CN109627759B - PA66 reinforced material and preparation method and application thereof - Google Patents

PA66 reinforced material and preparation method and application thereof Download PDF

Info

Publication number
CN109627759B
CN109627759B CN201811627585.4A CN201811627585A CN109627759B CN 109627759 B CN109627759 B CN 109627759B CN 201811627585 A CN201811627585 A CN 201811627585A CN 109627759 B CN109627759 B CN 109627759B
Authority
CN
China
Prior art keywords
mah
parts
weight
antioxidant
screw extruder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811627585.4A
Other languages
Chinese (zh)
Other versions
CN109627759A (en
Inventor
朱怀才
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinoplast New Material Ltd
Original Assignee
Sinoplast New Material Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinoplast New Material Ltd filed Critical Sinoplast New Material Ltd
Priority to CN201811627585.4A priority Critical patent/CN109627759B/en
Publication of CN109627759A publication Critical patent/CN109627759A/en
Application granted granted Critical
Publication of CN109627759B publication Critical patent/CN109627759B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation

Abstract

The invention provides a PA66 reinforced material and a preparation method and application thereof. The PA66 reinforced material comprises the following components in parts by weight: PA 6639-65 parts, (vinyl POSS, MAH) -g-PP 5-10 parts and reinforced fiber 30-50 parts. The PA66 reinforced material is prepared by the method that (vinyl POSS, MAH) -g-PP is generated by the reaction of vinyl POSS and MAH-g-PP, and then the (vinyl POSS, MAH) -g-PP is melt-blended with PA66 and reinforced fibers. The 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.

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. Wherein, the temperature resistant grade of the PBT is low; although the PPS has higher temperature-resistant grade, the color matching is difficult, and the requirement of personalized color is difficult to meet; PA has good heat resistance and coloring property, but also has a disadvantage of high dielectric constant and dielectric loss.
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.
The methods for reducing the dielectric constant of the polymer material mainly include two methods: 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.
CN 107987525a discloses a semi-aromatic polyamide composite material for nano injection molding and a preparation method thereof, which adopts semi-aromatic polyamide and semi-aromatic polyamide-long chain aliphatic polyamide composite as matrix resin, improves heat resistance and adhesive force of the nano injection molding material, reduces water absorption, but does not improve dielectric properties of the material. CN 105694447a discloses a polyamide resin composition for NMT with LDS (laser direct structuring) function, which has higher cohesive force and lower shrinkage rate, and can be laser direct structuring, but also does not relate to improvement of dielectric properties.
Therefore, in order to meet the requirements of 5G products, a nano injection molding material with lower dielectric constant and dielectric loss is to be developed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a PA66 reinforced material, a preparation method and application thereof. The PA66 reinforced material has high heat resistance and mechanical strength, low dielectric constant and dielectric loss, 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:
in a first aspect, the invention provides a PA66 reinforced material, which comprises the following components in parts by weight:
PA 6639-65 parts;
5-10 parts of (vinyl POSS, MAH) -g-PP;
30-50 parts of reinforcing fiber.
In the present invention, the (vinyl POSS, MAH) -g-PP refers to PP (polypropylene) grafted with vinyl POSS (cage silsesquioxane) and MAH (maleic anhydride).
According to the invention, PA66 (polyhexamethylene adipamide) is used as a base material and is matched with (vinyl POSS, MAH) -g-PP and reinforcing fibers at a specific ratio, so that the obtained PA66 reinforcing material has high heat resistance and mechanical strength, and low dielectric constant and dielectric loss.
PA66 is used as a base material of the nano injection molding material, has excellent mechanical property and thermal property, and has higher adhesive force with metal; the (vinyl POSS, MAH) -g-PP has the effects of reducing the dielectric constant and dielectric loss of the PA66 reinforced material and improving the heat resistance and mechanical strength, and when the content of the (vinyl POSS, MAH) -g-PP is too small, the effect is not obvious, and when the content of the (vinyl POSS, MAH) -g-PP is too large, the effect of improving the dielectric property of the PA66 reinforced material is not obviously improved, but the crystallization of PA66 is influenced, so that the comprehensive properties (including the flow property, the mechanical property and the thermal property) of the PA66 reinforced material are reduced.
In the present invention, the PA66 may be 39 parts, 40 parts, 42 parts, 43 parts, 45 parts, 46 parts, 48 parts, 50 parts, 52 parts, 53 parts, 55 parts, 56 parts, 58 parts, 60 parts, 62 parts, 63 parts, 65 parts, or the like by weight.
The weight parts of the (vinyl POSS, MAH) -g-PP can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts and the like.
The reinforcing fiber may be 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, or the like by weight.
As a preferred technical scheme of the invention, the vinyl POSS in the (vinyl POSS, MAH) -g-PP is octavinyl POSS.
Preferably, the grafting ratio of the vinyl POSS in the (vinyl POSS, MAH) -g-PP is 3-5%; for example, it may be 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, or 5%, etc.
In a preferred embodiment of the present invention, the reinforcing fibers are glass fibers. The glass fiber has a reinforcing effect on 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 impact strength of the material.
Preferably, the length of the glass fiber is 3-4 mm; 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.
Preferably, the diameter of the glass fiber is 10 to 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.
As a preferable technical scheme of the invention, the PA66 reinforced material also comprises 0.4-0.6 part (for example, 0.4 part, 0.42 part, 0.45 part, 0.48 part, 0.5 part, 0.52 part, 0.55 part, 0.58 part or 0.6 part and the like) of antioxidant.
Preferably, the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 2-3:1 (e.g., 2:1, 2.2:1, 2.3:1, 2.5:1, 2.6:1, 2.8:1, or 3:1, etc.).
Preferably, the hindered phenol antioxidant is antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) ].
Preferably, the phosphite antioxidant is antioxidant 168 (tris (2, 4-di-tert-butyl) phenyl phosphite).
In a preferred embodiment of the present invention, the PA 66-reinforced material further comprises 0.5-0.8 parts (e.g., 0.5 parts, 0.52 parts, 0.55 parts, 0.58 parts, 0.6 parts, 0.62 parts, 0.65 parts, 0.68 parts, 0.7 parts, 0.72 parts, 0.75 parts, 0.78 parts, or 0.8 parts) of a lubricant.
Preferably, the lubricant is PETS (pentaerythritol stearate) or EBS (ethylene bis stearamide).
In a second aspect, the present invention provides a preparation method of the PA66 reinforced material, where the preparation method includes:
mixing (vinyl POSS, MAH) -g-PP with PA66, an optional antioxidant and an optional 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, and carrying out melt blending to obtain the PA66 reinforcing material.
As a preferred technical scheme of the invention, the preparation method of the (vinyl POSS, MAH) -g-PP comprises the following steps: vinyl POSS and an initiator are dispersed in an organic solvent and react with MAH-g-PP in a double-screw extruder to obtain (vinyl POSS, MAH) -g-PP.
Preferably, the vinyl POSS comprises 7-10% by weight of the MAH-g-PP, for example, 7%, 7.2%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8%, 9%, 9.2%, 9.5%, 9.8%, 10%, or the like.
Preferably, the initiator comprises 0.3-0.5% by weight of the MAH-g-PP, for example 0.3%, 0.32%, 0.35%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48%, 0.5%, etc.
Preferably, the initiator is dicumyl peroxide (DCP).
Preferably, the organic solvent is tetrahydrofuran.
Preferably, the method of making the (vinyl POSS, MAH) -g-PP further comprises mixing 0.15-0.3% (e.g., 0.15%, 0.18%, 0.2%, 0.22%, 0.23%, 0.25%, 0.26%, 0.28%, or 0.3%, etc.) antioxidant B215 by weight of the MAH-g-PP with the MAH-g-PP.
The main function of adding the antioxidant B215 is to relieve the degradation of the MAH-g-PP in the reaction process.
Preferably, the reaction uses a double screw extruder extrusion temperature of 185-; the screw rotation speed is 280-310r/min, for example 280r/min, 285r/min, 290r/min, 295r/min, 300r/min, 305r/min or 310 r/min.
As the preferred technical scheme of the invention, the melt blending uses the twin-screw extruder extrusion temperature of 280-; 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 comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP 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 7-10 parts by weight of vinyl POSS and 0.3-0.5 part by weight of initiator in 70-100 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 carrying out reaction while extruding to obtain (vinyl POSS, MAH) -g-PP;
(2) mixing the (vinyl POSS, MAH) -g-PP 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 the reinforcing fiber from a side feeding port of the double-screw extruder, setting the extrusion temperature at 280-300 ℃ and the screw rotation speed at 320-360r/min, and extruding to obtain the PA66 reinforcing material.
In a third aspect, the invention provides a use of the PA66 reinforced material, and the PA66 reinforced material is used as a nano injection molding material of electronic products.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts (vinyl POSS, MAH) -g-PP and other components to be matched with each other under specific proportion, the obtained PA66 reinforced material has higher heat resistance and mechanical strength, lower dielectric constant and dielectric loss, the tensile strength of the material is 190MPa, the bending strength of the material is 280MPa, the bending modulus of the material is 6600-13000MPa, the impact strength of the material is 180-280J/m, the Heat Distortion Temperature (HDT) of the material is 225-270 ℃, the dielectric constant of the material is 2.9-3.2, and the dielectric loss factor of the material is 0.21-0.33, and the material 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 limitations of the present invention.
The sources of the raw materials adopted in the embodiment of the invention are as follows:
PA 66: EP158 by Huafeng, Zhejiang;
MAH-g-PP: shenyang Ketong with KT-1, MAH grafting rate of 0.8%;
glass fiber: 995-13P of Erwins Corning.
Example 1
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
Figure BDA0001928300870000061
Figure BDA0001928300870000071
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 0.3 part by weight of antioxidant B215, adding the mixture from a main feed port of a double-screw extruder, dissolving 10 parts by weight of octavinyl POSS and 0.5 part by weight of initiator DCP in 100 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, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP 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 280 ℃ and the screw rotation speed to be 320r/min, and extruding to obtain the PA66 reinforced material.
Example 2
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
Figure BDA0001928300870000072
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 0.3 part by weight of antioxidant B215, adding the mixture from a main feed port of a double-screw extruder, dissolving 10 parts by weight of octavinyl POSS and 0.5 part by weight of initiator DCP in 100 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, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP 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 285 ℃ and the screw rotation speed to 330r/min, and extruding to obtain the PA66 reinforced material.
Example 3
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
Figure BDA0001928300870000081
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 0.3 part by weight of antioxidant B215, adding the mixture from a main feed port of a double-screw extruder, dissolving 10 parts by weight of octavinyl POSS and 0.5 part by weight of initiator DCP in 100 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, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP 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 ℃ and the screw rotation speed to be 340r/min, and extruding to obtain the PA66 reinforced material.
Example 4
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
Figure BDA0001928300870000091
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 0.3 part by weight of antioxidant B215, adding the mixture from a main feed port of a double-screw extruder, dissolving 10 parts by weight of octavinyl POSS and 0.5 part by weight of initiator DCP in 100 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, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP 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 at 295 ℃ and the screw rotation speed at 350r/min, and extruding to obtain the PA66 reinforced material.
Example 5
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
Figure BDA0001928300870000101
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 0.3 part by weight of antioxidant B215, adding the mixture from a main feed port of a double-screw extruder, dissolving 10 parts by weight of octavinyl POSS and 0.5 part by weight of initiator DCP in 100 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, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP 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 ℃ and the screw rotation speed to be 360r/min, and extruding to obtain the PA66 reinforced material.
Example 6
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
Figure BDA0001928300870000102
Figure BDA0001928300870000111
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 0.3 part by weight of antioxidant B215, adding the mixture from a main feeding port of a double-screw extruder, dissolving 7 parts by weight of octavinyl POSS and 0.3 part by weight of initiator in 70 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 rotation speed to be 285r/min, and carrying out reaction while extruding to obtain (octavinyl POSS, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP 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 280 ℃ and the screw rotation speed to be 320r/min, and extruding to obtain the PA66 reinforced material.
Example 7
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
Figure BDA0001928300870000112
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 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 0.42 part by weight of initiator 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 carrying out reaction while extruding to obtain (octavinyl POSS, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP obtained in the step (1) with PA66, an antioxidant and a lubricant, adding the mixture from a main feed inlet of a double-screw extruder, adding glass fiber from a side feed inlet, setting the extrusion temperature to be 290 ℃ and the screw rotation speed to be 325r/min, and extruding to obtain the PA66 reinforced material.
Example 8
The embodiment provides a PA66 reinforced material, which comprises the following components in parts by weight:
PA 6659 parts;
10 parts of (octavinyl POSS, MAH) -g-PP;
30 parts of glass fiber;
wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.
The preparation method of the PA66 reinforced material comprises the following steps:
(1) mixing 100 parts by weight of MAH-g-PP with 0.3 part by weight of antioxidant B215, adding the mixture from a main feed port of a double-screw extruder, dissolving 10 parts by weight of octavinyl POSS and 0.5 part by weight of initiator DCP in 100 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, MAH) -g-PP;
(2) and (2) uniformly mixing the (octavinyl POSS, MAH) -g-PP 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 setting the screw rotation speed to be 330r/min, and extruding to obtain the PA66 reinforced material.
Comparative example 1
The difference from example 1 is that instead of (octavinyl POSS, MAH) -g-PP, the same amount of MAH-g-PP was used, and the other components, amounts and preparation steps were the same as in example 1.
Comparative example 2
The difference from example 1 is that instead of (octavinyl POSS, MAH) -g-PP, the same amount of octavinyl POSS was used, and the other components, amounts and preparation steps were the same as in example 1.
Comparative example 3
The difference from example 3 is that the weight part of (octavinyl POSS, MAH) -g-PP is 13 parts, and other components, amounts and preparation steps are the same as those of example 3.
The PA66 reinforcement materials provided in examples 1-8 and comparative examples 1-3 above were tested for their performance, with the test criteria and results shown in table 1 below:
TABLE 1
Figure BDA0001928300870000131
According to the data in table 1, the PA66 reinforced material provided by the invention has high heat resistance and mechanical strength, low dielectric constant and dielectric loss, good fluidity, and easy processing, and can be used as a nano injection molding material for electronic products. When MAH-g-PP or octavinyl POSS is used to replace (octavinyl POSS, MAH) -g-PP (comparative example 1), the heat resistance and mechanical properties of the PA66 reinforced material are obviously deteriorated, and the dielectric constant and dielectric loss are increased; when the content of (octavinyl POSS, MAH) -g-PP was too high (comparative example 3), the dielectric properties of the resulting PA66 reinforcement were not significantly improved compared to example 3, but the mechanical properties and heat resistance were significantly reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (17)

1. The PA66 reinforced material is characterized in that the PA66 reinforced material is composed of the following components in parts by weight:
Figure FDA0003165962380000011
the vinyl POSS in the (vinyl POSS, MAH) -g-PP is octavinyl POSS;
the grafting rate of the vinyl POSS in the (vinyl POSS, MAH) -g-PP is 3-5%;
the lubricant is PETS or EBS;
the preparation method of the PA66 reinforced material comprises the following steps:
mixing (vinyl POSS, MAH) -g-PP 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, and carrying out melt blending to obtain a PA66 reinforcing material;
the preparation method of the (vinyl POSS, MAH) -g-PP comprises the following steps: vinyl POSS and an initiator are dispersed in an organic solvent and react with MAH-g-PP in a double-screw extruder to obtain (vinyl POSS, MAH) -g-PP.
2. The PA66 reinforcing material of claim 1, wherein the reinforcing fibers are glass fibers.
3. The PA66 reinforcing material of claim 2, wherein the glass fibers have a length of 3-4 mm.
4. The PA66 reinforcing material of claim 2, wherein the glass fibers have a diameter of 10-13 μ ι η.
5. The PA66 reinforced material of claim 1, wherein the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 2-3: 1.
6. The PA66 reinforcing material of claim 5, wherein the hindered phenolic antioxidant is antioxidant 1010.
7. The PA66 reinforcing material as claimed in claim 5, wherein the phosphite antioxidant is antioxidant 168.
8. A process for the preparation of a PA66 reinforcement according to any one of claims 1 to 7, characterized in that the process comprises:
mixing (vinyl POSS, MAH) -g-PP 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, and carrying out melt blending to obtain a PA66 reinforcing material;
the preparation method of the (vinyl POSS, MAH) -g-PP comprises the following steps: vinyl POSS and an initiator are dispersed in an organic solvent and react with MAH-g-PP in a double-screw extruder to obtain (vinyl POSS, MAH) -g-PP.
9. The method of claim 8 wherein said vinyl POSS comprises 7-10% by weight of said MAH-g-PP.
10. The method of claim 8, wherein said initiator is present in an amount of 0.3 to 0.5% by weight of said MAH-g-PP.
11. The method of claim 8, wherein the initiator is dicumyl peroxide.
12. The method according to claim 8, wherein the organic solvent is tetrahydrofuran.
13. The method of claim 8, wherein the method of preparing the (vinyl POSS, MAH) -g-PP further comprises mixing 0.15-0.3% by weight of the MAH-g-PP of antioxidant B215 with the MAH-g-PP.
14. The method as claimed in claim 8, wherein the extrusion temperature of the twin-screw extruder used in the method for preparing (vinyl POSS, MAH) -g-PP is 185-200 ℃ and the screw rotation speed is 280-310 r/min.
15. The preparation method as claimed in claim 8, wherein the extrusion temperature of the twin-screw extruder used for melt blending is 280-300 ℃, and the screw rotation speed is 320-360 r/min.
16. The method of claim 8, comprising the steps of:
(1) mixing 100 parts by weight of MAH-g-PP 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 7-10 parts by weight of vinyl POSS and 0.3-0.5 part by weight of initiator in 70-100 parts by weight of tetrahydrofuran, adding the mixture from a fourth zone of the double-screw extruder, setting the extrusion temperature to 185-200 ℃ and the screw rotation speed to 280-310r/min, and carrying out reaction while extruding to obtain (vinyl POSS, MAH) -g-PP;
(2) mixing the (vinyl POSS, MAH) -g-PP 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 at 280-300 ℃ and the screw rotation speed at 320-360r/min, and obtaining the PA66 reinforcing material after extrusion.
17. Use of the PA66 reinforcement material according to any of claims 1-7, wherein the PA66 reinforcement material is used as a nano-injection molding material for electronic products.
CN201811627585.4A 2018-12-28 2018-12-28 PA66 reinforced material and preparation method and application thereof Active CN109627759B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811627585.4A CN109627759B (en) 2018-12-28 2018-12-28 PA66 reinforced material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811627585.4A CN109627759B (en) 2018-12-28 2018-12-28 PA66 reinforced material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109627759A CN109627759A (en) 2019-04-16
CN109627759B true CN109627759B (en) 2022-01-11

Family

ID=66079183

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811627585.4A Active CN109627759B (en) 2018-12-28 2018-12-28 PA66 reinforced material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109627759B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111334037B (en) * 2020-04-23 2023-01-03 广东中塑新材料有限公司 PA1010 composite material and preparation method thereof
CN111363356B (en) * 2020-04-24 2023-03-28 广东中塑新材料有限公司 PPS composite material and preparation method and application thereof
CN111334038B (en) * 2020-04-26 2023-03-17 广东中塑新材料有限公司 PA66 reinforced material and preparation method and application thereof
CN111378276B (en) * 2020-04-29 2023-03-24 广东中塑新材料有限公司 PA9T composite material and preparation method thereof
CN111410841B (en) * 2020-05-06 2023-01-03 广东中塑新材料有限公司 PA46 composite material and preparation method thereof
CN112095169A (en) * 2020-09-24 2020-12-18 福建拓烯新材料科技有限公司 Antibacterial high-strength polypropylene fiber, preparation method and fabric

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103382302A (en) * 2013-07-02 2013-11-06 浙江俊尔新材料股份有限公司 Red phosphorus flame-retardant nylon composition and preparation method thereof
CN104448813A (en) * 2014-11-25 2015-03-25 浙江俊尔新材料股份有限公司 Glass fiber reinforced polyamide 66 composite material, and preparation method and application thereof
CN104610717A (en) * 2015-02-10 2015-05-13 海安县中山合成纤维有限公司 Glass fiber reinforced nylon 66 composite
CN107011651A (en) * 2017-04-28 2017-08-04 湖南工业大学 A kind of nano composite material of POSS/ nylon monomer-cast nylons 6 and its preparation method and application
CN107033456A (en) * 2017-04-28 2017-08-11 东华大学 One kind is based on POSS organic-inorganic hybrid nanometers compatilizer and its preparation and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103382302A (en) * 2013-07-02 2013-11-06 浙江俊尔新材料股份有限公司 Red phosphorus flame-retardant nylon composition and preparation method thereof
CN104448813A (en) * 2014-11-25 2015-03-25 浙江俊尔新材料股份有限公司 Glass fiber reinforced polyamide 66 composite material, and preparation method and application thereof
CN104610717A (en) * 2015-02-10 2015-05-13 海安县中山合成纤维有限公司 Glass fiber reinforced nylon 66 composite
CN107011651A (en) * 2017-04-28 2017-08-04 湖南工业大学 A kind of nano composite material of POSS/ nylon monomer-cast nylons 6 and its preparation method and application
CN107033456A (en) * 2017-04-28 2017-08-11 东华大学 One kind is based on POSS organic-inorganic hybrid nanometers compatilizer and its preparation and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PA6/POSS纳米杂化材料的结构与性能;丁筠 等;《合成树脂及塑料》;20111231;第28卷(第5期);摘要,第83-84页第3节 *
POSS grafting on PPgMA by one-step reactive blending;Alberto Fina,et al.;《POLYMER》;20081108;第50卷(第1期);第218-226页 *

Also Published As

Publication number Publication date
CN109627759A (en) 2019-04-16

Similar Documents

Publication Publication Date Title
CN109627759B (en) PA66 reinforced material and preparation method and application thereof
CN111718581B (en) Low-dielectric-constant low-dielectric-loss reinforced polyphenylene sulfide composite material special for 5G antenna oscillator and preparation method and application thereof
CN107573683B (en) Low-dielectric-constant glass fiber reinforced polyamide material and preparation method thereof
CN105504803B (en) A kind of high fluidity fiber reinforced nylon composite material and preparation method thereof
CN109679304B (en) PBT/PCT composite material and preparation method and application thereof
CN103862589B (en) A kind of melt blending prepares the method for polyamide-based heat-conductive composite material
CN103030885B (en) Long glass-fiber reinforced polypropylene material with low emission and high performance and production method thereof
CN104788930A (en) Super-tough PC/ABS alloy and preparation method thereof
CN111763383B (en) Good-touch glass fiber reinforced polypropylene composite and preparation method thereof
CN107541049B (en) Graphene-continuous glass fiber reinforced halogen-free flame-retardant weather-resistant PPO/HIPS alloy material and preparation method thereof
CN111334039A (en) Reinforced polyamide 66 composition and method for making same
CN111423723A (en) Reinforced polyphenylene sulfide composition for 5G and preparation method thereof
CN110862684A (en) POK/PPS composite material and preparation method thereof
CN111073244B (en) Polycarbonate composition and preparation method thereof
CN103554902A (en) Nylon composite material and preparation method thereof
CN111334037B (en) PA1010 composite material and preparation method thereof
CN115433458A (en) Graphene/carbon fiber reinforced nylon 66 composition and preparation method thereof
CN106893250B (en) A kind of ABS resin composition being blow molded with high fondant-strength, good appearance
CN111334038B (en) PA66 reinforced material and preparation method and application thereof
WO2023160154A1 (en) Pbt/pet composite material, and preparation method therefor and use thereof
CN111500030B (en) PBT composite material and preparation method and application thereof
CN111363356B (en) PPS composite material and preparation method and application thereof
CN109385077B (en) Nylon 10T easily-electroplated composite material, preparation method thereof and electroplated blank
CN108690341B (en) Compatilizer for PC/ABS alloy and PC/ABS alloy
CN111349332B (en) PC composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: PA66 reinforcing material and its preparation method and Application

Effective date of registration: 20220616

Granted publication date: 20220111

Pledgee: Shenzhen small and medium sized small loan Co.,Ltd.

Pledgor: Sinoplast New Material Ltd.

Registration number: Y2022440020093

PE01 Entry into force of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20230821

Granted publication date: 20220111

Pledgee: Shenzhen small and medium sized small loan Co.,Ltd.

Pledgor: Sinoplast New Material Ltd.

Registration number: Y2022440020093

PC01 Cancellation of the registration of the contract for pledge of patent right