CN113372555A - Composite material with low dielectric constant and low dielectric loss as well as preparation method and application thereof - Google Patents

Composite material with low dielectric constant and low dielectric loss as well as preparation method and application thereof Download PDF

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CN113372555A
CN113372555A CN202110708415.4A CN202110708415A CN113372555A CN 113372555 A CN113372555 A CN 113372555A CN 202110708415 A CN202110708415 A CN 202110708415A CN 113372555 A CN113372555 A CN 113372555A
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low dielectric
sulfur
polymer
reaction kettle
glycidyl ether
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CN113372555B (en
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张兴宏
冯展彬
曹晓翰
张旭阳
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The invention discloses a composite material with low dielectric constant and low dielectric loss, a preparation method and application thereof, wherein the composite material comprises a sulfur-containing polymer; the sulfur-containing polymer is prepared by carrying out anion ring-opening copolymerization on a sulfur-containing carbon monomer, an epoxy monomer and anhydride under the action of a catalyst; the epoxy monomer is selected from the group consisting of trifluoropropylene oxide, 3- (2,2,3, 3-tetrafluoropropoxy) -1, 2-propylene oxide, hexafluoropropylene oxide, heptafluorobutylethylene oxide, octafluoropentyloxy-1, 2-propylene oxide, nonafluoropentylylene oxide, perfluoro-2-methyl-2, 3-cyclopentane oxide, tridecafluoroheptylethylene oxide, glycidyl ether, hexadecyl fluorononyl ether, naphthyl glycidyl ether, anthryl glycidyl ether, azo-phenyl glycidyl ether and biphenyl glycidyl ether. The composite material disclosed by the invention has low dielectric constant and low dielectric loss under high frequency, and the polymer main chain has no water-absorbing group, so that the composite material is expected to be widely applied to the field of 5G mobile phone antenna materials.

Description

Composite material with low dielectric constant and low dielectric loss as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of sulfur-containing polymers, in particular to a composite material with low dielectric constant and low dielectric loss, a preparation method thereof and application thereof in preparation of 5G mobile phone antenna materials.
Background
With the coming of the fifth generation mobile communication (5G) era, electronic devices such as mobile phones and the like need to operate rapidly at high frequency (GHz) and high speed, and the data transmission amount is also increased rapidly. Compared with 4G communication, the 5G communication has higher transmission speed and lower electromagnetic wave covering capability, so that the dielectric constant of the material to be propagated is lower; high-speed operation of electronic devices at high frequencies causes problems such as increased heat generation, and therefore, materials having lower dielectric loss are required. In order to meet the design requirements of 5G equipment, especially mobile phone antennas, the polymer material needs to have the characteristics of low dielectric constant, low dielectric loss and the like.
The 5G mobile phone antenna is mostly made of polyimide materials, and the traditional Polyimide (PI) film has high TgAnd wide operation temperature, but the dielectric loss is large, and the material is easy to absorb moisture in the air, so that the application of the material in 5G mobile phone antenna materials is influenced, and at present, the material with low dielectric constant and loss and good moisture absorption performance can be prepared by modifying based on a PI film. The PI film is prepared by adopting a two-step process of synthesizing polyamic acid and film-forming imidization, a large amount of solvents such as DMAc and the like are needed in the process, the preparation cost is relatively high, and the generated large amount of organic solvents can cause great pollution to the environment; in addition, the moisture absorption performance of PI is difficult to be optimized even though it is modified, and therefore, it is required to develop a novel polymer having low moisture absorption, low dielectric constant and low dielectric loss at high frequency for use in 5G mobile phone antenna materials.
Disclosure of Invention
In view of the above problems in the prior art, the present invention discloses a composite material with sulfur-containing polymer as main base material, which comprisesHas the advantages of low dielectric constant and low dielectric loss at high frequency (GHz), and higher TgAnd tensile strength, and the polymer main chain has no water-absorbing group, so that the polymer is expected to be widely applied to the field of 5G mobile phone antenna materials.
The specific technical scheme is as follows:
a low dielectric constant, low dielectric loss composite material comprising a sulfur-containing polymer;
the sulfur-containing polymer is prepared by carrying out anion ring-opening copolymerization on a sulfur-containing carbon monomer, an epoxy monomer and anhydride under the action of a catalyst;
the epoxy monomer is selected from one or more of trifluoropropylene oxide, 3- (2,2,3, 3-tetrafluoropropoxy) -1, 2-propylene oxide, hexafluoropropylene oxide, heptafluorobutylethylene oxide, octafluoropentyloxy-1, 2-propylene oxide, nonafluoropentylylene oxide, perfluoro-2-methyl-2, 3-epoxypentane, tridecafluoroheptylethylene oxide, glycidyl ether, hexadecyl fluorononyl ether, naphthyl glycidyl ether, anthryl glycidyl ether, azo-phenyl glycidyl ether and biphenyl glycidyl ether.
The invention discloses a composite material with low dielectric constant and low dielectric loss under high frequency, which takes a sulfur-containing polymer as a main substrate, and the sulfur-containing polymer prepared by screening a specific epoxy monomer has low dielectric constant and low dielectric loss and takes higher T into considerationgAnd tensile strength, and the polymer backbone is free of water absorbing groups.
Tests show that the selection of the epoxy monomer type is particularly important, and is the key to whether low dielectric constant and low dielectric loss can be obtained, and the screening of the epoxy monomer containing fluorine, or the epoxy monomer containing benzene ring, anthracene ring and naphthalene ring, or the epoxy monomer containing liquid crystal elements is the premise of obtaining low dielectric constant and low dielectric loss.
Preferably, the epoxy monomer is selected from one or more of hexafluoropropylene oxide, heptafluorobutyl ethylene oxide, octafluorobutyl ethylene oxide, tridecafluoroheptyl ethylene oxide, glycidyl ether hexadecafluorononyl ether, octafluoropentyloxy-1, 2-propylene oxide, naphthyl glycidyl ether, anthryl glycidyl ether, azophenyl glycidyl ether, biphenyl glycidyl ether.
Further preferably, the epoxy monomer is selected from one or more of tridecafluoroheptyl ethylene oxide, glycidyl ether hexadecafluorononyl ether, azophenyl glycidyl ether and biphenyl glycidyl ether.
It has been found through experiments that the sulfur-containing polymer prepared has lower dielectric constant and dielectric loss with the preference of the epoxy monomer types.
In the invention:
the sulfur-containing carbon-monomer is selected from carbon oxysulfide and/or carbon disulfide;
the anhydride is selected from one or more of maleic anhydride, 2, 3-difluoromaleic anhydride, glutaric anhydride, phthalic anhydride, tetrafluorophthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, trichlorophthalic anhydride, diglycolic anhydride and thiohydroxy acetic anhydride;
the catalyst is selected from a zinc-cobalt double metal cyanide complex (Zn-Co (III) DMCC), a salicylaldehyde diimine chromium chloride complex (salen. CrCl), a salicylaldehyde diimine cobalt chloride complex (salen. CoCl), beta-diimine zinc, Triethylboron (TEB), dodecyl trimethyl ammonium bromide (DTMeAB), 1, 8-diazo heterodouble spiro [ 5.4.0%]Undec-7-ene (DBU), bis (triphenylphosphine) ammonium chloride (PPNCl), tetraphenylphosphonium bromide (PPh)4Br), tetraphenylphosphonium chloride (PPh)4Cl), tetrabutylammonium chloride (NBu)4Cl).
Preferably:
the molar ratio of the catalyst to the epoxy monomer and the anhydride is 1: 100-500: 150 to 1000;
the molar ratio of the epoxy monomer to the anhydride is 1:0.5 to 2;
the molar ratio of the catalyst to the sulfur-containing carbon-monomer is 1: 120-600 parts;
the temperature of the anion ring-opening copolymerization is 30-120 ℃, and the time is 2-50 h.
Further preferably:
the molar ratio of the catalyst to the epoxy monomer is 1:300 to 500 parts by weight; the catalyst has higher catalytic activity at the molar ratio through experiments.
The molar ratio of the epoxy monomer to the anhydride is 1:2, the molar ratio of the sulfur-containing carbon-monomer to the epoxy monomer is 1.2: 1. at this molar ratio, the resulting sulfur-containing polymer has a low dielectric constant and dielectric loss.
Preferably, the composite material further comprises a polymer additive and/or a nano porous material;
the polymer additive is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride and polyimide;
the nano-porous material is selected from one or more of polyhedral oligomeric silsesquioxanes (POSS), silicon dioxide aerogel, graphene oxide aerogel and two-dimensional transition metal carbon/nitride (Mxenes) aerogel.
By further adding the high molecular additive and the nano porous material, the dielectric constant and the dielectric loss of the sulfur-containing polymer can be further reduced, and the T of the composite material can be remarkably improvedgAnd tensile strength.
Preferably, the raw materials comprise the following components in percentage by weight:
60-90% of a sulfur-containing polymer;
5-20% of a polymer additive;
5-20% of the nano porous material.
Further preferably, the raw materials comprise the following components in percentage by weight:
70-80% of a sulfur-containing polymer;
10-15% of a polymer additive;
10-15% of nano porous material.
The invention also discloses a preparation method of the composite material with low dielectric constant and low dielectric loss, which comprises the following steps:
(1) blending a sulfur-carbon-containing monomer, an epoxy monomer, acid anhydride, a catalyst and an optionally added solvent, carrying out anion ring-opening polymerization, and carrying out post-treatment to obtain a sulfur-containing polymer;
(2) and (2) blending the sulfur-containing polymer prepared in the step (1), the selectively added high molecular additive and the selectively added nano porous material, and performing hot pressing to obtain the composite material with low dielectric constant and low dielectric loss.
In the step (1):
the solvent which can be selectively added is one or more selected from tetrahydrofuran, toluene, cyclohexane, N-hexane, N-dimethylformamide and N, N-dimethyl sulfoxide; whether or not to add the solvent is selected specifically depending on the state (liquid or solid state) of the monomer. The amount of solvent added is such that the monomer is completely dissolved.
The post-treatment comprises dissolving, settling and drying treatment.
The composite material prepared by the preparation process and the specific raw materials has the advantages of low dielectric constant and low dielectric loss under high frequency and higher TgAnd tensile strength, and the main chain of the polymer has no water-absorbing group, so that the polymer is expected to be used as a 5G mobile phone antenna material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the sulfur-containing polymer-based composite material disclosed by the invention has the characteristics of low dielectric constant and low dielectric loss under high frequency (GHz);
(2)Tgthe mechanical strength is high, so that the normal use of the prepared mobile phone antenna material under the condition of high-frequency operation and high heat generation can be ensured;
(3) the main chain of the molecule is a hydrophobic chain, so that the moisture absorption of the material is inhibited, and the long-term use of the mobile phone antenna material prepared from the material can be ensured;
(4) the reaction process is simple and feasible, the reaction temperature is lower, the product structure is controllable, a large amount of organic solvent is not generated, and the industrial production is easy to realize.
Detailed Description
The present invention will be described in further detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto.
Example 1
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; adding a zinc-cobalt double metal cyanide complex (Zn-Co (III) DMCC), trifluoro propylene oxide (TFPO), Maleic Anhydride (MA) (the molar ratio of the TFPO to the MA is 1:2) and 2mL tetrahydrofuran into a reaction kettle in sequence, wherein the molar ratio of the catalyst to the TFPO is 1: 100. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the TFPO is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 30 ℃ for reaction for 2 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 2
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding a salicylaldehyde diimine chromium chloride complex (salen. CrCl), 3- (2,2,3, 3-tetrafluoropropoxy) -1, 2-propylene oxide (TFPP), Maleic Anhydride (MA) (the molar ratio of the TFPP to the MA is 1:2) and 2mL of tetrahydrofuran into a reaction kettle, wherein the molar ratio of a catalyst to the TFPP is 1: 200. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the TFPP is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 40 ℃ for reaction for 6 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 3
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; to the reaction kettle were added successively salicylaldiminato cobalt chloride complex (salen. cocl), hexafluoropropylene oxide (TFTO), Maleic Anhydride (MA) (molar ratio of TFTO to MA was 1:2), and 2mL tetrahydrofuran, with molar ratio of catalyst to TFTO being 1: 300. The reaction kettle was closed and taken out from the glove box, charged with carbonyl sulfide (COS) at a molar ratio of COS to TFTO of 1.2:1 at room temperature, and placed in an oil bath pan at 50 ℃ for reaction for 10 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 4
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; the reaction kettle was charged with beta-zinc diimine, Heptafluorobutyloxirane (HTFO), Maleic Anhydride (MA) (HTFO to MA molar ratio of 1:2), and 2mL tetrahydrofuran in sequence, with the catalyst to HTFO molar ratio of 1: 400. The reaction kettle was closed and taken out of the glove box, charged with carbonyl sulfide (COS) at room temperature in a molar ratio of COS to HTFO of 1.2:1, and placed in an oil bath at 60 ℃ for reaction for 14 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 5
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; triethylboron (TEB), dodecyltrimethylammonium bromide (DTMeAB), octafluoropentyloxy-1, 2-propylene oxide (OTFO), Maleic Anhydride (MA) (the molar ratio of OTFO to MA is 1:2), and 2mL of tetrahydrofuran are added to the reaction kettle in sequence, the molar ratio of the catalyst to OTFO being 1: 500. The reaction kettle was closed and taken out of the glove box, charged with carbonyl sulfide (COS) at a molar ratio of 1.2:1 at room temperature, and placed in an oil bath at 70 ℃ for reaction for 18 h. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 6
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; triethylboron (TEB), 1, 8-diazohetero-bis-spiro [5.4.0] undec-7-ene (DBU), nonafluoropentyl oxirane (PFPO), Maleic Anhydride (MA) (PFPO to MA molar ratio of 1:2), and 2mL tetrahydrofuran were added to the reactor in sequence, the catalyst to PFPO molar ratio being 1: 100. The reaction kettle was closed and taken out of the glove box, charged with carbonyl sulfide (COS) at a molar ratio of 1.2:1 at room temperature, and placed in an oil bath kettle at 80 ℃ for reaction for 22 h. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 7
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; triethylboron (TEB), bis (triphenylphosphine) ammonium chloride (PPNCl), perfluoro-2-methyl-2, 3-epoxypentane (TFFO), Maleic Anhydride (MA) (molar ratio of TFFO to MA is 1:2), and 2mL tetrahydrofuran were added to the reaction kettle in sequence, with the molar ratio of catalyst to TFHO being 1: 200. After the reaction kettle was closed and taken out from the glove box, Carbon Oxysulfide (COS) was charged at room temperature with a molar ratio of COS to TFFO of 1.2:1, and placed in an oil bath pan at 90 ℃ for reaction for 26 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 8
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding Triethylboron (TEB) and tetraphenylphosphonium bromide (PPh) into a reaction kettle4Br), tridecafluoroheptyl oxirane (TFHO), Maleic Anhydride (MA) (1: 2 molar ratio of TFHO to MA) and 2mL of tetrahydrofuran, the molar ratio of catalyst to TFHO being 1: 300. Seal the reaction kettleAfter closing and taking out from the glove box, Carbon Oxysulfide (COS) is filled in the glove box under the condition of room temperature, the molar ratio of the COS to the TFHO is 1.2:1, and the glove box is placed in an oil bath kettle at the temperature of 90 ℃ for reaction for 26 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 9
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding Triethylboron (TEB) and tetraphenylphosphonium chloride (PPh) into a reaction kettle4Cl), glycidyl ether hexadecyl fluorononyl ether (GHFE), Maleic Anhydride (MA) (molar ratio of GHFE to MA is 1:2) and 2mL tetrahydrofuran, the molar ratio of catalyst to GHFE is 1: 400. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the GHFE is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 100 ℃ for reaction for 30 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 10
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; the zinc-cobalt double metal cyanide complex (Zn-Co (III) DMCC), Naphthyl Glycidyl Ether (NGE), Maleic Anhydride (MA) (NGE and MA molar ratio is 1:2) and 2mL tetrahydrofuran are added into a reaction kettle in sequence, and the molar ratio of the catalyst to NGE is 1: 500. After the reaction kettle was closed and taken out from the glove box, Carbon Oxysulfide (COS) was charged at room temperature with a molar ratio of COS to NGE of 1.2:1, and the mixture was placed in an oil bath at 120 ℃ for reaction for 38 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 11
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding salicylaldehyde diimine chromium chloride complex (salen. CrCl), anthryl glycidyl ether (AnGE), Maleic Anhydride (MA) (the molar ratio of AnGE to MA is 1:2) and 2mL tetrahydrofuran into a reaction kettle, wherein the molar ratio of the catalyst to AnGE is 1: 100. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the AngE is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 30 ℃ for reaction for 42 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 12
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; salicylaldehyde diimine cobalt chloride complex (salen. CoCl), azophenyl glycidyl ether (AZGE), Maleic Anhydride (MA) (the molar ratio of AZGE to MA is 1:2) and 2mL tetrahydrofuran are sequentially added into a reaction kettle, and the molar ratio of the catalyst to the AZGE is 1: 200. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the AZGE is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 40 ℃ for reaction for 46 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 13
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; adding beta-diimine zinc, biphenyl glycidyl ether (APGE), Maleic Anhydride (MA) (the molar ratio of APGE to MA is 1:2) and 2mL of tetrahydrofuran into a reaction kettle in sequence, wherein the molar ratio of the catalyst to APGE is 1: 300. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to APGE is 1.2:1, and the reaction kettle is placed in an oil bath kettle at 50 ℃ for reaction for 50 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, drying the polymer in vacuum until the weight is constant, and carrying out hot pressing at 120 ℃ for 15min to obtain the sulfur-containing polymer.
Example 14
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; adding a zinc-cobalt double metal cyanide complex (Zn-Co (III) DMCC), trifluoro propylene oxide (TFPO), Maleic Anhydride (MA) (the molar ratio of the TFPO to the MA is 1:0.5) and 2mL tetrahydrofuran into a reaction kettle in sequence, wherein the molar ratio of the catalyst to the TFPO is 1: 100. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the TFPO is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 30 ℃ for reaction for 2 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer with 5 wt.% of cage-type Polysilsesquioxane (POSS) and 5 wt.% of polytetrafluoroethylene, and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 15
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding salicylaldehyde diimine chromium chloride complex (salen. CrCl), 3- (2,2,3, 3-tetrafluoropropoxy) -1, 2-propylene oxide (TFPP), 2, 3-difluoromaleic anhydride (DFMA) (the molar ratio of TFPP to DFMA is 1:1) and 2mL of toluene into a reaction kettle, wherein the molar ratio of the catalyst to the TFPP is 1: 200. The reaction kettle was closed and taken out of the glove box, and then charged with carbon disulfide (CS) at room temperature2)，CS2The molar ratio of the TFPP to the TFPP is 1.2:1, and the mixture is put into an oil bath kettle at the temperature of 40 ℃ for reaction for 6 hours. After the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, and then mixing ethanol/deionized waterPrecipitating the polymer in the solvent, repeatedly washing for three times, and drying in vacuum to constant weight to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 10 wt.% of silica aerogel and 10 wt.% of polyvinylidene fluoride, and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 16
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; to the reaction kettle were added successively salicylaldiminato cobalt chloride complex (salen. cocl), hexafluoropropylene oxide (TFTO), Glutaric Anhydride (GA) (molar ratio of TFTO GA 1:1.5), and 2mL cyclohexane, at a molar ratio of catalyst to TFTO 1: 300. The reaction kettle was closed and taken out from the glove box, charged with carbonyl sulfide (COS) at a molar ratio of COS to TFTO of 1.2:1 at room temperature, and placed in an oil bath pan at 50 ℃ for reaction for 10 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 15 wt.% of graphene oxide aerogel and 15 wt.% of polyimide and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 17
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; beta-zinc diimine, heptafluorobutyl oxirane (HTFO), Phthalic Anhydride (PA) (the molar ratio of HTFO to PA is 1:2) and 2ml of n-hexane are added to a reaction kettle in sequence, and the molar ratio of the catalyst to the HTFO is 1: 400. The reaction kettle was closed and taken out of the glove box, and then charged with carbon disulfide (CS) at room temperature2)，CS2The molar ratio to HTFO was 1.2:1, and the reaction was carried out in an oil bath at 60 ℃ for 14 h. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. Finally, the sulfur-containing polymer was mixed with 20 wt.% of a two-dimensional transition goldThe sulfur-containing polymer composite material can be obtained by physically blending carbon/nitride (Mxenes) aerogel and 20 wt.% of polytetrafluoroethylene and hot-pressing.
Example 18
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; triethylboron (TEB), dodecyltrimethylammonium bromide (DTMeAB), octafluoropentyloxy-1, 2-propylene oxide (OTFO), tetrafluorophthalic anhydride (TFPA) (the molar ratio of OTFO to TFPA is 1:0.5) and 2mL of N, N-dimethylformamide are added to the reaction kettle in sequence, and the molar ratio of the catalyst to OTFO is 1: 500. The reaction kettle was closed and taken out of the glove box, charged with carbonyl sulfide (COS) at a molar ratio of 1.2:1 at room temperature, and placed in an oil bath at 70 ℃ for reaction for 18 h. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 5 wt.% of cage-type Polysilsesquioxane (POSS) and 5 wt.% of polyvinylidene fluoride, and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 19
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding Triethylboron (TEB) and 1, 8-diazo heterobis-spiro [5.4.0]]Undec-7-ene (DBU), nonafluoropentylalkyloxirane (PFPO), tetrahydrophthalic anhydride (THPA) (PFPO to THPA molar ratio 1:1) and 2mL of N, N-dimethyl sulfoxide (DMSO) at a catalyst to PFPO molar ratio of 1: 100. The reaction kettle was closed and taken out of the glove box, and then charged with carbon disulfide (CS) at room temperature2)，CS2The molar ratio of PFPO to the reaction mixture was 1.2:1, and the reaction mixture was placed in an oil bath at 80 ℃ for 22 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. Finally mixing the sulfur-containing polymer with 10 wt.% silica aerogel and 10wt. -%The polyimide is physically blended and hot pressed to obtain the sulfur-containing polymer composite material.
Example 20
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; triethylboron (TEB), bis (triphenylphosphine) ammonium chloride (PPNCl), perfluoro-2-methyl-2, 3-epoxypentane (TFFO), tetrachlorophthalic anhydride (TCPA) (molar ratio of TFFO to TCPA 1:1.5) and 2mL tetrahydrofuran were added to the reactor in sequence, the molar ratio of catalyst to TFFO being 1: 200. After the reaction kettle was closed and taken out from the glove box, Carbon Oxysulfide (COS) was charged at room temperature with a molar ratio of COS to TFFO of 1.2:1, and placed in an oil bath pan at 90 ℃ for reaction for 26 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer with 15 wt.% of graphene oxide aerogel and 15 wt.% of polytetrafluoroethylene and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 21
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding Triethylboron (TEB) and tetraphenylphosphonium bromide (PPh) into a reaction kettle4Br), tridecafluoroheptyl oxirane (TFHO), trichlorophthalic anhydride (CPA) (1: 2 molar ratio of TFHO to CPA) and 2mL of toluene, 1:300 molar ratio of catalyst to TFHO. The reaction kettle was closed and taken out of the glove box, and then charged with carbon disulfide (CS) at room temperature2)，CS2The molar ratio of TFHO to TFHO is 1.2:1, and the reaction solution is put in an oil bath pan at 100 ℃ for 30 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. Finally, the sulfur-containing polymer is physically blended with 20 wt.% of two-dimensional transition metal carbon/nitride (Mxenes) aerogel and 20 wt.% of polyvinylidene fluoride, and hot pressed to obtain the final productTo sulfur-containing polymer composites.
Example 22
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding Triethylboron (TEB) and tetraphenylphosphonium chloride (PPh) into a reaction kettle4Cl), glycidyl ether hexadecafluorononyl ether (GHFE), Diethylene Glycol Anhydride (DGA) (molar ratio of GHFE to DGA is 1:0.5) and 2mL cyclohexane, the molar ratio of catalyst to GHFE being 1: 400. The reaction kettle was closed and taken out of the glove box, and then charged with carbonyl sulfide (COS) at room temperature in a molar ratio of COS to GHFE of 1.2:1, and placed in an oil bath at 110 ℃ for reaction for 34 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer with 5 wt.% of cage-type Polysilsesquioxane (POSS) and 5 wt.% of polyimide, and performing hot pressing to obtain the sulfur-containing polymer composite material.
Example 23
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding Triethylboron (TEB) and tetrabutylammonium chloride (NBu) into a reaction kettle4Cl), Naphthyl Glycidyl Ether (NGE), dehydroxyacetic anhydride (TDGA) (NGE to TDGA molar ratio 1:1) and 2mL of n-hexane, catalyst to NGE molar ratio 1: 500. The reaction kettle was closed and taken out of the glove box, and then charged with carbon disulfide (CS) at room temperature2)，CS2The molar ratio of the obtained product to NGE was 1.2:1, and the obtained product was placed in an oil bath at 120 ℃ for reaction for 38 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 10 wt.% of silica aerogel and 10 wt.% of polytetrafluoroethylene, and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 24
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; adding a zinc-cobalt double metal cyanide complex (Zn-Co (III) DMCC), anthryl glycidyl ether (AnGE), Maleic Anhydride (MA) (the molar ratio of AnGE to MA is 1:1.5) and 2mL of N, N-dimethylformamide into a reaction kettle in sequence, wherein the molar ratio of the catalyst to AnGE is 1: 100. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the AngE is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 30 ℃ for reaction for 42 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 15 wt.% of graphene oxide aerogel and 15 wt.% of polyvinylidene fluoride, and carrying out hot pressing to obtain the sulfur-containing polymer composite material.
Example 25
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; salicylaldehyde diimine chromium chloride complex (salen. CrCl), azophenyl glycidyl ether (AZGE), 2, 3-difluoromaleic anhydride (DFMA) (the molar ratio of AZGE to DFMA is 1:2) and 2mL of N, N-dimethyl sulfoxide are sequentially added into a reaction kettle, and the molar ratio of a catalyst to AZGE is 1: 200. The reaction kettle was closed and taken out of the glove box, and then charged with carbon disulfide (CS) at room temperature2)，CS2The molar ratio of the AZGE to the AZGE is 1.2:1, and the mixture is placed in an oil bath kettle at 40 ℃ for reaction for 46 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer with 20 wt.% of two-dimensional transition metal carbon/nitride (Mxenes) aerogel and 20 wt.% of polyimide, and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 26
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; salicylaldehyde diimine cobalt chloride complex (salen. CoCl), biphenyl glycidyl ether (APGE), Glutaric Anhydride (GA) (the molar ratio of APGE to GA is 1:0.5) and 2mL tetrahydrofuran are sequentially added into a reaction kettle, and the molar ratio of the catalyst to APGE is 1: 300. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to APGE is 1.2:1, and the reaction kettle is placed in an oil bath kettle at 50 ℃ for reaction for 50 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer with 5 wt.% of cage-type Polysilsesquioxane (POSS) and 5 wt.% of polytetrafluoroethylene, and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 27
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding salicylaldehyde diimine chromium chloride complex (salen. CrCl), anthryl glycidyl ether (AnGE), tridecafluoroheptyl ethylene oxide (TFHO), tetrafluorophthalic anhydride (TFPA) (the molar ratio of AnGE, TFHO and TFPA is 1:1:2) and 2mL of toluene into a reaction kettle, wherein the molar ratio of the catalyst to AnGE and TFHO is 1:400: 400. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the AngE is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 60 ℃ for reaction for 50 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 10 wt.% of silica aerogel and 10 wt.% of polyvinylidene fluoride, and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 28
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding salicylaldehyde diimine chromium chloride complex (salen. CrCl), azobenzene glycidyl ether (AZGE), tridecafluoroheptyl ethylene oxide (TFHO), tetrafluorophthalic anhydride (TFPA) (the molar ratio of AZGE, TFHO and TFPA is 1:1:2) and 2mL cyclohexane into a reaction kettle, wherein the molar ratio of the catalyst to AZGE and TFHO is 1:500: 500. And (3) sealing the reaction kettle, taking out the reaction kettle from the glove box, filling carbonyl sulfide (COS) with the molar ratio of the COS to AZGE and TFHO of 1.2:1:1 at room temperature, and placing the reaction kettle in an oil bath kettle at 70 ℃ for reaction for 50 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 10 wt.% of graphene oxide aerogel and 10 wt.% of polyimide and hot-pressing to obtain the sulfur-containing polymer composite material.
Example 29
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; sequentially adding salicylaldehyde diimine chromium chloride complex (salen. CrCl), azobenzene glycidyl ether (AZGE), tridecafluoroheptyl ethylene oxide (TFHO), tetrafluorophthalic anhydride (TFPA) (the molar ratio of AZGE, TFHO and TFPA is 1:1:2) and 2mL cyclohexane into a reaction kettle, wherein the molar ratio of the catalyst to AZGE and TFHO is 1:500: 500. And (3) sealing the reaction kettle, taking out the reaction kettle from the glove box, filling carbonyl sulfide (COS) with the molar ratio of the COS to AZGE and TFHO of 1.2:1:1 at room temperature, and placing the reaction kettle in an oil bath kettle at 70 ℃ for reaction for 50 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer and 10 wt.% of graphene oxide aerogel and carrying out hot pressing to obtain the sulfur-containing polymer composite material.
Comparative example 1
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; adding a zinc-cobalt double metal cyanide complex (Zn-Co (III) DMCC), epoxy propanol (Gly), Maleic Anhydride (MA) (the molar ratio of Gly to MA is 1:2) and 2mL of tetrahydrofuran into a reaction kettle in sequence, wherein the molar ratio of the catalyst to Gly is 1: 100. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the Gly is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 60 ℃ for reaction for 24 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer.
Comparative example 2
Before polymerization, a 10mL high-pressure reaction kettle is placed in a drying oven at 110 ℃ for 4h to remove water, and then the reaction kettle is placed in a glove box to be cooled to room temperature; adding a zinc-cobalt double metal cyanide complex (Zn-Co (III) DMCC), epoxy propanol (Gly), Maleic Anhydride (MA) (the molar ratio of Gly to MA is 1:2) and 2mL of tetrahydrofuran into a reaction kettle in sequence, wherein the molar ratio of the catalyst to Gly is 1: 100. The reaction kettle is closed and taken out from the glove box, Carbon Oxysulfide (COS) is filled in the reaction kettle at room temperature, the molar ratio of the COS to the Gly is 1.2:1, and the reaction kettle is placed in an oil bath kettle at the temperature of 60 ℃ for reaction for 24 hours. And after the reaction is finished, taking the product out of the reaction kettle, dissolving the product by using dichloromethane, precipitating the polymer in a mixed solvent of ethanol/deionized water, repeatedly washing the polymer for three times, and drying the polymer in vacuum until the weight of the polymer is constant to obtain the sulfur-containing polymer. And finally, physically blending the sulfur-containing polymer, 10 wt.% of graphene oxide aerogel and 10 wt.% of polyimide and hot-pressing to obtain the sulfur-containing polymer composite material.
And (3) performance testing:
1. the dielectric constants and dielectric losses of the sulfur-containing polymers and their materials were measured using a broadband dielectric relaxation spectrometer (type: GmbH Concept 40) from Novocontrol Technologies, Germany at a temperature of 25 ℃ and a frequency of 10-1011Hz；
2. T-measurement with Differential Scanning Calorimeter (DSC)gThe test temperature is 25-200 ℃, and the temperature rising and reducing speed is 10 ℃/min;
4. tensile strength was measured at room temperature using an Instron 2344 tensile machine, and the bars were dumbbell-shaped, 4mm wide and 50mm/min tensile rate.
The comparative data for the properties of the above examples and comparative examples are shown in table 1 below.
TABLE 1
Figure BDA0003132330060000201
Figure BDA0003132330060000211
Comparing the data in table 1, it can be seen that, with the increase of the fluorine content in the epoxy monomer, the dielectric constant and the dielectric loss of the prepared sulfur-containing polymer are both reduced obviously; compared with a single sulfur-containing polymer, the dielectric constant and the dielectric loss of the composite material prepared by adding the high-molecular additive and/or the nano porous material as the auxiliary agent are further reduced, and the heat resistance and the tensile strength are obviously improved; it is worth noting that when the content of fluorine in the adopted epoxy monomer is higher, the fluorine content and the added auxiliary agent generate a synergistic effect, so that the performance of the prepared composite material is improved more remarkably.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods.

Claims (10)

1. A low dielectric constant, low dielectric loss composite comprising a sulfur-containing polymer;
the sulfur-containing polymer is prepared by carrying out anion ring-opening copolymerization on a sulfur-containing carbon monomer, an epoxy monomer and anhydride under the action of a catalyst;
the epoxy monomer is selected from one or more of trifluoropropylene oxide, 3- (2,2,3, 3-tetrafluoropropoxy) -1, 2-propylene oxide, hexafluoropropylene oxide, heptafluorobutylethylene oxide, octafluoropentyloxy-1, 2-propylene oxide, nonafluoropentylylene oxide, perfluoro-2-methyl-2, 3-epoxypentane, tridecafluoroheptylethylene oxide, glycidyl ether, hexadecyl fluorononyl ether, naphthyl glycidyl ether, anthryl glycidyl ether, azo-phenyl glycidyl ether and biphenyl glycidyl ether.
2. The low dielectric constant, low dielectric loss composite of claim 1, wherein:
the sulfur-containing carbon-monomer is selected from carbon oxysulfide and/or carbon disulfide;
the anhydride is selected from one or more of maleic anhydride, 2, 3-difluoromaleic anhydride, glutaric anhydride, phthalic anhydride, tetrafluorophthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, trichlorophthalic anhydride, diglycolic anhydride and thiohydroxy acetic anhydride;
the catalyst is selected from one or more of zinc-cobalt double metal cyanide complex, salicylaldehyde diimine chromium chloride complex, salicylaldehyde diimine cobalt chloride complex, beta-diimine zinc, triethylboron, dodecyl trimethyl ammonium bromide, 1, 8-diazo hetero-spiro [5.4.0] undec-7-ene, bis (triphenylphosphine) ammonium chloride, tetraphenyl phosphine bromide, tetraphenyl phosphine chloride and tetrabutylammonium chloride.
3. The low dielectric constant, low dielectric loss composite of claim 1, wherein:
the molar ratio of the catalyst to the epoxy monomer and the anhydride is 1: 100-500: 150 to 1000;
the molar ratio of the epoxy monomer to the anhydride is 1:0.5 to 2;
the molar ratio of the catalyst to the sulfur-containing carbon-monomer is 1: 120-600 parts;
the temperature of the anion ring-opening copolymerization is 30-120 ℃, and the time is 2-50 h.
4. The low dielectric constant, low dielectric loss composite of claim 1 further comprising a polymeric additive and/or a nanoporous material;
the polymer additive is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride and polyimide;
the nano-porous material is selected from one or more of cage-type polysilsesquioxane, silicon dioxide aerogel, graphene oxide aerogel and two-dimensional transition metal carbon/nitride aerogel.
5. The low dielectric constant, low dielectric loss composite material of claim 4, wherein the feedstock composition comprises, in weight percent of feedstock:
60-90% of a sulfur-containing polymer;
5-20% of a polymer additive;
5-20% of the nano porous material.
6. A composite material with a low dielectric constant and low dielectric loss according to any one of claims 1 to 5, wherein the epoxy monomer is selected from one or more of hexafluoropropylene oxide, heptafluorobutyloxirane, octafluoropentyloxy-1, 2-propylene oxide, nonafluoropentylalkyloxirane, perfluoro-2-methyl-2, 3-epoxypentane, tridecafluoroheptylethylene oxide, glycidyl ether, hexadecyl fluorononyl ether, naphthyl glycidyl ether, anthryl glycidyl ether, azo-phenyl glycidyl ether and biphenyl glycidyl ether.
7. A composite material with low dielectric constant and low dielectric loss according to claim 6, wherein the epoxy monomer is selected from one or more of tridecafluoroheptyl oxirane, glycidyl ether hexadecafluorononyl ether, azophenyl glycidyl ether, biphenyl glycidyl ether.
8. A method for preparing a composite material with low dielectric constant and low dielectric loss according to any one of claims 1 to 7, comprising:
(1) blending a sulfur-carbon-containing monomer, an epoxy monomer, acid anhydride, a catalyst and an optionally added solvent, carrying out anion ring-opening polymerization, and carrying out post-treatment to obtain a sulfur-containing polymer;
(2) and (2) blending the sulfur-containing polymer prepared in the step (1), the selectively added high molecular additive and the selectively added nano porous material, and performing hot pressing to obtain the composite material with low dielectric constant and low dielectric loss.
9. The method for preparing a composite material with low dielectric constant and low dielectric loss according to claim 8, wherein in the step (1):
the solvent which can be selectively added is one or more selected from tetrahydrofuran, toluene, cyclohexane, N-hexane, N-dimethylformamide and N, N-dimethyl sulfoxide;
the post-treatment comprises dissolving, settling and drying treatment.
10. The use of the composite material with low dielectric constant and low dielectric loss as defined in any one of claims 1 to 7 for preparing 5G mobile phone antenna material.
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