CN117264411A - Low-dielectric polyamide/polyphenyl ether composite material capable of being directly molded by laser and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of high polymer materials, in particular to a polyamide/polyphenyl ether composite material which has low dielectric property and can be directly molded by laser and a preparation method thereof. The polyamide/polyphenyl ether composite material comprises the following raw material components: long carbon chain polyamide resin, polyphenyl ether resin, compatilizer and LDS auxiliary agent; the weight ratio of the long carbon chain polyamide resin, the polyphenyl ether resin, the compatilizer and the LDS auxiliary agent is (20-56): (10-30): (1-10): (3-8); the compatilizer is one or a combination of more of PPO grafted maleic anhydride, SEBS grafted maleic anhydride and POE grafted maleic anhydride. The polyamide/polyphenyl ether composite material provided by the invention has good processing performance and mechanical performance, and simultaneously has the characteristics of low dielectric property and a laser direct forming function.

Description

Low-dielectric polyamide/polyphenyl ether composite material capable of being directly molded by laser and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a polyamide/polyphenyl ether composite material which has low dielectric property and can be directly molded by laser and a preparation method thereof.

Background

The laser direct structuring (Laser Di rect Structur ing, LDS) technology is a novel manufacturing technology that can selectively form three-dimensional circuits on plastic surfaces by laser activation and electroless plating processes. The circuit design is more flexible and precise, the mechanical function and the electrical function of the material are integrated into a whole, the space is saved, the miniaturization of the product is facilitated, and the product development process is accelerated. Based on the processing advantages, LDS materials of PC, PC/ABS, PA and LCP substrates and the like are widely used in the fields of communication antennas, sensors, automobile electronics, medical equipment and the like.

With the advent of the 5G era, the higher electromagnetic wave frequency band and faster transmission speed require materials with low dielectric, low delay and high wave transmission properties, but the PC, PC/ABS substrate LDS materials commonly used for antennas at present cannot meet the functions of high mechanical strength, low dielectric and laser direct forming at the same time.

The long carbon chain nylon generally refers to nylon with methylene content of more than or equal to 10 in chain segments, and has smaller density, lower water absorption, better low-temperature toughness, better chemical resistance and better dimensional stability compared with the short carbon chain nylon 6 and nylon 66 with the largest dosage. The long carbon chain nylon has higher mechanical strength than Polycarbonate (PC), but has higher dielectric constant and dielectric loss than PC (60 Hz: PA612, dielectric constant 4.0-6.0, dielectric loss 0.02-0.03, PC dielectric constant 3.0, dielectric loss 0.0009).

Polyphenylene Oxide (PPO) is the material with the lowest water absorption rate, the lowest dielectric constant (2.5-2.8) and the lowest dielectric loss tangent (0.008-0.0042) in five engineering plastics, but the modified polyphenylene oxide (mPPO) is mainly adopted in practical application due to the poor fluidity and difficult processing, such as PPO/PA alloy, PPO/H I PS alloy, PPO/PS alloy and the like.

Chinese patent publication No. CN 110951236A describes a PPO-based laser direct structuring additive that uses polyketone, polyethylene, polypropylene as carbonization modifier to obtain a higher plating index, but has lower strength.

Chinese patent publication No. CN 110655792A discloses a low dielectric laser direct structuring composite material suitable for 5G communication, wherein the base resin used is polyphenylene ether, polyimide, polyphenylene sulfide, liquid crystal polymer, etc., but the processability of the polyphenylene ether is not considered to be improved by polyamide.

Chinese patent publication No. CN 107418185A discloses a low coefficient of linear expansion polyphenylene ether/nylon 610 alloy, but dielectric properties are not considered.

The Chinese patent application with publication number of CN 114479410A discloses a low dielectric loss LDS engineering plastic, which realizes the regulation and control of material polarization rate through the change of the dosage of PPO and polyhydroxy ether, reduces dielectric loss, but has obviously lower tensile strength and bending strength.

In summary, how to develop a material with good processability and mechanical strength, and simultaneously with low dielectric and laser direct structuring functions to meet market requirements is an urgent problem in the art.

Disclosure of Invention

In order to solve the defects of the prior art in the background technology, the invention provides a polyamide/polyphenyl ether composite material with low dielectric and laser direct forming, which has the following technical scheme:

the polyamide/polyphenyl ether composite material with low dielectric property and laser direct forming comprises the following raw material components: long carbon chain polyamide resin, polyphenyl ether resin, compatilizer and LDS auxiliary agent; the weight ratio of the long carbon chain polyamide resin, the polyphenyl ether resin, the compatilizer and the LDS auxiliary agent is (20-56): (10-30): (1-10): (3-8); the compatilizer is one or a combination of more of SEBS grafted maleic anhydride, POE grafted maleic anhydride and PPO grafted maleic anhydride. Among them, PPO-g-MAH, that is, PPO grafted maleic anhydride, is preferable as the compatibilizer.

In some embodiments, the composition comprises the following raw materials in parts by weight: 20-56 parts of long carbon chain polyamide resin, 10-30 parts of polyphenyl ether resin, 1-10 parts of compatilizer, 3-8 parts of LDS auxiliary agent, 10-50 parts of reinforcing agent, 0.1-1 part of antioxidant and 0-5 parts of other auxiliary agents.

In some embodiments, the long carbon chain polyamide resin has a characteristic viscosity of 2.2 to 2.6dL/g; the long carbon chain polyamide resin has amide groups in the repeated units of the molecular main chain, and the number of methylene groups between adjacent amide groups is more than 10; the long carbon chain polyamide resin comprises one or more of PA11, PA12, PA610, PA612, PA1010, PA1012 and PA 1212.

In some embodiments, the LDS aid is a laser sensitive additive; the LDS auxiliary agent comprises one or a combination of more of spinel metal oxide, organic metal complex and copper complex. Copper chromium-based oxides are preferred.

In some embodiments, the polyphenylene ether resin has an intrinsic viscosity of 0.3 to 0.5dL/g.

In some embodiments, the antioxidant comprises one or more combinations of hindered phenolic antioxidants, semi-hindered phenolic antioxidants, hindered amine antioxidants, phosphate antioxidants, phosphite antioxidants. Hindered amine antioxidants are preferred.

In some embodiments, the reinforcing agent comprises one or more of fiberglass, glass microspheres, mineral fines. Low dielectric glass fibers are preferred.

In some embodiments, the other adjuvants include one or more combinations of toner, color master, lubricant. The other auxiliaries are preferably additives which do not affect the dielectric properties and LDS properties.

The invention also provides a preparation method of the polyamide/polyphenyl ether composite material which has low dielectric property and can be directly molded by laser, comprising the following steps:

s100, weighing raw material components of the polyamide/polyphenyl ether composite material except the reinforcing agent according to a certain weight, and mixing to obtain a mixture M;

s200, weighing the reinforcing agent according to a certain weight;

s300, adding the mixture M into a double-screw extruder through a main feeding port, adding the reinforcing agent into the double-screw extruder through a side feeding port, and performing melt extrusion granulation in the double-screw extruder to obtain the polyamide/polyphenyl ether composite material with low dielectric property and laser direct forming.

Compared with the prior art, the polyamide/polyphenyl ether composite material with low dielectric property and laser direct molding has the following technical effects:

the polyamide/polyphenyl ether composite material provided by the invention has good processing performance and mechanical performance, and simultaneously has the characteristics of low dielectric property and a laser direct forming function.

Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.

Detailed Description

For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in connection with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

The invention provides a preparation method of a polyamide/polyphenyl ether composite material with low dielectric property and laser direct forming, which comprises the following steps:

(1) Weighing the long carbon chain polyamide resin, the polyphenyl ether resin, the compatilizer, the LDS auxiliary agent, the antioxidant and other auxiliary agents according to a certain weight, and mixing to obtain a mixture M;

(2) Weighing the reinforcing agent according to a certain weight;

(3) Adding the mixture M into a double-screw extruder through a main feeding port, adding the reinforcing agent into the double-screw extruder through a side feeding port, and performing melt extrusion granulation in the double-screw extruder to obtain the polyamide/polyphenyl ether composite material with low dielectric property and laser direct forming.

Wherein the melt extrusion temperature in the twin-screw extruder is 240-280 ℃, the length-diameter ratio of the screw of the twin-screw extruder is (40-60): 1, and the rotational speed of the screw is (300-500) rpm.

The invention provides a formula of a polyamide/polyphenyl ether composite material which has low dielectric property and can be directly molded by laser, which comprises the following steps: the composite material comprises the following raw material components in parts by weight: 20-56 parts of long carbon chain polyamide resin, 10-30 parts of polyphenyl ether resin, 1-10 parts of compatilizer, 3-8 parts of LDS auxiliary agent, 10-50 parts of reinforcing agent, 0.1-1 part of antioxidant and 0-5 parts of other auxiliary agents.

The invention also provides examples and comparative examples shown in the following table:

the formulations (unit: parts by weight) of examples and comparative examples provided by the present invention are shown in table 1 below:

TABLE 1

In table 1, the types of raw material components in examples and comparative examples were selected to be the same, and the components were specifically:

the selected long carbon chain polyamide resin is PA612, and the viscosity is 2.4dL/g; the polyphenylene oxide resin is commercial PPO resin, and the viscosity of the polyphenylene oxide resin is 0.45dL/g; the selected compatilizer is PPO-g-MAH, and the grafting rate is 1.0% -1.5%; the LDS auxiliary agent is commercially available copper chrome black, wherein the content of Fe/Mg/Co is equal<1.0%; the selected reinforcing agent is commercial chopped low dielectric glass fiber, the dielectric constant is 4.2-4.8, and the dielectric loss tangent value is less than or equal to 10 ^-3 The method comprises the steps of carrying out a first treatment on the surface of the The antioxidant is selected from the commercial 1098/168; the lubricant selected was the commercially available pentaerythritol stearate PETS.

According to the formulation of table 1, the raw material components in the examples and comparative examples were prepared as follows to prepare polyamide/polyphenylene ether composites which are low dielectric and laser direct structuring, according to the following preparation method:

(1) Weighing the long carbon chain polyamide resin, the polyphenyl ether resin, the compatilizer, the LDS auxiliary agent, the antioxidant and other auxiliary agents according to a certain weight, and mixing to obtain a mixture M;

(2) Weighing the reinforcing agent according to a certain weight;

(3) Adding the mixture M into a double-screw extruder through a main feeding port, adding the reinforcing agent into the double-screw extruder through a side feeding port, and performing melt extrusion granulation in the double-screw extruder to obtain the polyamide/polyphenyl ether composite material with low dielectric property and laser direct forming.

The double-screw extruder is provided with 10 barrels in total, a main feeding port is arranged on the 1 st barrel, a side feeding port is arranged on the 6 th barrel, the temperatures of all areas of the double-screw extruder are 245 ℃, 250 ℃, 255 ℃, 260 ℃, 265 ℃, 270 ℃, 265 ℃, 260 ℃ and 260 ℃ in sequence from 1 to 10 areas, the temperature of a machine head is 270 ℃, the length-diameter ratio of a screw of the double-screw extruder is 40:1, and the screw rotating speed is 400rpm.

The low dielectric and laser direct formable polyamide/polyphenylene ether composites prepared in examples and comparative examples were subjected to the related index test, and the test results are shown in Table 2 below

TABLE 2

Wherein, the tensile strength is measured according to a standard of I S0 527-2, the sample size is 1A type (gauge length 115mm, parallel portion 10mm×4 mm), and the tensile speed is 5 mm/min; the bending strength test standard is ISO 178; the impact strength test standard of the simply supported beam is I SO 179-1, the sample size is 80mm multiplied by 10mm multiplied by 4mm (if a notch exists, the notch remains 8mm in width); the dielectric constant and dielectric loss were tested according to ASTM-D50 standard; the adhesion of the coating after laser direct structuring was evaluated by performing a hundred-cell test according to ASTM D3359-97. The adhesive force level of the hundred-grid test is divided into the following parts according to the percentage of the total area of the falling part of the plating layer: 0B (the shedding portion exceeds 65%), 1B (the shedding portion is 35% -65%), 2B (the shedding portion is 15-35%), 3B (the shedding portion is 5% -15%), 4B (the shedding portion is less than 5%), 5B (no complete lattice shedding). The higher the hundred grade is, the better the coating adhesion is, and the laser direct forming performance is better.

From the test results in table 2, it can be seen that:

the polyamide/polyphenyl ether composite material prepared by the embodiments 1-3 has good processing performance and mechanical performance, and simultaneously has the characteristics of low dielectric property and a laser direct forming function.

From the results of inventive examples 1-3, the dielectric constant and dielectric loss decreased as the PPO content increased;

as can be seen from the comparison of example 2 and comparative example 1, the addition of PPO as an alloy component significantly reduced the dielectric constant of the polyamide composite material.

As can be seen from the comparison of example 2 and comparative example 2, the addition of a suitable amount of the compatibilizer PPO-g-MAH results in improved compatibility of PPO with PA612, improved mechanical properties, improved melt index, and easier extrusion and molding. Comparative example 2 was free of compatibilizing agent and the PPO was poorly compatible with PA612, resulting in brittle materials, poor flowability, poor appearance, and even affecting the adhesion of the coating.

Comparative example 3 no LDS auxiliary was added, and as can be seen from the comparison results of example 2 and comparative example 3, comparative example 3 was significantly deteriorated in laser direct structuring property due to the absence of the LDS auxiliary. According to the above, the technical scheme of the invention comprises at least the following design principles and inventive concepts:

in the invention, polyphenyl ether resin, compatilizer, LDS auxiliary agent, low dielectric glass fiber and other auxiliary agents are added into long carbon chain polyamide resin. Wherein, the added polyphenyl ether resin plays a role in reducing dielectric constant and dielectric loss; the PPO grafted maleic anhydride compatilizer is added to play a role in improving the compatibility of the long carbon chain polyamide resin and PPO; the LDS auxiliary agent is added to enable the material to be subjected to chemical plating after laser activation; through the coordination of the components, the polyamide/polyphenyl ether composite material has good processing performance and mechanical performance, and simultaneously has the characteristics of low dielectric property and a laser direct forming function.

In conclusion, PPO belongs to a nonpolar material, a long carbon chain polyamide material belongs to a polar semi-crystalline material, and the compatibility of the PPO and the polar semi-crystalline material is poor. The polyamide/polyphenyl ether composite material provided by the invention has the characteristics of high heat resistance and low dielectric property of PPO resin, and the characteristics of easiness in processing, stable size, low water absorption, chemical resistance and the like of long carbon chain nylon.

It should be noted that:

"LDS" is collectively referred to as "Laser Di rect Structur i ng," which means laser direct structuring.

"PPO" is a common abbreviation for polyphenylene ether; the SEBS is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as a middle elastic block, and is called Styrene Ethy l ene Buty l ene Styrene in English and is called SEBS for short;

"POE" English full name Po l yo l ya l tha O l f i n, also known as polyethylene octene co-elastomer, is a POE elastic composite material.

In addition to the actual choices presented in the specific examples above, the weight ratio of the long carbon chain polyamide resin, polyphenylene ether resin, compatibilizer to LDS auxiliary agent is between (20-56): (10-30): (1-10): (3-8) including but not limited to the above embodiment;

in addition to the practical choices embodied in the specific embodiments described above, the long carbon chain polyamide resin may preferably be one or more combinations of PA11, PA12, PA610, PA612, PA1010, PA1012, PA1212, and characterized by: the characteristic viscosity is 2.2-2.6, and the number of the methylene groups between the adjacent amide groups is more than 10, including but not limited to the practical selection shown in the embodiment;

in addition to the actual choices presented in the above specific examples, it is preferred that the polyphenylene ether resin have a characteristic viscosity in the range of 0.3 to 0.5dL/g, including but not limited to the actual choices presented in the above examples;

in addition to the practical choices presented in the specific embodiments above, preferably the compatibilizer is one or more of PPO grafted maleic anhydride, SEBS grafted maleic anhydride, POE grafted maleic anhydride, preferably the compatibilizer is PPO-g-MAH;

in addition to the practical options presented in the above specific embodiments, preferably, the LDS aid is a laser sensitive additive; for example, it may be preferred that one or more combinations of spinel metal oxides, organometallic complexes, copper complexes, including but not limited to the actual choices presented by the above embodiments;

in addition to the actual choices presented in the specific embodiments above, preferably, the antioxidant may be selected from one or more of hindered phenolic antioxidants, semi-hindered phenolic antioxidants, hindered amine antioxidants, phosphate antioxidants, phosphite antioxidants, including, but not limited to, the actual choices presented in the embodiments above;

in addition to the actual choices presented in the above embodiments, preferably, the reinforcing agent may be one or more of fiberglass, glass beads, mineral powder, including but not limited to the actual choices presented in the above embodiments;

in addition to the actual choices presented in the above embodiments, the other adjuvants may preferably be selected from one or more of toners, color masters, lubricants, including, but not limited to, the actual choices presented in the above embodiments;

in summary, the specific parameters or some common reagents or raw materials in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limiting; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (9)

1. The polyamide/polyphenyl ether composite material with low dielectric property and laser direct forming is characterized by comprising the following raw material components: long carbon chain polyamide resin, polyphenyl ether resin, compatilizer and LDS auxiliary agent;

the weight ratio of the long carbon chain polyamide resin, the polyphenyl ether resin, the compatilizer and the LDS auxiliary agent is (20-56): (10-30): (1-10): (3-8);

the compatilizer is one or a combination of more of PPO grafted maleic anhydride, SEBS grafted maleic anhydride and POE grafted maleic anhydride.

2. The low dielectric and laser direct structuring polyamide/polyphenylene ether composite material according to claim 1, wherein: the composite material comprises the following raw material components in parts by weight:

20-56 parts of long carbon chain polyamide resin, 10-30 parts of polyphenyl ether resin, 1-10 parts of compatilizer, 3-8 parts of LDS auxiliary agent, 10-50 parts of reinforcing agent, 0.1-1 part of antioxidant and 0-5 parts of other auxiliary agents.

3. The low dielectric and laser direct structuring polyamide/polyphenylene ether composite material according to claim 1, wherein: the characteristic viscosity of the long carbon chain polyamide resin is 2.2-2.6 dL/g;

the long carbon chain polyamide resin has amide groups in the repeated units of the molecular main chain, and the number of methylene groups between adjacent amide groups is more than 10;

the long carbon chain polyamide resin comprises one or more of PA11, PA12, PA610, PA612, PA1010, PA1012 and PA 1212.

4. The low dielectric and laser direct structuring polyamide/polyphenylene ether composite material according to claim 1, wherein: the LDS auxiliary agent is a laser sensitive additive; the LDS auxiliary agent comprises one or a combination of more of spinel metal oxide, organic metal complex and copper complex.

5. The low dielectric and laser direct structuring polyamide/polyphenylene ether composite material according to claim 1, wherein: the polyphenylene ether resin has a characteristic viscosity of 0.3 to 0.5dL/g.

6. The low dielectric and laser direct structuring polyamide/polyphenylene ether composite according to claim 2, wherein: the antioxidant comprises one or more of hindered phenol antioxidant, semi-hindered phenol antioxidant, hindered amine antioxidant, phosphate antioxidant and phosphite antioxidant.

7. The low dielectric and laser direct structuring polyamide/polyphenylene ether composite according to claim 2, wherein: the reinforcing agent comprises one or more of glass fiber, glass microsphere and mineral powder.

8. The low dielectric and laser direct structuring polyamide/polyphenylene ether composite according to claim 2, wherein: the other auxiliary agents comprise one or more of toner, color master and lubricant.

9. A method for preparing a low dielectric and laser direct structuring polyamide/polyphenylene ether composite material according to any one of claims 1 to 8, comprising the steps of:

s100, weighing raw material components of the polyamide/polyphenyl ether composite material except the reinforcing agent according to a certain weight, and mixing to obtain a mixture M;

s200, weighing the reinforcing agent according to a certain weight;

s300, adding the mixture M into a double-screw extruder through a main feeding port, adding the reinforcing agent into the double-screw extruder through a side feeding port, and performing melt extrusion granulation in the double-screw extruder to obtain the polyamide/polyphenyl ether composite material with low dielectric property and laser direct forming.