed is 450 rpm) on the materials by a double-screw extruder, cooling, drying and granulating to obtain the PA reinforced material.
The PP composites of this comparative example were tested using ISO standards and the results are shown in table 6 below.
TABLE 6
Unlike example 1, the glass fibers and compatibilizer of this comparative example were not kneaded by an internal mixer and were directly extrusion pelletized in twin screw extrusion. Because the residence time of the plastic melt and the glass fiber in the double-screw extruder is short, the dispersion and distribution effects are poor, the mutual contact opportunity among the resin, the compatilizer and the glass fiber is less, the compatibility effect is poor, and the performance of the material is also reduced. In example 1, glass fibers and a compatilizer are mixed in an internal mixer to obtain full contact, and then are extruded together with other components in a double screw, so that the combination effect of plastic and glass fibers is good, and the material performance is excellent.
Comparative example 3
The preparation raw materials are as follows:
PA6 22Kg with low melt index and melt index of 40g/10min
70Kg of glass fiber
1250 mesh talcum powder 2Kg
8Kg of functional compatilizer
Lubricant EBS 0.4Kg
Antioxidant 1.0Kg.
The preparation process is the same as in example 1.
The PA reinforcements of this comparative example were tested using ISO standards and the results are given in table 7 below.
TABLE 7
Unlike example 1, example 1 was formulated using two different melt index PA 6. In the injection molding process, because of the difference of melt indexes of two PA6 resin melts, the PA6 resin melt with low melt index has low flow rate and forms a central main fluid layer with glass fiber (difficult to flow); the high-melting-point PA6 resin melt is relatively fast in flow velocity, and the mobile phase forms turbulence before the main flow, 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 can not be generated. Moreover, according to the turbulent flow effect of the fluid, the plastic with low melt index is easy to be in front of turbulent flow when flowing, thus contacting with the mold wall with low temperature at first, 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 is finally formed to be wound or coated with the PA6 resin with low melt index, and meanwhile, the PA6 resin and the glass fibers which are radially arranged form a multi-layer grid structure, 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
Unlike example 1, no functional compatibilizer was added, and other conditions and preparation process were unchanged.
The PA reinforcements of this comparative example were tested using ISO standards and the results are given in table 8 below.
TABLE 8
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (8)

1. The ultra-high strength, low-warpage and low-floating fiber PA reinforcing material is characterized by comprising the following raw materials in parts by weight:
20 to 40 parts of PA6
55-80 parts of glass fiber
2-8 parts of mineral powder
2-8 parts of functional compatilizer
0.2 to 0.6 part of lubricant
0.2 to 1.5 portions of antioxidant;
the functional compatilizer is a maleic anhydride grafted ethylene-octene copolymer, wherein the mass fraction of maleic anhydride in the maleic anhydride grafted ethylene-octene copolymer is 2% -3%, and the grafting rate is more than or equal to 1%;
the PA6 comprises a high melt index PA6 and a low melt index PA6, wherein the melt index of the high melt index PA6 is 70-100 g/10min, and the melt index of the low melt index PA6 is 30-50 g/10min; in PA6, the high melt index PA6 accounts for 40-50%, and the low melt index PA6 accounts for 40-60%;
the glass fiber is subjected to alkali treatment or acid treatment, and the glass fiber is selected from glass fibers with the length of 3mm and the diameter of 15-17 mu m;
the glass fiber is processed in one of the following two modes:
alkaline treatment: a. immersing the glass fiber into sodium hydroxide solution for 8-12 h at 30-65 ℃; b. naturally airing the soaked glass fiber, and putting the glass fiber into a baking oven at 150 ℃ for baking;
acid treatment: a. immersing the glass fiber into an acrylic acid or acrylic ester solution for 8-12 h at the temperature of 30-65 ℃; b. naturally airing the soaked glass fiber, and putting the glass fiber into a baking oven at 150 ℃ for baking.
2. The ultra-high strength, low warpage, low fiber floating PA-reinforced material of claim 1, wherein said mineral powder is at least one of talc, kaolin, mica powder.
3. The ultra-high strength, low warpage, low fiber floating PA-reinforced material according to claim 1, wherein the antioxidant is one or a mixture of several of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 1098.
4. The ultra-high strength, low warpage, low fiber floating PA-reinforced material of claim 1, wherein said lubricant is one or a mixture of several of lubricant EBS, lubricant PETS and lubricant paraffin.
5. The ultra-high strength, low warpage, low fiber floating 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/10min; in PA6, the high melt index PA6 accounts for 50 percent, and the low melt index PA6 accounts for 50 percent.
6. The ultra-high strength, low warpage, low fiber floating PA reinforcement material of claim 1, prepared from the following raw materials in parts by weight:
20 to 22 parts of PA6
65-70 parts of glass fiber
2-3 parts of mineral powder
5-8 parts of functional compatilizer
0.4 part of lubricant
1.0 part of antioxidant.
7. The process for preparing the ultra-high strength, low warpage, low fiber floating PA reinforcement material according to any one of claims 1 to 6, comprising the steps of:
s1, drying PA6 at 100-120 ℃ for 2-4 hours;
s2, weighing the glass fiber, the functional compatilizer, the lubricant and the antioxidant according to a proportion, stirring for 1-3 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, the mineral powder and the PA6 according to the proportion, and stirring for 5-10 minutes in a high-speed stirrer;
s5, finally, extruding the materials through a double-screw extruder, cooling, drying and granulating to obtain the PA reinforcing material.
8. The process for preparing an ultra-high strength, low warpage, low fiber floating PA-reinforced material according to claim 7, wherein the extrusion process conditions are as follows: the extrusion temperature is 220-250 ℃, and the host rotation speed is 400-550 rpm.
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石安富.《合成树脂与塑料手册》.上海科学技术出版社,146. *
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