CN111334038B - PA66 reinforced material and preparation method and application thereof - Google Patents

PA66 reinforced material and preparation method and application thereof Download PDF

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CN111334038B
CN111334038B CN202010338522.8A CN202010338522A CN111334038B CN 111334038 B CN111334038 B CN 111334038B CN 202010338522 A CN202010338522 A CN 202010338522A CN 111334038 B CN111334038 B CN 111334038B
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CN111334038A (en
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朱怀才
罗海威
谭善兴
徐文明
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Guangdong Sinoplast New Materials Co ltd
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Guangdong Sinoplast Advanced Material 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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention provides a PA66 reinforced material and a preparation method thereof. The PA66 reinforced material is prepared from the following raw materials: PA66, vinyl POSS-g- (EMA-co-GMA), reinforcing fiber, antioxidant and lubricant. The PA66 reinforced material is prepared by the method of firstly adopting the reaction of vinyl POSS and EMA-co-GMA to generate vinyl POSS-g- (EMA-co-GMA), and then melting and blending the vinyl POSS-g- (EMA-co-GMA), the PA66 and the reinforced fiber. The PA66 reinforced material provided by the invention has lower dielectric constant and dielectric loss, has higher heat resistance and mechanical strength, and can be well used as a nano injection molding material of electronic products.

Description

PA66 reinforced material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer composite materials, relates to a nano injection molding material, and particularly relates to a PA66 reinforced material and a preparation method and application thereof.
Background
The nano injection molding material is a polymer composite material which can be well combined with a metal material through a nano injection molding technology, and is mainly applied to electronic products such as mobile phones, computers and the like. The resins commonly used for the nano injection molding material include PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), PA (polyamide), and the like.
With the development of electronic information technology, the requirement of electronic products for electromagnetic signal transmittance is higher and higher. The 5G era is coming, which has more stringent requirements on the electromagnetic retardation and loss of electronic devices than 4G. The application of vacuum ion plating technology also requires that the nano injection molding material has higher heat resistance. Therefore, the development of the heat-resistant low-dielectric nano injection molding material has important significance for the development of electronic products. In the resin commonly used by the nano injection molding material, the temperature-resistant grade of PBT is lower; PA has good heat resistance, but has a disadvantage of high dielectric constant and dielectric loss.
There are two main methods for reducing the dielectric constant of polymer materials: firstly, the polarizability of the material is reduced through molecular design; and secondly, forming the nano microporous material containing the air gap. The second method mostly adopts foaming materials, so that the comprehensive mechanical property of the materials is poor and the use requirements are difficult to meet. The first method is usually achieved by high molecular blending.
For example, CN 107987525A discloses a semi-aromatic polyamide composite material for nano injection molding and a preparation method thereof, the semi-aromatic polyamide and the semi-aromatic polyamide-long chain aliphatic polyamide composite are used as matrix resin, so that the heat resistance and the adhesive force of the nano injection molding material are improved, the water absorption rate is reduced, but the dielectric property of the material is not improved. CN105694447A discloses a polyamide resin composition for NMT with LDS (laser direct structuring) function, which has higher adhesive force and lower shrinkage rate, and can be laser direct structuring, but also does not relate to improvement of dielectric properties.
CN109627759A discloses a PA66 reinforced material, a preparation method and an application thereof. The PA66 reinforced material comprises the following components in parts by weight: PA6639-65 parts, (vinyl POSS, MAH) -g-PP 5-10 parts and reinforced fiber 30-50 parts. The PA66 reinforced material is prepared by a method of firstly adopting vinyl POSS and MAH-g-PP to react to generate (vinyl POSS, MAH) -g-PP, and then melting and blending the (vinyl POSS, MAH) -g-PP with PA66 and reinforced fibers. Although the PA66 reinforced material provided by the invention solves the problem of low dielectric constant, the (vinyl POSS, MAH) -g-PP is a graft, the content of reactive functional groups is low, and the addition amount of the (vinyl POSS, MAH) -g-PP in the polymer is large, so that the mechanical properties (particularly crystalline materials) of the polymer are greatly influenced.
In order to meet the requirements of 5G products, a nano injection molding material with low dielectric constant and good heat resistance and mechanical properties is to be developed.
Disclosure of Invention
In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a PA66 reinforced material. The PA66 reinforced material has lower dielectric constant and dielectric loss, higher heat resistance and mechanical strength, and can be used as a nano injection molding material of electronic products.
In order to achieve the purpose, the invention adopts the following technical scheme:
the PA66 reinforced material is prepared from the following raw materials in parts by weight:
Figure BDA0002467526960000021
Figure BDA0002467526960000031
the vinyl POSS-g- (EMA-co-GMA) refers to EMA-co-GMA grafted with vinyl POSS (cage-like silsesquioxane).
The invention takes PA66 (polyhexamethylene adipamide) as a base material, and the PA66 is matched with the vinyl POSS-g- (EMA-co-GMA) and the reinforcing fiber in a proper proportion, so that the obtained PA66 reinforcing material has higher heat resistance and mechanical strength, and lower dielectric constant and dielectric loss.
The inventor finds that the addition of the vinyl POSS-g- (EMA-co-GMA) to the PA66 material can better reduce the dielectric constant and dielectric loss of the PA66 reinforced material compared with other materials (such as (octavinyl POSS, MAH) -g-PP), and simultaneously can enable the obtained PA66 reinforced material to have higher heat resistance and mechanical strength.
In some embodiments, the PA6 reinforced material is prepared from raw materials comprising, in parts by weight:
Figure BDA0002467526960000032
in some of these embodiments, the parts by weight of PA66 may be 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 67 parts, and the like.
In some of these embodiments, the parts by weight of the vinyl POSS-g- (EMA-co-GMA) may be 3 parts, 4 parts, 5 parts, 6 parts, and the like.
In some of these embodiments, the weight fraction of the reinforcing fibers may be 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 parts, etc.
In some of these embodiments, the vinyl POSS-g- (EMA-co-GMA) has a grafting ratio of 2 to 6% of vinyl POSS; for example, it may be 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, 5.2%, 5.5%, 5.8%, 6%, etc.
In some of these embodiments, the vinyl POSS-g- (EMA-co-GMA) has a grafting ratio of 4 to 6% of the vinyl POSS.
In some of these embodiments, the vinyl POSS of the vinyl POSS-g- (EMA-co-GMA) is an octavinyl POSS.
In some of these embodiments, the method of preparing the vinyl POSS-g- (EMA-co-GMA) comprises the steps of: dispersing vinyl POSS and an initiator in an organic solvent, and reacting with EMA-co-GMA in a double-screw extruder to obtain the vinyl POSS-g- (EMA-co-GMA).
In some of these embodiments, the weight of the vinyl POSS is 6-9% of the weight of the EMA-co-GMA, e.g., may be 6%, 6.2%, 6.7%, 7%, 7.2%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8%, 9%, etc.
In some of these embodiments, the initiator is present in an amount of 0.3 to 0.5% by weight of the EMA-co-GMA, and may be, for example, 0.3%, 0.32%, 0.35%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48%, 0.5%, or the like.
In some of these embodiments, the initiator is tert-butyl peroxybenzoate.
In some of these embodiments, the organic solvent is tetrahydrofuran.
In some of these embodiments, the method of preparing the vinyl POSS-g- (EMA-co-GMA) further comprises: antioxidant B215 was mixed with EMA-co-GMA.
In some embodiments, the antioxidant B215 is present in an amount of 0.15 to 0.3% by weight (e.g., 0.15%, 0.18%, 0.2%, 0.22%, 0.23%, 0.25%, 0.26%, 0.28%, 0.3%, etc.) of the EMA-co-GMA.
In some of these examples, the reaction is carried out using a twin screw extruder having an extrusion temperature of 185-200 deg.C, such as 185 deg.C, 188 deg.C, 190 deg.C, 192 deg.C, 193 deg.C, 195 deg.C, 196 deg.C, 198 deg.C, or 200 deg.C, to produce the vinyl POSS-g- (EMA-co-GMA); the screw speed is 280-310r/min, for example 280r/min, 285r/min, 290r/min, 295r/min, 300r/min, 305r/min or 310 r/min.
In some of these embodiments, the reinforcing fibers are glass fibers. The glass fiber has a reinforcing effect on the PA66 reinforcing material, and the reduction of the dosage of the glass fiber causes the reduction of the bending strength, the bending modulus and the tensile strength of the material.
In some of these embodiments, the glass fibers have a length of 3-4mm; for example, it may be 3mm, 3.1mm, 3.2mm, 3.3mm, 3.4mm, 3.5mm, 3.6mm, 3.7mm, 3.8mm, 3.9mm, 4mm, or the like.
In some of these embodiments, the glass fibers have a diameter of 10-13 μm; for example, it may be 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, 12.5 μm or 13 μm.
The length and diameter of the above preferred glass fiber are combined to consider the influence on the surface effect and mechanical property of the obtained PA66 reinforced material. The longer the fiber length, the higher the impact strength of the resulting PA66 reinforcement, but the worse the surface effect. In terms of diameter, the smaller the diameter in a certain range, the less and the smaller the surface cracks of the obtained PA66 reinforced material, the higher the strength of the material, but the smaller the diameter, the lower the pressure bearing capacity of the glass fiber, and the lower the mechanical properties of the PA66 reinforced material.
In some of the embodiments, the antioxidant consists of a hindered phenolic antioxidant and a phosphite antioxidant in a mass ratio of 2-3 (e.g. 2.
In some of these embodiments, the hindered phenolic antioxidant is antioxidant 1098 (N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine).
In some of these examples, the phosphite antioxidant is antioxidant 168 (phenyl tris (2, 4-di-tert-butyl) phosphite).
In some of these embodiments, the lubricant is a smectite-based lubricant (such as E-wax) or EBS (ethylene bis stearamide).
In another aspect, the present invention provides a preparation method of the PA66 reinforced material, including the following steps:
mixing vinyl POSS-g- (EMA-co-GMA) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding reinforcing fibers from a side feeding port of the double-screw extruder, carrying out melt blending, and extruding to obtain the PA66 reinforcing material.
In some of the examples, the extrusion temperature of the twin-screw extruder used for melt blending in the preparation of PA66 reinforcement is 280-300 ℃, and may be, for example, 280 ℃, 282 ℃, 285 ℃, 290 ℃, 292 ℃, 295 ℃, 298 ℃, 300 ℃ or the like; the screw rotation speed is 320-360r/min, for example 320r/min, 325r/min, 330r/min, 335r/min, 340r/min, 345r/min, 350r/min, 355r/min or 360 r/min.
As a preferred technical scheme of the invention, the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.15-0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 6-9 parts by weight of vinyl POSS and 0.3-0.5 part by weight of initiator in 60-90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 185-200 ℃ and the screw rotation speed to be 280-310r/min, and reacting while extruding to obtain vinyl POSS-g- (EMA-co-GMA);
(2) Mixing the vinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding a reinforcing fiber from a side feeding port of the double-screw extruder, setting the extrusion temperature to be 280-300 ℃ and the screw rotation speed to be 320-360r/min, and carrying out melt blending to obtain the PA66 reinforcing material after extrusion.
In a third aspect, the invention provides a use of the PA66 reinforced material, and an application of the PA66 reinforced material as or in preparation of a nano injection molding material for electronic products.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, vinyl POSS-g- (EMA-co-GMA) and other components are matched with each other at a specific ratio, so that the obtained PA66 reinforced material has low dielectric constant and dielectric loss, high heat resistance and mechanical strength, tensile strength of 157-200MPa, bending strength of 240-296MPa, bending modulus of 7300-13500MPa, impact strength of 180-260J/m, heat Distortion Temperature (HDT) of 239-260 ℃, dielectric constant of 2.88-3.12 and dielectric loss factor of 0.17-0.3, and can be used as a nano injection molding material of electronic products.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The sources of the raw materials adopted in the embodiment of the invention are as follows:
PA66: EP158 by Huafeng, zhejiang;
EMA-co-GMA: the content of BF-7M, GMA of Sumitomo is 6%;
glass fiber: 995-13P for Erwining; the length is 3-4mm, and the diameter is 10-13 μm.
Example 1
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000071
Figure BDA0002467526960000081
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 9 parts by weight of octavinyl POSS and 0.5 part by weight of initiator tert-butyl peroxybenzoate in 90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 200 ℃ and the screw rotation speed to be 310r/min, and carrying out reaction while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the grafting of the octavinyl POSS was 5%.
(2) Uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port of the double-screw extruder, setting the extrusion temperature to be 280 ℃ and the screw rotation speed to be 320r/min, carrying out melt blending, and extruding to obtain the PA66 reinforced material.
Example 2
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000082
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 9 parts by weight of octavinyl POSS and 0.5 part by weight of initiator tert-butyl peroxybenzoate in 90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 200 ℃ and the screw rotation speed to be 310r/min, and carrying out reaction while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the grafting of the octavinyl POSS was 5%.
(2) Uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port of the double-screw extruder, setting the extrusion temperature to 285 ℃ and the screw rotation speed to 330r/min, carrying out melt blending, and extruding to obtain the PA66 reinforced material.
Example 3
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000091
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 9 parts by weight of octavinyl POSS and 0.5 part by weight of initiator tert-butyl peroxybenzoate in 90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 200 ℃ and the screw rotation speed to be 310r/min, and reacting while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the grafting of the octavinyl POSS was 5%.
(2) Uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port of the double-screw extruder, setting the extrusion temperature to be 290 ℃ and the screw rotation speed to be 340r/min, and carrying out melt blending to obtain the PA66 reinforced material after extrusion.
Example 4
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000101
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 9 parts by weight of octavinyl POSS and 0.5 part by weight of initiator tert-butyl peroxybenzoate in 90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 200 ℃ and the screw rotation speed to be 310r/min, and carrying out reaction while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the octavinyl POSS grafting was 5%.
(2) Uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port, setting the extrusion temperature to be 295 ℃, setting the screw rotation speed to be 350r/min, carrying out melt blending, and extruding to obtain the PA66 reinforced material.
Example 5
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000111
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 9 parts by weight of octavinyl POSS and 0.5 part by weight of initiator tert-butyl peroxybenzoate in 90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 200 ℃ and the screw rotation speed to be 310r/min, and reacting while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the octavinyl POSS grafting was 5%.
(2) Uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port, setting the extrusion temperature to be 300 ℃, setting the screw rotation speed to be 360r/min, carrying out melt blending, and extruding to obtain the PA66 reinforced material.
Example 6
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000112
Figure BDA0002467526960000121
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 6 parts by weight of octavinyl POSS and 0.3 part by weight of initiator tert-butyl peroxybenzoate in 60 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 185 ℃ and the screw rotating speed to be 285r/min, and reacting while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the grafting yield of the octavinyl POSS was 2.8%.
(2) And (2) uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port, setting the extrusion temperature to be 290 ℃, setting the screw rotation speed to be 340r/min, carrying out melt blending, and extruding to obtain the PA66 reinforced material.
Example 7
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000122
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 8 parts by weight of octavinyl POSS and 0.44 part by weight of initiator tert-butyl peroxybenzoate in 80 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 195 ℃ and the screw rotation speed to be 295r/min, and reacting while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the grafting of the octavinyl POSS was 4%.
(2) And (2) uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port, setting the extrusion temperature to be 290 ℃, setting the screw rotation speed to be 340r/min, carrying out melt blending, and extruding to obtain the PA66 reinforced material.
Example 8
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
Figure BDA0002467526960000131
the preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 9 parts by weight of octavinyl POSS and 0.5 part by weight of initiator BPO (dibenzoyl peroxide) in 90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 200 ℃ and the screw rotation speed to be 310r/min, and reacting while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the grafting of the octavinyl POSS was 2%.
(2) Uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port of the double-screw extruder, setting the extrusion temperature to be 290 ℃ and the screw rotation speed to be 340r/min, and carrying out melt blending to obtain the PA66 reinforced material after extrusion.
Example 9
The embodiment provides a PA66 reinforced material which is prepared from the following components in parts by weight:
PA66 parts;
6 parts of octavinyl POSS-g- (EMA-co-GMA);
and 30 parts of glass fiber.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA and 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 9 parts by weight of octavinyl POSS and 0.5 part by weight of initiator tert-butyl peroxybenzoate in 90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to be 200 ℃ and the screw rotation speed to be 310r/min, and reacting while extruding to obtain octavinyl POSS-g- (EMA-co-GMA); the grafting of the octavinyl POSS was 5%.
(2) And (2) uniformly mixing the octavinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with PA66, adding the mixture from a main feeding port of a double-screw extruder, adding glass fiber from a side feeding port, setting the extrusion temperature to be 290 ℃ and the screw rotation speed to be 340r/min, and extruding to obtain the PA66 reinforced material.
Comparative example 1
The difference from example 1 is that instead of octavinyl POSS-g- (EMA-co-GMA), the same amount of EMA-co-GMA is used, and the other components, amounts and preparation steps are the same as in example 1.
Comparative example 2
The difference from example 1 is that instead of octavinyl POSS-g- (EMA-co-GMA), an equivalent amount of octavinyl POSS is used, and the other components, amounts and preparation steps are the same as in example 1.
Comparative example 3
The difference from example 3 is that instead of octavinyl POSS-g- (EMA-co-GMA) an equivalent amount of (octavinyl POSS, MAH) -g-PP was used, and the other components, amounts and preparation steps were the same as in example 3.
Wherein, (octavinyl POSS, MAH) -g-PP was prepared with reference to CN109679304A, and the grafting ratio of the octavinyl POSS was 5%.
Comparative example 4
The difference from example 3 is that the weight part of octavinyl POSS-g- (EMA-co-GMA) is 7 parts, and other components, amounts and preparation steps are the same as those of example 3.
The PA66 reinforcement materials provided in examples 1-9 and comparative examples 1-4 above were tested for their performance, with the test criteria and results shown in table 1 below:
TABLE 1
Figure BDA0002467526960000151
Figure BDA0002467526960000161
According to the data in the table 1, the octavinyl POSS-g- (EMA-co-GMA) modified PA66 reinforced material provided by the invention has higher heat resistance and mechanical strength, lower dielectric constant and dielectric loss, and can be used as a nano injection molding material of electronic products.
As can be seen by comparing the data of example 1 and comparative examples 1-2, when EMA-co-GMA or octavinyl POSS is used instead of octavinyl POSS-g- (EMA-co-GMA), both result in a significant increase in the dielectric constant and dielectric loss of the resulting PA66 reinforcement material.
As can be seen from the comparison between the data of example 3 and comparative example 3, when the same amount of (octavinyl POSS, MAH) -g-PP is used instead of octavinyl POSS-g- (EMA-co-GMA), the dielectric constant and dielectric loss of the obtained PA66 reinforced material are increased, and the mechanical property and heat resistance are also obviously reduced, and the inventor finds that the effect of reducing the dielectric constant and dielectric loss of the PA66 reinforced material similar to that of the octavinyl POSS-g- (EMA-co-GMA) can be achieved by further increasing the amount of the (octavinyl POSS, MAH) -g-PP, but the mechanical property and heat resistance of the material are further reduced by increasing the amount of the (octavinyl POSS, MAH) -g-PP. It can be seen that compared with (octavinyl POSS, MAH) -g-PP, the vinyl POSS-g- (EMA-co-GMA) disclosed by the invention can be used for better reducing the dielectric constant and dielectric loss of the PA66 composite material at a lower dosage, and meanwhile, the obtained PA66 composite material has higher heat resistance and mechanical strength.
It can be seen from the data of comparative example 3 and comparative example 4 that when the amount of octavinyl POSS-g- (EMA-co-GMA) is too much, the dielectric properties of the resulting PA66 reinforcement are not significantly improved, but the mechanical properties and heat resistance are significantly reduced. It is shown that when the addition amount of the octavinyl POSS-g- (EMA-co-GMA) reaches 6 parts, the dielectric constant and the dielectric loss of the material cannot be reduced any more by increasing the dosage of the octavinyl POSS-g- (EMA-co-GMA), at the moment, the dielectric constant and the dielectric loss of the PA66 reinforced material are reduced to the maximum extent by the octavinyl POSS-g- (EMA-co-GMA), and the mechanical property and the heat resistance of the PA66 reinforced material are reduced due to the excessive addition amount of the octavinyl POSS-g- (EMA-co-GMA).
In examples 4 and 5, the mechanical properties and heat resistance of the crystallized PA66 reinforcement material, such as flexural strength, flexural modulus, tensile strength, and impact strength, are significantly improved due to the increased amount of glass fiber, but the dielectric properties are reduced due to the excessive amount of glass fiber.
As can be seen from the comparison of the data of examples 3 and 6-7, examples 6 and 7 show that the dielectric constant and dielectric loss were higher than those of example 3 at the same amount of octavinyl POSS-g- (EMA-co-GMA) addition, since the POSS grafting ratio was lower than 5% in example 3 when octavinyl POSS-g- (EMA-co-GMA) was prepared. Meanwhile, the higher the POSS content (the higher the grafting ratio), the higher the mechanical property of the material. The higher the POSS content in a certain range, the lower the dielectric constant and dielectric loss of the PA66 reinforced material, and the higher the mechanical property.
As can be seen by comparing the data (mechanical properties, dielectric properties) of example 3 with that of example 8, the PA66 reinforcement of example 8 has higher dielectric constant and dielectric loss than example 3 at the same amount of octavinyl POSS-g- (EMA-co-GMA) added, because the initiator tert-butyl peroxybenzoate has better grafting efficiency to octavinyl POSS-g- (EMA-co-GMA) than to initiator BPO (dibenzoyl peroxide).
Example 9 does not contain antioxidant and lubricant, which causes various performance degradation of the PA66 reinforced material, because the PA66 reinforced material is oxidized and degraded at high temperature due to the lack of antioxidant in the extrusion stage, and simultaneously, the fluidity of the material is deteriorated due to the lack of lubricant, so that more shear heat is generated to promote the oxidative degradation of the material.
In conclusion, it can be seen that various components and amounts have a certain influence on the performance of the PA66 reinforcement material.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as being within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (12)

1. The PA66 reinforced material is characterized by being prepared from the following raw materials in parts by weight:
44-67 parts of PA (polyamide);
3-6 parts of vinyl POSS-g- (EMA-co-GMA);
30-50 parts of reinforcing fiber;
0.4-0.6 part of antioxidant;
0.5-0.8 part of lubricant;
the grafting ratio of the vinyl POSS in the vinyl POSS-g- (EMA-co-GMA) is 4-6%;
the vinyl POSS in the vinyl POSS-g- (EMA-co-GMA) is octavinyl POSS.
2. The PA66 reinforcement according to claim 1, characterized in that, in parts by weight,
44-66 parts of PA 66;
4-6 parts of vinyl POSS-g- (EMA-co-GMA);
30-40 parts of reinforcing fibers.
3. The PA66 reinforcement material of claim 1, wherein the preparation method of the vinyl POSS-g- (EMA-co-GMA) comprises the following steps: dispersing vinyl POSS and an initiator in an organic solvent, and reacting with EMA-co-GMA in a double-screw extruder to obtain the vinyl POSS-g- (EMA-co-GMA).
4. The PA66 reinforcement material as claimed in claim 3, wherein the initiator is tert-butyl peroxybenzoate.
5. The PA66 reinforcement material of claim 3, wherein the vinyl POSS
The weight of (a) is 6-9% of that of the EMA-co-GMA; and/or the weight of the initiator is 0.3-0.5% of the weight of the EMA-co-GMA.
6. The PA66 reinforcement material according to any of claims 1-5, characterized in that the reinforcement fibers are glass fibers; and/or the lubricant is E wax or ethylene bis stearamide.
7. The PA66 reinforcement material according to claim 6, wherein the glass fibers have a length of 3-4mm and/or a diameter of 10-13 μm.
8. The PA66 reinforced material according to any one of claims 1 to 5, wherein the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 2-3.
9. The PA66 reinforcement according to claim 8, wherein the hindered phenolic antioxidant is N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine;
the phosphite antioxidant is tris (2, 4-di-tert-butyl) phenyl phosphite.
10. A method for preparing a PA66 reinforcement according to any of claims 1 to 9, characterized in that it comprises the following steps: mixing the vinyl POSS-g- (EMA-co-GMA) with the PA66, the antioxidant and the lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding the reinforcing fiber from a side feeding port of the double-screw extruder, melting and blending the mixture, and extruding the mixture to obtain the PA66 reinforcing material.
11. The method for preparing a PA66 reinforced material according to claim 10, characterized by comprising the following steps:
(1) Mixing 100 parts by weight of EMA-co-GMA with 0.15-0.3 part by weight of antioxidant B215, and
adding 6-9 parts by weight of vinyl POSS and 0.3-0.5 part by weight of initiator into a main feeding port of a double-screw extruder, dissolving the mixture in 60-90 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, wherein the extrusion temperature is 185-200 ℃, the screw rotation speed is 280-310r/min, and reacting while extruding to obtain the vinyl POSS-g- (EMA-co-GMA);
(2) Mixing the vinyl POSS-g- (EMA-co-GMA) obtained in the step (1) with the PA66, the antioxidant and the lubricant, adding the mixture from a main feeding port of a double-screw extruder, adding the reinforcing fiber from a side feeding port of the double-screw extruder, setting the extrusion temperature to be 280-300 ℃ and the screw rotation speed to be 320-360r/min, carrying out melt blending, and extruding to obtain the PA66 reinforcing material.
12. Use of the PA66 reinforcement material of any of claims 1 to 9 as a nano-injection molding material for or in the manufacture of electronic products.
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