CN113234242B

CN113234242B - Double-bond-terminated polyphenyl ether and epoxidized polybutadiene resin co-crosslinked polymer capable of being used for 5G high-speed high-frequency communication and preparation method thereof

Info

Publication number: CN113234242B
Application number: CN202110730050.5A
Authority: CN
Inventors: 刘鹏波; 代天文; 邹华维
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2021-06-29
Filing date: 2021-06-29
Publication date: 2022-05-24
Anticipated expiration: 2041-06-29
Also published as: CN113234242A

Abstract

The invention belongs to the technical field of low-dielectric polymer materials for 5G high-speed high-frequency communication, and particularly relates to a co-crosslinked polymer of double-bond-terminated polyphenyl ether and epoxidized polybutadiene resin for 5G high-speed high-frequency communication and a preparation method thereof. The co-crosslinked polymer is prepared by reacting and curing double-bond-terminated polyphenyl ether and epoxidized polybutadiene under the action of a crosslinking agent and a curing agent. The polymer overcomes the difficulty of poor compatibility of polyphenyl ether and other resins, has the advantages of high glass transition temperature, high heat resistance, low dielectric constant and low dielectric loss, is used as a low dielectric material for 5G high-speed high-frequency communication, and has good application prospect.

Description

Double-bond-terminated polyphenyl ether and epoxidized polybutadiene resin co-crosslinked polymer capable of being used for 5G high-speed high-frequency communication and preparation method thereof

Technical Field

The invention belongs to the technical field of low dielectric polymer materials for 5G high-speed high-frequency communication, and particularly relates to a double-bond-terminated polyphenyl ether and epoxidized polybutadiene resin co-crosslinked polymer for 5G high-speed high-frequency communication and a preparation method thereof.

Background

In 6

months

6 and 6 days 2019, the ministry of China industry and informatization officially issued 5G commercial license plates to China telecom, China Mobile, China Unicom and China radio and television, marking that China formally enters the fifth generation mobile communication (5G) era. Communication technology has been used as a cross science in multiple fields, and has been driving the development of other disciplines, including materials science. The communication technology is from 1G to 5G, and the maximum transmission rate of mobile communication signals is increased to 1Gbps by 10 ten thousand times from the original 10kbps (bit per second) after the development process of 40 years. And when the development reaches the 5G era, the maximum transmission rate of signals is expected to reach 10Gbps, and the development of communication technology can greatly change the existing life style of human beings.

In the existing 5G technology, sub-6GHz (sub-6GHz) and millimeter wave (millimeter wave) are generally adopted for signal transmission. The millimeter wave generally refers to electromagnetic waves with a frequency band of 30-300 GHz and a wavelength of 1-10 mm. In the millimeter wave frequency band, when an electric field passes through a medium, heat loss is aggravated due to alternating polarization of medium molecules and lattice back-and-forth collision. Fig. 1 shows the loss of a polymer dielectric material when subjected to an electromagnetic wave, and it can be seen that the material resonates due to the change of dielectric polarization under the action of an alternating electromagnetic field, so that dielectric loss occurs, and the dielectric loss increases with the increase of frequency. Therefore, millimeter waves for 5G high-frequency communication induce a larger loss in the polymer dielectric material.

Therefore, the PCB substrate material for 5G high frequency communication needs to satisfy the following performance requirements:

1. the dielectric constant is as small as possible, and the dielectric constant is kept stable in a certain high-frequency range, so that the delay of signals in the transmission process is reduced;

2. the dielectric loss is small. The smaller the dielectric loss is, the smaller the signal loss is, and the signal transmission quality is further improved;

3. low thermal expansion coefficient, high heat resistance and high peeling strength.

The Copper Clad Laminate (CCL) is a plate-like material produced by impregnating electronic glass fiber cloth or other reinforcing materials with resin, coating copper foil on one or both surfaces, and hot-pressing. And forming a conductive pattern circuit on the plate by carrying out selective hole processing, etching, copper electroplating and the like on the copper-clad plate, and finally obtaining the printed circuit board. When the traditional copper-clad plate is used as a base material of a high-performance PCB, the traditional copper-clad plate has the defects of poor dielectric property, high Coefficient of Thermal Expansion (CTE), poor heat resistance, poor humidity resistance and the like. With the development of 5G technology, higher technical requirements are put forward on PCB boards, and copper-clad plates are developed towards the directions of low dielectric constant, low dielectric loss, low thermal expansion coefficient, high heat resistance and the like.

Polyphenylene Oxide (PPO) has an extremely low dielectric constant and dielectric loss over a wide frequency range. And the polyphenyl ether has excellent comprehensive performance, has the advantages of high heat resistance, high glass transition temperature, low water absorption and the like, so that the polyphenyl ether is one of ideal materials for manufacturing the high-frequency high-speed copper-clad plate. However, conventional polyphenylene ethers also have significant drawbacks, mainly manifested by high melt viscosity, poor flowability, poor compatibility with other resins, and poor processability. Therefore, the polyphenyl ether can not be directly and independently used as the material of the high-frequency high-speed copper-clad plate.

On the other hand, 1, 2-polybutadiene, as a nonpolar polymer, has a low dielectric constant (D)_k2.6, 1GHz and at 23 ℃), has wide application prospect in PCB. However, 1, 2-polybutadiene has a low glass transition temperature and needs to be modified with other materials to improve its glass transition temperature and heat resistance.

Chinese invention patent "CN 201510923049.9 polyphenylene ether resin composition, prepreg, metal foil-clad laminate, and printed wiring board" provides a polyphenylene ether resin composition containing: a modified polyphenylene ether copolymer in which phenolic hydroxyl groups at the molecular terminals of the polyphenylene ether copolymer are modified with a compound having a carbon-carbon unsaturated double bond; a polymer substance having a weight average molecular weight larger than that of the modified polyphenylene ether copolymer, having at least one structure selected from a polystyrene skeleton, a polybutadiene skeleton and a (meth) acrylate skeleton, and having a softening point of 110 ℃ or lower; and 1 compound having 2 or more carbon-carbon unsaturated double bonds in a molecule, having a melting point of 30 ℃ or less, and being compatible with the modified polyphenylene ether copolymer, wherein the content of the polymer substance is 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total of the modified polyphenylene ether copolymer and the compound compatible with the modified polyphenylene ether copolymer, and the compound compatible with the modified polyphenylene ether copolymer contains a compound selected from a polyfunctional acrylate compound, a polyfunctional methacrylate compound, and a divinylbenzene compound.

The resin composition utilizes the dielectric property, high temperature resistance, high glass transition temperature and other properties of the polyphenyl ether and polybutadiene framework material. However, the conventional polyphenylene ether is incompatible with other resins (e.g., polybutadiene), and therefore in this embodiment, a (meth) acrylate skeleton is also introduced into the polybutadiene skeleton, and a compound having 2 or more carbon-carbon unsaturated double bonds in 1 molecule and having a melting point of 30 ℃ or less and being compatible with the modified polyphenylene ether copolymer is added to the composition.

However, the addition of (meth) acrylate backbone or other compounds is disadvantageous to fully utilize various properties of the backbone of polyphenylene ether and polybutadiene, as compared to the simple polyphenylene ether or 1, 2-polybutadiene materials, such that the dielectric properties, thermal properties, glass transition temperature, etc. of polyphenylene ether and polybutadiene materials cannot be fully utilized in the composition. The application requirements of the material in 5G high-frequency communication are not met.

Disclosure of Invention

Based on the problems in the prior art, the invention provides a co-crosslinked polymer of end double bond polyphenylene oxide and epoxidized polybutadiene resin for 5G high-speed high-frequency communication and a preparation method thereof, and the purpose is as follows: the molecular weight of the polyphenyl ether is reduced through a redistribution mechanism, and the end group of the polyphenyl ether is modified, so that the obtained low molecular weight double-bond-terminated polyphenyl ether and the epoxidized polybutadiene can be successfully compatible, and therefore, the co-crosslinking modification is realized, and the material with low dielectric constant, low dielectric loss, high glass transition temperature and high heat resistance is obtained.

A co-crosslinked polymer is prepared through reaction between polyphenyl ether with terminal double bonds and epoxidized polybutadiene under the action of cross-linking agent and solidifying agent, and solidifying.

Preferably, the number average molecular weight of the polyphenylene ether with terminal double bonds is 1000-6000, preferably 2000-3000, and more preferably 2500, and/or the number average molecular weight of the epoxidized polybutadiene is 1000-2000, and the preferred epoxidized polybutadiene is epoxidized polybutadiene with side chain epoxy group number of 4-7, side chain double bond number of 16-25, and Mn of 1300;

and/or the weight ratio of the amount of the epoxidized polybutadiene to the double-bond-terminated polyphenyl ether is 100:10-40, preferably 100: 20.

preferably, the polyphenylene ether with terminal double bonds is prepared by the following method:

(1) mixing polyphenyl ether and bisphenol A for reaction to obtain hydroxyl-terminated polyphenyl ether; the molecular weight of the hydroxyl-terminated polyphenylene ether is lower than that of the polyphenylene ether;

(2) and mixing and reacting the double-end hydroxyl polyphenylene oxide and methacrylic anhydride to obtain the double-end bond polyphenylene oxide.

Preferably, the number average molecular weight of the polyphenylene ether is 10000-; and/or the number average molecular weight of the hydroxyl-terminated polyphenylene ether is 1500-7000, preferably 2477.

Preferably, in the step (1), the reaction is carried out under the action of an initiator, preferably the initiator is acyl peroxide, further preferably the initiator is benzoyl peroxide, and the dosage weight ratio of the polyphenylene oxide to the initiator is preferably 10:0.1-10:3, preferably 10: 1; and/or the reaction temperature is 50-100 ℃, preferably 90 ℃; and/or the reaction time is 4-6 h; and/or the solvent for the reaction is at least one of toluene, dichloromethane, chloroform, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, dimethylformamide or mesitylene, preferably toluene; and/or, the reaction is carried out under an inert atmosphere; and/or the dosage weight ratio of the polyphenyl ether to the bisphenol A is 10:0.1-10:3, preferably 10: 1;

and/or, in the step (2), the reaction is carried out under the action of a base, preferably the base is triethylamine, and preferably the weight ratio of the hydroxyl-terminated polyphenylene oxide to the base is 100:10-100:30, preferably 100: 21; the reaction temperature is 40-120 ℃, and preferably 80 ℃; and/or the reaction time is 3-9h, preferably 5 h; and/or the solvent for the reaction is at least one of toluene, dichloromethane, chloroform, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, dimethylformamide or mesitylene, preferably toluene; and/or the weight ratio of the hydroxyl-terminated polyphenyl ether to the methacrylic anhydride is 100:10-100:60, preferably 100: 42.

Preferably, the method comprises the following steps:

reacting the end double bond polyphenyl ether and the epoxidized polybutadiene under the action of a cross-linking agent and a curing agent, and curing to obtain the modified polyphenylene oxide/epoxidized polybutadiene.

Preferably, the crosslinking agent is at least one of dicumyl peroxide (DCP), dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl peroxyacetate, tert-butyl peroxybenzene, diisobutyl peroxide, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, benzoyl peroxide or benzoyl peroxide derivatives, preferably dicumyl peroxide;

and/or the curing agent is selected from at least one of aliphatic amine, aromatic amine, linear low molecular weight amine or curing accelerator, the aliphatic amine comprises at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethylenediamine, m-xylene diamine or m-xylene diamine Mannich base, the aromatic amine is selected from at least one of m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone or polyarylether diamine, the organic acid anhydride comprises at least one of phthalic anhydride, maleic anhydride, methylnadic anhydride or methylhexahydrophthalic anhydride, the linear low molecular weight amine comprises polyamide resin, phenol novolac resin, polyphenol resin, arylamine formaldehyde resin or polysulfide compound, the linear low molecular weight amine has a molecular weight of 200, 2000, preferably 200, 600 or 2000, the curing accelerator comprises at least one of naphthenate, vanadium pentoxide, aniline derivative, quaternary ammonium salt, imidazole or imidazole derivative, the naphthenate is one of cobalt naphthenate, zinc naphthenate, manganese naphthenate or lead naphthenate, the aniline derivative is preferably dimethylaniline, the quaternary ammonium salt is preferably at least one of tetramethylammonium chloride or tetrabutylammonium bromide, and the curing agent is preferably a combination of methyl hexahydrophthalic anhydride and imidazole;

And/or the weight ratio of the dosage of the epoxidized polybutadiene to the cross-linking agent is 100:0.01-100:10, preferably 100: 2; and/or the dosage weight ratio of the epoxidized polybutadiene to the curing agent is 100:20-100:120, preferably 100: 78; and/or the curing conditions are as follows: sequentially treating at 139 deg.C for 60-120min, at 175 deg.C for 120-240min, and at 188 deg.C for 60-120min, preferably sequentially treating at 139 deg.C for 90min and 175 deg.C for 180 min; treating at 188 deg.C for 90 min;

and/or the curing agent is selected from methyl hexahydrophthalic anhydride and imidazole, and the weight ratio of the epoxidized polybutadiene to the methyl hexahydrophthalic anhydride to the imidazole is 100 (20-120) to (0.1-10), and preferably 100 to 77 to 1.

The invention also provides a preparation method of the co-crosslinked polymer, which comprises the following specific steps:

(3.1) mixing the double-bond-terminated polyphenylene ether and the epoxidized polybutadiene at 40 to 120 ℃, preferably at 90 ℃;

(3.2) heating to 90-130 ℃, preferably 110 ℃, adding a cross-linking agent, and stirring for 5-60 min, preferably 10 min;

(3.3) maintaining the temperature at 90-130 ℃, preferably at 110 ℃, adding a curing agent, and stirring for 5-60 min, preferably 10 min; obtaining mixed resin;

and (3.4) vacuumizing to remove air bubbles in the mixed resin in the step (3.3), and curing in a mold to obtain the resin.

Preferably, in the step (3.4), the vacuumizing condition is 80-130 ℃, preferably 100 ℃, and the vacuumizing time is 15-120 min, preferably 30 min.

The invention also provides the application of the co-crosslinked polymer as a PCB substrate material or a radome, and the PCB substrate material is preferably used for manufacturing 5G communication equipment.

In the present invention, JP-100 is a partially pendant double bond epoxidized polybutadiene resin produced by Nippon Caoda corporation.

The technical scheme of the invention achieves the following technical effects:

1. the co-crosslinked polymer has the advantages of high glass transition temperature and high temperature resistance, and has a wide applicable temperature range.

2. The co-crosslinked polymer has very low dielectric constant and dielectric loss, and is very suitable for low dielectric materials for 5G high-speed high-frequency communication.

3. The invention utilizes redistribution mechanism to reduce the molecular weight of polyphenylene oxide and modify the end group of polyphenylene oxide, so that the polyphenylene oxide has good compatibility with epoxidized polybutadiene, and the polyphenylene oxide and the epoxidized polybutadiene can be smoothly mixed and modified. Overcomes the difficulty of incompatibility of traditional polyphenyl ether and other resin (such as 1, 2-polybutadiene). Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.

The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Drawings

FIG. 1 is a schematic diagram of the loss of a polymer dielectric material when subjected to electromagnetic waves;

FIG. 2 is the NMR hydrogen spectrum of PPO-OH in example 1;

FIG. 3 is the NMR hydrogen spectrum of R-PPO in example 1;

FIG. 4 is a schematic diagram of the cross-linking reaction of R-PPO with JP-100 according to the present invention;

FIG. 5 is a schematic structural view of a co-crosslinked polymer made according to the present invention;

fig. 6 is SEM characterization results of the samples obtained in example 1 and comparative example.

Detailed Description

The following examples and experimental examples used the following starting materials and reagents:

the reagents used in the examples of the invention were as follows:

polyphenylene ether (molecular weight 13000-;

bisphenol A (BPA), Benzoyl Peroxide (BPO), toluene, methanol and triethylamine are purchased from a chemical reagent factory of Synechol;

methacrylic anhydride, methylhexahydrophthalic anhydride, imidazole were purchased from Shanghai Allantin, Inc.;

The epoxidized polybutadiene resin was JP-100, available from Caoda, Japan, Inc.

Example 1

This example prepares a polymer co-crosslinked with a terminal double bond polyphenylene ether and an epoxidized polybutadiene resin by the following steps:

1. preparation of hydroxyl-terminated polyphenylene oxide (PPO-OH):

1) adding 600g of PPO, 60g of BPA and 1350ml of toluene into a 3000ml three-neck flask, introducing nitrogen to remove air in the flask, stirring and heating to 90 ℃;

2) after PPO and BPA are completely dissolved (about 30min), a toluene solution of BPO (wherein the BPO is 60g, and the toluene is 600ml) is dripped by using a dropping funnel for 2h, and the reaction is carried out for 4h after the dripping is finished.

3) After the reaction was completed, the mixture was poured into a beaker, cooled to room temperature, precipitated with frozen methanol (mixture to methanol volume ratio of about 1:1.5 to 2), filtered, and washed twice.

4) With Na₂CO₃Aqueous solution (50g Na)₂CO₃1000ml of water) to remove excess BPO. Washing the mixture twice with deionized water; finally, washing and filtering the mixture by using frozen methanol, and placing the mixture in an oven to remove methanol solvent (the temperature is 70 ℃ and the time is 3 hours) to obtain PPO-OH.

The hydrogen nuclear magnetic resonance spectrum of PPO-OH is shown in FIG. 2, and chemical shifts of hydroxyl hydrogen appear around 4.2ppm and 8.2 ppm. This indicates the successful preparation of PPO-OH.

The molecular weights of PPO and PPO-OH are shown in the following table,

TABLE 1 molecular weights of PPO and PPO-OH

As is clear from the table, the number average molecular weight of PPO in this example is 14818 and the number average molecular weight of PPO-OH is 2477, indicating that the molecular weight of PPO-OH is significantly lower than that of PPO by the redistribution reaction in this step.

2. Preparation of end double bond polyphenylene oxide (R-PPO):

1) adding 157g of toluene and PPO-OH50g into a 500ml three-neck flask, heating to 40 ℃, and completely dissolving under stirring;

2) after the solution is completely dissolved, 10.5g of triethylamine and 21g of methacrylic anhydride are added;

3) heating to 80 ℃, reacting for 5h, and finishing the reaction;

4) washing the reacted solution with frozen methanol until polymer precipitates;

5) vacuum-pumping, filtering and drying to obtain the low molecular weight PPO (i.e. end double bond polyphenylene oxide, R-PPO) containing double bonds.

The hydrogen nuclear magnetic resonance spectrum of R-PPO is shown in figure 3, and the peaks are obvious at two positions of 5.15-5.30ppm and 5.70-5.80ppm, and correspond to the peak of H on C, which shows that methacrylic anhydride is well grafted to two ends of PPO-OH.

3. Preparation of the Co-crosslinked Polymer:

the reaction process of this step is shown in FIG. 4. The schematic structure of the resulting co-crosslinked polymer is shown in FIG. 5. The method comprises the following specific steps:

1) Adding 100phr of JP-100 into a three-neck flask, heating to 90 ℃, adding 10/20/30/40phr of R-PPO, and fully stirring to uniformly mix the materials;

2) fully stirring the mixture of the R-PPO and the JP-100 until no obvious solid particles appear in the system;

3) heating to 110 deg.C, adding 2phrDCP, and stirring for 10 min;

4) keeping the temperature at 110 ℃ constant, adding 77phr of methyl hexahydrophthalic anhydride (HHMPA) and 1phr of imidazole into the system, and stirring for 10 min;

5) quickly pouring the mixed resin into a beaker when the resin is hot, vacuumizing for 30min at 100 ℃, and removing bubbles in the system;

6) and pouring the vacuumized resin into a tetrafluoro mold, and curing according to the programmed temperature. Curing conditions are as follows: 90min at 139 ℃ and 180min at 175 ℃; and (3) performing temperature regulation at 188 ℃ for 90min to obtain the product.

The manner in which the co-crosslinked polymer prepared in this example is represented in the experimental examples and the amounts of the raw materials are shown in the following table:

TABLE 2 amount of raw materials used in step 3 of this example

Comparative example

1) Adding 100phr of JP-100 into a three-neck flask, heating to 90 ℃, and fully stirring to uniformly mix the materials;

2) heating to 110 deg.C, adding 2phrDCP, and stirring for 10 min;

3) keeping the temperature at 110 ℃ constant, adding 77phr of methyl hexahydrophthalic anhydride (HHMPA) and 1phr of imidazole into the system, and stirring for 10 min;

4) Quickly pouring the mixed resin into a beaker when the resin is hot, vacuumizing for 30min at 100 ℃, and removing bubbles in the system;

5) and pouring the vacuumized resin into a tetrafluoro mold, and curing according to the programmed temperature. Curing conditions are as follows: 90min at 139 ℃ and 180min at 175 ℃; and (3) performing temperature regulation at 188 ℃ for 90min to obtain the product.

The sample obtained in the comparative example was designated as "pure JP-100 curing System" in the experimental example.

Experimental example 1 glass transition temperature

The glass transition temperatures of the samples obtained in the examples and comparative examples were tested by DMA (dynamic thermodynamic analysis Q800) using a three-point bending mode. The test conditions were: the temperature is increased from 0 ℃ to 250 ℃, and the temperature increasing speed is 5 ℃/min. The glass transition temperature (Tg) results of the obtained samples are shown in table 3.

TABLE 3 glass transition temperatures of examples and comparative examples

For the neat JP-100 cure system, the glass transition temperature Tg is about 120 ℃ and when R-PPO is added, the Tg increases significantly to 190 ℃ and 200 ℃ showing a high Tg transition. As the fraction of R-PPO increases, its Tg will remain substantially unchanged around 190-200 ℃. It can be seen that the addition of R-PPO allows the co-crosslinked polymer of the present invention to have a higher glass transition temperature relative to JP-100, thereby broadening the service temperature of the material.

Experimental example 2 micro-morphology

SEM characterization of brittle fracture sections of a pure JP-100 curing system and a JP-100/R-PPO (100/30) sample is shown in FIG. 6. The surface of the pure JP-100 cured system was found to be smooth by SEM. After the addition of R-PPO, the surface of the JP-100/R-PPO (100/30) system remained smooth. And the DMA test of experimental example 1 shows that the JP-100/R-PPO (100/30) system has only one loss peak, which shows that the compatibility of the R-PPO in the co-crosslinked polymer of the invention and the JP-100 is better.

EXAMPLE 3 thermogravimetric analysis (TGA)

The results of the thermogravimetric analysis of the samples of examples and comparative examples are shown in table 4.

TABLE 4 thermogravimetric analysis of the examples and comparative examples

As can be seen from the table, the decomposition of the pure JP-100 cured system started around 275 ℃. After the R-PPO is added, the initial thermal decomposition temperature of the system is increased to 340 ℃, and the thermal decomposition temperature of the polymer is obviously increased. And the change of the initial thermal decomposition temperature is not obvious as the addition amount of the R-PPO is changed within 10-40 phr.

This shows that the co-crosslinked polymer of the present invention has better high temperature resistance than JP-100, a low dielectric material.

Experimental example 4 dielectric property test

The dielectric constants of the samples of examples and comparative examples were measured using a broadband dielectric resistance relaxation spectrometer, and the results are shown in table 5.

TABLE 5 dielectric constant of samples of examples and comparative examples

As can be seen from the data in the table, the dielectric constant for the prototype JP-100 cured system is around 3.

With the increase of the addition amount of the R-PPO, the dielectric constant of the sample has a change rule of firstly decreasing and then increasing. When the addition amount of the R-PPO is 20phr, the dielectric constant is the lowest (2.55) and the loss factor is the lowest.

From the results obtained in the present experimental examples, it is understood that when the amount of R-PPO added is 20phr, the copolymer system exhibits excellent low dielectric properties, and is most suitable for use as a high-speed, high-frequency, low-dielectric material in the examples of the present invention.

In conclusion, in the co-crosslinked polymer of the end double-bond polyphenyl ether and the epoxidized polybutadiene resin, the end double-bond polyphenyl ether and the epoxidized polybutadiene have good compatibility, and can be smoothly co-crosslinked to form a network polymer after being mixed and cured. The polymer has the advantages of high glass transition temperature and high temperature resistance, and the applicable temperature range is wide; and the dielectric constant and the dielectric loss are lower, so that the material is suitable for being used as a high-speed high-frequency low-dielectric material. The co-crosslinked polymer has good application prospect.

Claims

1. A co-crosslinked polymer characterized by: the epoxy modified polyphenylene oxide is prepared by reacting and curing double-bond-terminated polyphenylene oxide and epoxidized polybutadiene under the action of a cross-linking agent and a curing agent;

The number average molecular weight of the end double bond polyphenyl ether is 1000-6000, and the number average molecular weight of the epoxidized polybutadiene is 1000-2000;

the weight ratio of the dosage of the epoxidized polybutadiene to the double-bond-terminated polyphenyl ether is 100: 10-40;

the cross-linking agent is at least one of dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl peroxyacetate, tert-butyl peroxybenzene, diisobutyryl peroxide, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyacetate, benzoyl peroxide or benzoyl peroxide derivatives.

2. A co-crosslinked polymer according to claim 1, wherein: the number average molecular weight of the end double bond polyphenyl ether is 2000-3000, and/or the epoxidized polybutadiene is epoxidized polybutadiene containing 4-7 side chain epoxy groups, 16-25 side chain double bonds and 1300 Mn;

and/or the dosage weight ratio of the epoxidized polybutadiene to the end double bond polyphenyl ether is 100: 20.

3. a co-crosslinked polymer according to claim 2, wherein: the number average molecular weight of the end double bond polyphenyl ether is 2500.

4. The co-crosslinked polymer of claim 1, wherein: the end double bond polyphenylene oxide is prepared by the following method:

(1) mixing polyphenyl ether and bisphenol A for reaction to obtain double-end hydroxyl polyphenyl ether; the molecular weight of the hydroxyl-terminated polyphenylene ether is lower than that of the polyphenylene ether;

5. A co-crosslinked polymer according to claim 4, wherein: the number average molecular weight of the polyphenyl ether is 10000-; and/or the number average molecular weight of the hydroxyl-terminated polyphenylene ether is 1500-7000.

6. A co-crosslinked polymer according to claim 5, wherein: the number average molecular weight of the polyphenyl ether is 10000-25000; and/or the number average molecular weight of the double-end hydroxyl polyphenylene ether is 2477.

7. A co-crosslinked polymer according to claim 6, wherein: the polyphenylene ether had a number average molecular weight of 14818.

8. A co-crosslinked polymer according to claim 4, wherein: in the step (1), the reaction is carried out under the action of an initiator; and/or the temperature of the reaction is 50-100 ℃; and/or the reaction time is 4-6 h; and/or the solvent for the reaction is at least one of toluene, dichloromethane, chloroform, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, dimethylformamide or mesitylene; and/or, the reaction is carried out under an inert atmosphere; and/or the dosage weight ratio of the polyphenyl ether to the bisphenol A is 10:0.1-10: 3;

And/or, in the step (2), the reaction is carried out under the action of alkali; the reaction temperature is 40-120 ℃; and/or the reaction time is 3-9 h; and/or the solvent for the reaction is at least one of toluene, dichloromethane, chloroform, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, dimethylformamide or mesitylene; and/or the weight ratio of the double-end hydroxyl polyphenylene oxide to the methacrylic anhydride is 100:10-100: 60.

9. A co-crosslinked polymer according to claim 8, wherein: in the step (1), the initiator is acyl peroxide, and the weight ratio of the polyphenyl ether to the initiator is 10:0.1-10: 3; and/or the temperature of the reaction is 90 ℃; and/or the solvent of the reaction is toluene; and/or the dosage weight ratio of the polyphenyl ether to the bisphenol A is 10: 1;

and/or in the step (2), the alkali is triethylamine, and the weight ratio of the bis-hydroxy-terminated polyphenyl ether to the alkali is 100:10-100: 30; the temperature of the reaction is 80 ℃; and/or the reaction time is 5 h; and/or the solvent of the reaction is toluene; and/or the weight ratio of the hydroxyl-terminated polyphenyl ether to the methacrylic anhydride is 100: 42.

10. A co-crosslinked polymer according to claim 9, wherein: in the step (1), the initiator is benzoyl peroxide, and the weight ratio of the polyphenyl ether to the initiator is 10: 1;

and/or in the step (2), the weight ratio of the hydroxyl-terminated polyphenyl ether to the alkali is 100: 21.

11. A process for the preparation of a co-crosslinked polymer according to any of claims 1 to 10, characterized in that it comprises the following steps:

and (3) reacting the end double bond polyphenyl ether and the epoxidized polybutadiene under the action of a cross-linking agent and a curing agent, and curing to obtain the modified epoxy polybutadiene.

12. The method of claim 11, wherein:

the curing agent is at least one of aliphatic amine, aromatic amine, organic acid anhydride, linear low molecular weight amine or curing accelerator, the aliphatic amine comprises at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine or ethylenediamine, the aromatic amine is at least one of metaphenylene amine, diaminodiphenyl methane, diaminodiphenyl sulfone, polyarylether diamine, metaxylene diamine or metaxylene diamine Mannich base, the organic acid anhydride comprises at least one of phthalic anhydride, maleic anhydride, methylnadic anhydride or methylhexahydrophthalic anhydride, the linear low molecular weight amine comprises polyamide resin, novolac resin, polyphenol resin, arylamine formaldehyde resin or polysulfide compound, the linear low molecular weight amine has a molecular weight of 200-2000, and the curing accelerator comprises naphthenate, and m-xylene diamine, At least one of vanadium pentoxide, aniline, an aniline derivative, a quaternary ammonium salt, imidazole or an imidazole derivative, wherein the naphthenate is one of cobalt naphthenate, zinc naphthenate, manganese naphthenate or lead naphthenate;

And/or the dosage weight ratio of the epoxidized polybutadiene to the cross-linking agent is 100:0.01-100: 10; and/or the weight ratio of the dosage of the epoxidized polybutadiene to the dosage of the curing agent is 100:20-100: 120; and/or, the curing conditions are as follows: sequentially treating at 139 deg.C for 60-120min, at 175 deg.C for 120-240min, and at 188 deg.C for 60-120 min;

and/or the curing agent is selected from methyl hexahydrophthalic anhydride and imidazole, and the weight ratio of the usage amount of the epoxidized polybutadiene, the methyl hexahydrophthalic anhydride and the imidazole is 100 (20-120) to 0.1-10.

13. The method of claim 12, wherein: the cross-linking agent is dicumyl peroxide;

and/or the linear low molecular weight amine has a molecular weight of 200, 600 or 2000, the aniline derivative is dimethylaniline, the quaternary ammonium salt is at least one of tetramethylammonium chloride or tetrabutylammonium bromide, and the curing agent is a combination of methyl hexahydrophthalic anhydride and imidazole;

and/or the dosage weight ratio of the epoxidized polybutadiene to the cross-linking agent is 100: 2; and/or the dosage weight ratio of the epoxidized polybutadiene to the curing agent is 100: 78; and/or, the curing conditions are as follows: sequentially treating at 139 deg.C for 90min and 175 deg.C for 180 min; treating at 188 deg.C for 90 min;

And/or the curing agent is selected from methyl hexahydrophthalic anhydride and imidazole, and the weight ratio of the usage amount of the epoxidized polybutadiene, the methyl hexahydrophthalic anhydride and the imidazole is 100:77: 1.

14. The production method according to any one of claims 11 to 13, characterized in that: the specific process comprises the following steps:

(3.1) mixing the end double bond polyphenylene ether and the epoxidized polybutadiene at 40-120 ℃;

(3.2) heating to 90-130 ℃, adding a cross-linking agent, and stirring for 5-60 min;

(3.3) maintaining the temperature at 90-130 ℃, adding a curing agent, and stirring for 5-60 min; obtaining mixed resin;

15. The method of claim 14, wherein: the specific process comprises the following steps:

(3.1) mixing the double-bond-terminated polyphenylene ether and the epoxidized polybutadiene at 90 ℃;

(3.2) heating to 110 ℃, adding a cross-linking agent, and stirring for 10 min;

(3.3) maintaining the temperature at 110 ℃, adding a curing agent, and stirring for 10 min; obtaining mixed resin;

16. The method of claim 14, wherein: in the step (3.4), the vacuumizing condition is that the vacuumizing is carried out for 15min to 120min at the temperature of 80 ℃ to 130 ℃.

17. The method of claim 16, wherein: in the step (3.4), the vacuumizing condition is that the vacuumizing is carried out for 30min at the temperature of 100 ℃.

18. Use of the co-crosslinked polymer according to any one of claims 1 to 10 as a PCB substrate material or radome.

19. Use according to claim 18, characterized in that: the PCB substrate material is used for manufacturing 5G communication equipment.