CN109627759B

CN109627759B - PA66 reinforced material and preparation method and application thereof

Info

Publication number: CN109627759B
Application number: CN201811627585.4A
Authority: CN
Inventors: 朱怀才
Original assignee: Sinoplast New Material Ltd
Current assignee: Sinoplast New Material Ltd
Priority date: 2018-12-28
Filing date: 2018-12-28
Publication date: 2022-01-11
Anticipated expiration: 2038-12-28
Also published as: CN109627759A

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:

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

wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.

(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

wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.

(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

wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.

(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

wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.

(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

wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.

(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;

Example 7

wherein the length of the glass fiber is 3-4mm, and the diameter is 10-13 μm.

(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

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.

(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

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

1. The PA66 reinforced material is characterized in that the PA66 reinforced material is composed of the following components in parts by weight:

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;

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:

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.