CN113461910B - Polyethylidene norbornene divinyl biphenyl copolymer and preparation method thereof - Google Patents
Polyethylidene norbornene divinyl biphenyl copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer organic synthesis, and discloses a poly (ethylidene norbornene) divinyl biphenyl copolymer and a preparation method thereof. The prepared poly (ethylidene norbornene) divinyl biphenyl copolymer product does not contain chloride ions, potassium ions and the like, can effectively react with organic groups, and has the characteristics of excellent thermal stability, oil resistance, corrosion resistance, high-energy ray particle resistance and the like; the performance optimization of carbon element materials such as graphene, carbon nanotubes, carbon fibers and the like can be realized; the heat resistance, weather resistance, mechanical strength and the like of the traditional high polymer material can be greatly improved; the prepared poly (ethylidene norbornene) divinyl biphenyl copolymer adhesive, coating, printing ink and the like have the excellent performances of super-strong binding power, heat resistance, mechanical property, high strength, high toughness, high air tightness, low dielectric, high insulation and the like.
Description
Technical Field
The invention relates to a preparation method of a poly (ethylidene) norbornene divinyl biphenyl copolymer, in particular to a preparation method of a vinyl-containing poly (norbornene) biphenyl copolymer, belonging to the technical field of high-molecular organic synthesis.
Background
The poly (ethylidene norbornene) is an important poly (norbornene) high polymer material, and is an organic polymer containing a plurality of chemically reactive vinyl groups in the poly (norbornene) molecule. Due to the particularity of the molecular structure, the oil-resistant and heat-resistant rubber has unique properties such as excellent oil resistance, high temperature resistance and mechanical strength, and can react with various substances. After the ethylidene norbornene and the second monomer are copolymerized, the comprehensive performance of the product can be further improved, so that the product requirements under special conditions are met.
The main chain of the vinyl polynorbornene is a typical carbon chain structure, the side group is surrounded by a bio-based ethylene group, and the vinyl has a reaction crosslinking effect and can be compatible with other vinyl monomer reaction systems such as divinyl biphenyl and the like. The poly (ethylidene norbornene) divinyl biphenyl copolymer thermosetting resin has the advantages of high thermal stability, outstanding mechanical strength, high hardness, high strength, high toughness, high insulation, high air tightness, high weather resistance, high transparency and the like, especially has outstanding performances of water vapor resistance, salt mist resistance, ultraviolet resistance, high-energy ray resistance and the like, and does not contain chloride ions, sodium ions and the like. The raw material sources widely comprise petroleum-based monomers and bio-based monomers, and the raw material is low in price and environment-friendly. The application forms of the product comprise coatings, adhesives, printing ink, rubber, plastics, composite materials and the like, so the development and research of the poly (ethylidene norbornene) divinyl biphenyl copolymer have great market value.
The copolymerization and reaction of ethylidene norbornene and divinyl biphenyl face many challenges, and are highlighted by large difference of reactivity ratios of two monomers, non-uniform catalytic polymerization reaction system and easy poisoning of catalyst by functional groups. Wherein free electron pairs (particularly nitrogen atoms and oxygen atoms) on the functional substituent of the ethylidene norbornene can deactivate the catalyst through the complexation with an active catalytic center, so that the activity of the catalyst is reduced, the polymerization is inhibited, and the traditional polymerization method is difficult to realize the high-efficiency copolymerization of the ethylidene norbornene and the divinyl biphenyl. In addition, relatively high catalyst loadings (based on rhodium, platinum metal content) can increase the rate of polymerization, but can result in polymer products having too high a level of residual metals that are difficult and expensive to remove. When polymerized in the presence of transition metal catalysts, the exo-isomers of functionalized norbornenes are polymerized at much higher rates than the corresponding endo-isomers produce polymer yields, which also increases the difficulty of polymerization between norbornene monomers and divinylbiphenyl. In fact, to the best of the inventors' knowledge, there is currently no efficient process that can achieve homopolymerization of higher levels of endo-functional norbornene with other vinyl monomers.
Disclosure of Invention
Aiming at the huge application prospect of the poly (ethylidene norbornene) copolymer and the defects of the prior art, the invention reports the poly (ethylidene norbornene) divinyl biphenyl copolymer and the preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a copolymer of polyethyl-methylene norbornene divinyl biphenyl has a structure shown in formula I:
wherein R is vinyl, epoxy or acrylic, m is the number of repeating units of ethylidene norbornene, and m is 20-100; n is the number of repeating units of divinyl biphenyl, and the value of n is 20-100.
Further, the structural unit of the above copolymer is characterized by a combination of a structure in which m is 50 to 100 for ethylidene norbornene and n is 80 to 100 for divinylbiphenyl repeating unit.
(1) When R is vinyl, the first preparation method of the poly (ethylidene norbornene) divinyl biphenyl copolymer provided by the invention comprises the following steps:
(A1) the compound I
Compound II
Mixing palladium tetrakis (triphenylphosphine) and a toluene solution, and carrying out metathesis polymerization reaction to obtain a first intermediate;
(A2) mixing a compound 4,4' -divinyl biphenyl, potassium carbonate, methyl iodide and an N, N-dimethylformamide solution, and carrying out a polymerization reaction to obtain a second intermediate;
(A3) mixing the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and anhydrous dichloromethane, and carrying out polymerization reaction to obtain a poly (ethylidene norbornene) divinyl biphenyl copolymer;
wherein the content of the first and second substances,
in step A1, the dosage ratio of the compound I, the compound II, the palladium tetrakis (triphenylphosphine) and the toluene is 1-1.5 mol: 0.2-0.5 mmol: 0.1-0.2 g: 30-40 mL; the temperature of the metathesis polymerization reaction is 70-80 ℃, and the time is 12-24 h;
in step A2, the compound 4,4' -divinylbiphenyl and methyl iodide are used in a ratio of 50-100 mL: 1.5-2.5 mL; the using amount of the potassium carbonate is 0.3-0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-12 h;
in step a3, the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid (TFA) and toluene were used in a ratio of 20 to 60 g: 20-50 g: 140-200 μ L: 200-300 mg: 1-1.5 mL: 300-500 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 48-72 h;
preferably, the first and second liquid crystal materials are,
in step A1, the dosage ratio of the compound I, the compound II, the palladium tetrakis (triphenylphosphine) and the toluene is 1.5 mol: 0.3 mmol: 0.15 g: 40 mL;
in step A2, the ratio of the amount of the compound 4,4' -divinylbiphenyl to the amount of methyl iodide is 100 mL: 2.5 mL; the using amount of the potassium carbonate is 0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL;
in step a3, the amount ratio of the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and toluene was 50 g: 40 g: 200 μ L: 200 mg: 1.5 mL: 300 mL; the time is preferably 72 hours.
(2) When R is an epoxy group, the second preparation method of the poly (ethylidene norbornene) divinyl biphenyl copolymer provided by the invention comprises the following steps:
(B1) the compound I
Compound II
Mixing palladium tetrakis (triphenylphosphine) and a toluene solution, and carrying out metathesis polymerization reaction to obtain a first intermediate;
(B2) mixing a compound 4,4' -divinyl biphenyl, potassium carbonate, methyl iodide and an N, N-dimethylformamide solution, and carrying out a polymerization reaction to obtain a second intermediate;
(B3) mixing the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and anhydrous dichloromethane, and carrying out polymerization reaction to obtain a vinyl poly (ethylidene norbornene) divinyl biphenyl copolymer;
(B4) carrying out epoxidation reaction on the vinyl poly ethylidene norbornene divinyl biphenyl copolymer, acetic acid, formic acid, hydrogen peroxide and dichloromethane to obtain an epoxy group poly ethylidene norbornene divinyl biphenyl copolymer;
wherein the content of the first and second substances,
in step B1, the dosage ratio of the compound I, the compound II, the palladium tetrakis (triphenylphosphine) and the toluene is 1-1.5 mol: 0.2-0.5 mmol: 0.1-0.2 g: 30-40 mL; the temperature of the metathesis polymerization reaction is 70-80 ℃, and the time is 12-24 h;
in step B2, the compound 4,4' -divinylbiphenyl and methyl iodide are used in a ratio of 50-100 mL: 1.5-2.5 mL; the dosage of the potassium carbonate is 0.3-0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-12 h;
in the step B3, the dosage ratio of the first intermediate to the second intermediate to the p-tert-butylphenol, the tungsten chloride, the trifluoroacetic acid and the toluene is 20-60 g: 20-50 g: 140-200 μ L: 200-300 mg: 1-1.5 mL: 300-500 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 48-72 h;
in the step B4, the dosage ratio of the vinyl poly (ethylidene) norbornene divinyl biphenyl copolymer to the acetic acid to the formic acid to the hydrogen peroxide to the dichloromethane is 50 g: 0.1-0.2 mL: 0.15-0.3mL, 450-550 mL: 300-500 mL; the reaction temperature is 0 ℃, and the reaction time is 48-72 hours;
preferably, the first and second liquid crystal materials are,
in step B1, the dosage ratio of the compound I, the compound II, the palladium tetrakis (triphenylphosphine) and the toluene is 1.5 mol: 0.3 mmol: 0.15 g: 40 mL;
in step B2, the compound 4,4' -divinylbiphenyl and methyl iodide were used in a ratio of 100 mL: 2.5 mL; the using amount of the potassium carbonate is 0.5 mmol; the dosage of N, N-dimethylformamide is 200 mL;
in step B3, the amount ratio of the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and toluene was 50 g: 40 g: 200 μ L: 200 mg: 1.5 mL: 300 mL; the time is preferably 72 hours.
In the step B4, the dosage ratio of the vinyl poly (ethylidene norbornene) divinyl biphenyl copolymer to the acetic acid to the formic acid to the hydrogen peroxide to the dichloromethane is 50 g: 0.15 mL: 0.15mL, 550 mL: 500 mL; the time is preferably 72 hours;
(3) when R is an acrylic group, the third preparation method of the poly (ethylidene norbornene) divinyl biphenyl copolymer provided by the invention comprises the following steps:
(C1) the compound I
Acrylic acid and p-diphenol are mixed for Diels-Alder reaction to obtainTo a first intermediate;
(C2) the first intermediate and the compound II
Mixing the palladium tetrakis (triphenylphosphine) and a toluene solution, and carrying out metathesis polymerization reaction to obtain a second intermediate;
(C3) mixing a compound 4,4' -divinyl biphenyl, potassium carbonate, methyl iodide and an N, N-dimethylformamide solution, and carrying out a polymerization reaction to obtain a third intermediate;
(C4) mixing the second intermediate, the third intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and anhydrous dichloromethane, and carrying out polymerization reaction to obtain a polyacrylic acid ethylidene norbornene divinyl biphenyl copolymer;
wherein the content of the first and second substances,
in the step C1, the dosage ratio of the compound I, the acrylic acid and the p-diphenol is 2-3 mol: 2-3 mol: 1.0-1.5 mmol; the reaction temperature is 150 ℃, and the reaction time is 10-24 h;
in the step C2, the dosage ratio of the first intermediate, the compound II, the tetrakis (triphenylphosphine) palladium and the toluene is 1-1.5 mol: 0.2-0.5 mmol: 0.1-0.2 g: 30-40 mL; the temperature of the metathesis polymerization reaction is 70-80 ℃, and the time is 12-24 h;
in step C3, the compound 4,4' -divinylbiphenyl and methyl iodide are used in a ratio of 50-100 mL: 1.5-2.5 mL; the dosage of the potassium carbonate is 0.3-0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-12 h;
in the step C4, the dosage ratio of the second intermediate to the third intermediate to the p-tert-butylphenol, the tungsten chloride to the trifluoroacetic acid to the dichloromethane is 250-300 mg: 200-450 mg: 140-200 μ L: 200-300 mg: 1-1.5 mL: 100-150 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 48-72 hours;
preferably, the first and second liquid crystal materials are,
in the step C1, the dosage ratio of the compound I, the acrylic acid and the p-diphenol is 2 mol: 3 mol: 1.5 mmol; the time is preferably 16 hours;
in step C2, the first intermediate, compound II, tetrakis (triphenylphosphine) palladium, and toluene were used in a ratio of 1.5 mmol: 1.8 mmol: 0.15 g: 40 mL;
in step C3, the compound 4,4' -divinylbiphenyl and methyl iodide were used in a ratio of 1 mL: 2.5 mL; the using amount of the potassium carbonate is 0.5 mmol; the dosage of the N, N-dimethylformamide is 20 mL;
in the step C4, the using ratio of the second intermediate to the third intermediate to the p-tert-butylphenol, tungsten chloride, trifluoroacetic acid to dichloromethane was 50 g: 40 g: 200 μ L: 200 mg: 1.5 mL: 300 mL; the time is preferably 72 hours.
The copolymer of the polyethyl-methylene norbornene divinyl biphenyl prepared by the invention comprises the following components:
the application of the prepared poly (ethylidene norbornene) divinyl biphenyl copolymer in preparing adhesives or coatings.
The invention has the following beneficial effects:
1. the prepared poly (ethylidene norbornene) divinyl biphenyl copolymer product can effectively react with organic groups, and has the characteristics of excellent thermal stability, oil resistance, corrosion resistance, high-energy ray particle resistance and the like.
2. The prepared poly (ethylidene norbornene) divinyl biphenyl copolymer product does not contain chloride ions, potassium ions and the like.
3. The prepared poly (ethylidene norbornene) divinyl biphenyl copolymer adhesive, coating, ink and the like have the excellent performances of super-strong binding power, heat resistance, mechanical property, high strength, high toughness, high air tightness, low dielectric, high insulation and the like.
4. The prepared poly (ethylidene norbornene) divinyl biphenyl copolymer can realize the optimization of the performance of carbon element materials, such as graphene, carbon nanotubes, carbon fibers and the like.
5. The prepared poly (ethylidene norbornene) divinyl biphenyl copolymer can greatly improve the heat resistance, weather resistance, mechanical strength and the like of the traditional high polymer material.
6. The preparation method is simple, the raw material sources are rich, and the preparation cost is low.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, unless otherwise specified, the starting materials for the preparation are commercially available or prepared by methods well known to those skilled in the art.
Example 1
A preparation method of vinyl poly ethylidene norbornene divinyl biphenyl comprises the following steps:
(1) synthesis of first intermediate poly (ethylidene norbornene) oligomer:
ethylidene norbornene (180g, 1.5mol), Grubbs' catalyst (0.25g, 0.3mmol), tetrakis (triphenylphosphine) palladium (0.15g, 0.13mmol) and 40mL of toluene solvent were mixed well and reacted at 70 ℃ for 24 hours. The crude product was purified using silica gel column chromatography eluting with dichloromethane/n-hexane (2: 1). 171g of a transparent liquid was obtained as a vinyl norbornene oligomer in a yield of 95%;
(2) and (3) synthesizing a second intermediate poly-divinyl-biphenyl oligomer:
4,4' -Divinylbiphenyl (100mL, 100g), methyl iodide (2.5mL, 5.7g), and potassium carbonate (0.5mmol, 70mg) were uniformly mixed with 200mL of N, N-dimethylformamide and reacted at 70 ℃ for 12 hours. The crude product was purified using a column chromatography on silica gel eluting with dichloromethane/acetone (2: 1). Obtaining 87g of light yellow transparent liquid which is polydivinylbiphenyl oligomer with the yield of 87%;
(3) synthesis of poly (ethylidene) norbornene divinyl biphenyl copolymer
Polyethylidene norbornene oligomer (50g), polydivinylbiphenyl oligomer (40g), p-tert-butylphenol (200. mu.L, 0.18g), tungsten chloride (200mg), trifluoroacetic acid (1.5mL) and toluene (300mL) were uniformly and gently reacted at 70 ℃ for 72 hours; a tan viscous solution was obtained. The product was isolated using 4L of methanol to give a white solid as 54g of vinyl polyethylenimine norbornene divinyl biphenyl copolymer in 60% yield.
The specific process is shown in the following figure:
according to the NMR spectra of the product obtained in this example, the product obtained in this example was a poly (ethylidene norbornene) divinyl biphenyl copolymer.
The product prepared in this example was heated to 180 ℃ to crosslink into a resin, and a weight loss at 300 ℃ was determined by a thermal weight loss Test (TGA), indicating that the copolymer prepared in this invention has excellent thermal stability.
Example 2
A preparation method of epoxy group poly ethylidene norbornene divinyl biphenyl comprises the following steps:
(1) synthesis of first intermediate poly (ethylidene norbornene) oligomer:
ethylidene norbornene (180g, 1.5mol), Grubbs' catalyst (0.25g, 0.3mmol), tetrakis (triphenylphosphine) palladium (0.15g, 0.13mmol) and 40mL of toluene solvent were mixed well and reacted at 70 ℃ for 24 hours. The crude product was purified using silica gel column chromatography eluting with dichloromethane/n-hexane (2: 1). 171g of a transparent liquid was obtained as a vinyl norbornene oligomer in a yield of 95%;
(2) and (3) synthesizing a second intermediate polydivinylbiphenyl oligomer:
4,4' -Divinylbiphenyl (100mL, 100g), methyl iodide (2.5mL, 5.7g), and potassium carbonate (0.5mmol, 70mg) were uniformly mixed with 200mL of N, N-dimethylformamide and reacted at 70 ℃ for 12 hours. The crude product was purified using a column chromatography on silica gel eluting with dichloromethane/acetone (2: 1). Obtaining 87g of light yellow transparent liquid which is polydivinylbiphenyl oligomer with the yield of 87%;
(3) synthesis of Polyethylidene norbornene Divinylbiphenyl copolymer:
polyethylidene norbornene oligomer (50g), polydivinylbiphenyl oligomer (40g), p-tert-butylphenol (200. mu.L, 0.18g), tungsten chloride (200mg), trifluoroacetic acid (1.5mL) and toluene (300mL) were allowed to react at 70 ℃ for 72 hours while being moderated and homogenized; a tan viscous solution was obtained. The product was isolated using 4L of methanol to yield 54g of a white solid in 60% yield as a copolymer of vinyl polyethylidene norbornene divinyl biphenyl.
(4) Synthesis of epoxy group polyethyl methylene norbornene divinyl biphenyl copolymer:
vinyl poly (ethylidene) norbornene divinyl biphenyl copolymer (50g), acetic acid (0.15mL), formic acid (0.15mL), dichloromethane (500mL) and hydrogen peroxide (550mL) were mixed uniformly and reacted in an ice water bath (0 ℃ C.) for 72 hours to obtain a pale yellow liquid. The product was isolated using 3L of acetone to give 40g of a white solid in 80% yield as epoxy polyethylenimine norbornene divinyl biphenyl copolymer.
The specific process is shown in the following figure:
according to the NMR spectra of the product obtained in this example, the product obtained in this example was an epoxy-based poly (ethylidene norbornene) divinyl biphenyl copolymer.
The product (10g) prepared in this example was mixed with isophorone diamine (3.1g), heated to 190 ℃ to crosslink into a resin, and subjected to a thermal weight loss reduction Test (TGA) to begin weight loss at 330 ℃, which indicates that the copolymer prepared in the present invention has excellent thermal stability.
Example 3
A preparation method of epoxy group poly ethylidene norbornene divinyl biphenyl comprises the following steps:
(1) synthesis of acrylic norbornene monomer:
ethylidene norbornene (2mol, 240g), acrylic acid (3mol, 216g) and p-diphenol (1.5mmol, 0.165g) were mixed well and reacted at 150 ℃ for 24 hours. Distillation under reduced pressure gave 433g of a liquid product, acrylic norbornene monomer, in a yield of 95%.
(2) Synthesis of first intermediate poly (ethylidene norbornene) oligomer:
acrylic norbornene monomer (180g), Grubbs' catalyst (0.25g, 0.3mmol), tetrakis (triphenylphosphine) palladium (0.15g, 0.13mmol) and 40mL of toluene solvent were mixed well and reacted at 70 ℃ for 24 hours. The crude product was purified using silica gel column chromatography eluting with dichloromethane/n-hexane (2: 1). 153g of a transparent liquid was obtained as an acrylic norbornene oligomer in a yield of 85%.
(3) And (3) synthesizing a second intermediate poly-divinyl-biphenyl oligomer:
4,4' -Divinylbiphenyl (100mL, 100g), methyl iodide (2.5mL, 5.7g), potassium carbonate (0.5mmol, 70mg) and 200mL of N, N-dimethylformamide were mixed well and reacted at 70 ℃ for 12 hours. The crude product was purified using a column chromatography on silica gel eluting with dichloromethane/acetone (2: 1). 87g of a pale yellow transparent liquid was obtained as polydivinylbiphenyl oligomer with a yield of 87%.
(4) Synthesis of Polyethylidene norbornene Divinylbiphenyl copolymer:
acrylic acid poly (ethylidene norbornene) oligomer (50g), poly (divinyl biphenyl) oligomer (40g), p-tert-butylphenol (200. mu.L, 0.18g), tungsten chloride (200mg), trifluoroacetic acid (1.5mL) and toluene (300mL) were uniformly and gently mixed, and reacted at 70 ℃ for 72 hours; a tan viscous solution was obtained. The product was isolated using 4L of methanol to give 50g of acrylic poly (ethylidene norbornene) divinyl biphenyl copolymer as a white solid in 55% yield.
The specific process is as follows:
according to the NMR spectrum of the product obtained in this example, the product obtained in this example was a poly (ethylidene) acrylate, norbornene, divinyl biphenyl copolymer.
The product (10g) obtained in this example was mixed with glycerol diglycidyl ether (4g), heated to 150 ℃ to crosslink into a resin, and subjected to a thermal weight loss Test (TGA) to begin weight loss at 320 ℃, which indicates that the copolymer obtained in the present invention has excellent thermal stability.
The synthesis process of the poly (ethylidene norbornene) divinyl biphenyl copolymer provided by the invention has the advantages of simple synthesis method, low cost, simple equipment, low investment and the like, and has wide application prospect.
From the above embodiments, a poly (ethylidene norbornene) divinyl biphenyl copolymer, a preparation method thereof, a carbon material-supported triphenylamine cobalt porphyrin dye composite catalyst, a preparation method and an application thereof are disclosed.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A copolymer of polyethyl-norbornene divinyl biphenyl having the structure:
wherein m is the number of the repeating units of the ethylidene norbornene, and the value of m is 20-100; n is the number of repeating units of divinyl biphenyl, and the value of n is 20-100.
2. The poly (ethylidene norbornene) divinyl biphenyl based copolymer of claim 1, wherein the number of ethylidene norbornene repeating units, m, ranges from 50 to 100 and the number of divinyl biphenyl repeating units, n, ranges from 80 to 100 in combination.
3. The method for preparing the polyethyl-norbornene-divinylbenzene copolymer as claimed in claim 1, wherein the steps are as follows:
(A1) the compound I
Compound II
Mixing palladium tetrakis (triphenylphosphine) and a toluene solution, and carrying out metathesis polymerization reaction to obtain a first intermediate;
(A2) mixing a compound 4,4' -divinyl biphenyl, potassium carbonate, methyl iodide and an N, N-dimethylformamide solution, and carrying out a polymerization reaction to obtain a second intermediate;
(A3) and mixing the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and anhydrous dichloromethane, and carrying out polymerization reaction to obtain the poly (ethylidene norbornene) divinyl biphenyl copolymer.
4. The method according to claim 3,
in step A1, the dosage ratio of the compound I, the compound II, the palladium tetrakis (triphenylphosphine) and the toluene is 1-1.5 mol: 0.2-0.5 mmol: 0.1-0.2 g: 30-40 mL; the temperature of the metathesis polymerization reaction is 70-80 ℃, and the time is 12-24 h;
in step A2, the compound 4,4' -divinylbiphenyl and methyl iodide are used in a ratio of 50-100 mL: 1.5-2.5 mL; the dosage of the potassium carbonate is 0.3-0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-12 h;
in step a3, the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid (TFA) and toluene were used in a ratio of 20 to 60 g: 20-50 g: 140-200 μ L: 200-300 mg: 1-1.5 mL: 300-500 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 48-72 h.
5. The method according to claim 4,
in step A1, the dosage ratio of the compound I, the compound II, the palladium tetrakis (triphenylphosphine) and the toluene is 1.5 mol: 0.3 mmol: 0.15 g: 40 mL;
in step A2, the ratio of the amount of the compound 4,4' -divinylbiphenyl to the amount of methyl iodide is 100 mL: 2.5 mL; the using amount of the potassium carbonate is 0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL;
in step a3, the amount ratio of the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and toluene was 50 g: 40 g: 200 μ L: 200 mg: 1.5 mL: 300 mL; the time period required was 72 hours.
6. The method for preparing the poly (ethylidene norbornene) divinylbenzene-based copolymer according to claim 1, comprising the steps of:
(B1) the compound I
Compound II
Mixing palladium tetrakis (triphenylphosphine) and a toluene solution, and carrying out metathesis polymerization reaction to obtain a first intermediate;
(B2) mixing a compound 4,4' -divinyl biphenyl, potassium carbonate, methyl iodide and an N, N-dimethylformamide solution, and carrying out a polymerization reaction to obtain a second intermediate;
(B3) mixing the first intermediate, the second intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and anhydrous dichloromethane, and carrying out polymerization reaction to obtain a vinyl poly (ethylidene norbornene) divinyl biphenyl copolymer;
(B4) and carrying out epoxidation reaction on the vinyl poly ethylidene norbornene divinyl biphenyl copolymer, acetic acid, formic acid, hydrogen peroxide and dichloromethane to obtain the epoxy poly ethylidene norbornene divinyl biphenyl copolymer.
7. The method according to claim 6,
in step B1, the dosage ratio of the compound I, the compound II, the palladium tetrakis (triphenylphosphine) and the toluene is 1-1.5 mol: 0.2-0.5 mmol: 0.1-0.2 g: 30-40 mL; the temperature of the metathesis polymerization reaction is 70-80 ℃, and the time is 12-24 h;
in step B2, the compound 4,4' -divinylbiphenyl and methyl iodide are used in a ratio of 50-100 mL: 1.5-2.5 mL; the dosage of the potassium carbonate is 0.3-0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-12 h;
in the step B3, the dosage ratio of the first intermediate to the second intermediate to the p-tert-butylphenol, the tungsten chloride, the trifluoroacetic acid and the toluene is 20-60 g: 20-50 g: 140-200 μ L: 200-300 mg: 1-1.5 mL: 300-500 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 48-72 h;
in the step B4, the dosage ratio of the vinyl poly (ethylidene norbornene) divinyl biphenyl copolymer to the acetic acid to the formic acid to the hydrogen peroxide to the dichloromethane is 50 g: 0.1-0.2 mL: 0.15-0.3mL, 450-550 mL: 300-500 mL; the reaction temperature is 0 ℃, and the reaction time is 48-72 hours.
8. The method of claim 1, wherein the copolymer is prepared by the method comprising the steps of,
(C1) the compound I
Mixing acrylic acid and p-diphenol to perform Diels-Alder reaction to obtain a first intermediate;
(C2) the first intermediate and the compound II
Mixing the palladium tetrakis (triphenylphosphine) and a toluene solution, and carrying out metathesis polymerization reaction to obtain a second intermediate;
(C3) mixing a compound 4,4' -divinyl biphenyl, potassium carbonate, methyl iodide and an N, N-dimethylformamide solution, and carrying out a polymerization reaction to obtain a third intermediate;
(C4) and mixing the second intermediate, the third intermediate, p-tert-butylphenol, tungsten chloride, trifluoroacetic acid and anhydrous dichloromethane, and carrying out polymerization reaction to obtain the polyacrylic acid ethylidene norbornene divinyl biphenyl copolymer.
9. The method according to claim 8,
in the step C1, the dosage ratio of the compound I, the acrylic acid and the p-diphenol is 2-3 mol: 2-3 mol: 1.0-1.5 mmol; the reaction temperature is 150 ℃, and the reaction time is 10-24 h;
in the step C2, the dosage ratio of the first intermediate, the compound II, the tetrakis (triphenylphosphine) palladium and the toluene is 1-1.5 mol: 0.2-0.5 mmol: 0.1-0.2 g: 30-40 mL; the temperature of the metathesis polymerization reaction is 70-80 ℃, and the time is 12-24 h;
in step C3, the compound 4,4' -divinylbiphenyl and methyl iodide are used in a ratio of 50-100 mL: 1.5-2.5 mL; the dosage of the potassium carbonate is 0.3-0.5 mmol; the dosage of the N, N-dimethylformamide is 200 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 8-12 h;
in the step C4, the dosage ratio of the second intermediate to the third intermediate to the p-tert-butylphenol, the tungsten chloride to the trifluoroacetic acid to the dichloromethane is 250-300 mg: 200-450 mg: 140-200 μ L: 200-300 mg: 1-1.5 mL: 100-150 mL; the temperature of the polymerization reaction is 70-80 ℃, and the time is 48-72 hours.
10. Use of the copolymers of the type polyethylenimine norbornene divinyl biphenyl of claim 1 for the preparation of adhesives or coatings.
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