CN115010613A - Allyl-containing diamine monomer, crosslinkable polyetherimide polymer, crosslinked polyetherimide film and preparation method thereof - Google Patents

Allyl-containing diamine monomer, crosslinkable polyetherimide polymer, crosslinked polyetherimide film and preparation method thereof Download PDF

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CN115010613A
CN115010613A CN202210817709.5A CN202210817709A CN115010613A CN 115010613 A CN115010613 A CN 115010613A CN 202210817709 A CN202210817709 A CN 202210817709A CN 115010613 A CN115010613 A CN 115010613A
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allyl
polyetherimide
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何钦政
代岩
贺高红
阮雪华
郭明钢
米盼盼
付佳辉
崔福军
潘伟民
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Panjin Institute of Industrial Technology Dalian University of Technology DUT
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Abstract

The invention provides an allyl-containing diamine monomer, a crosslinkable polyetherimide polymer, a crosslinked polyetherimide film and a preparation method thereof. The allyl-containing diamine monomer has the side group containing diallyl group and can be prepared by only one step; the allyl-containing cross-linkable polyetherimide polymer prepared by the method has the advantages of large molecular weight and narrow molecular weight distribution, and the preparation method has the advantages of short preparation period, high equipment utilization rate, uniform product molecular weight and lower cost; the allyl-containing crosslinkable polyetherimide film has the excellent comprehensive properties of no color, high transparency, high mechanical strength, good thermal stability and the like, and the preparation method has the advantages of mild and rapid crosslinking reaction, easily obtained reaction reagents, low cost and various crosslinking modes.

Description

Allyl-containing diamine monomer, crosslinkable polyetherimide polymer, crosslinked polyetherimide film and preparation method thereof
Technical Field
The invention relates to a high molecular material technology, in particular to an allyl-containing diamine monomer, a crosslinkable polyetherimide polymer, a crosslinked polyetherimide film and a preparation method thereof.
Background
Polyimide is a high-performance engineering material with excellent performance, has excellent high-temperature resistance, mechanical property, radiation resistance, dielectric property, solvent resistance and the like, and is widely applied to the fields of spaceflight, military affairs, electronics and the like. However, due to the conjugated semi-trapezoidal molecular chain structure composed of aromatic heterocycles in most polyimide molecules, the molecular chain of the polyimide is high in rigidity and difficult to rotate, so that the polyimide has poor solubility in an organic solvent, and is not melted or softened under thermal processing, and the application range of the polyimide is limited. Therefore, reducing the rigidity and improving the solubility and processability while maintaining its excellent heat resistance has been a hot spot of research on high-performance polyimides.
The introduction of cross-linkable groups is an effective method for improving the processability of polyimide, and the cross-linking groups do not react before forming and processing, and the cross-linking reaction is initiated during forming and processing or after forming to form an insoluble and infusible three-dimensional polymer network. Thus, the excellent solubility and processability of the polyimide are ensured, and the polyimide has more excellent thermal property after being formed.
There are two main ways to introduce crosslinking groups in polyimides, one is to introduce groups such as maleic anhydride, norbornene or alkynyl end-capping groups at the end of the polymer chain. The resin after crosslinking is brittle with polyimide terminated with maleic anhydride; the polyimide terminated by norbornene anhydride is crosslinked to form an aliphatic chain structure, the thermal stability is reduced to a certain extent, and the alkynyl terminated group is crosslinked to form a benzene ring, so that the defects of the two groups are overcome. The other is the introduction of side groups, such as carboxyl, bromine, etc., into the polymer chain. The carboxyl is used as a crosslinking group, a third micromolecule dihydric alcohol or diamine is required to be added as a crosslinking agent, and because the crosslinking reaction occurs in the formed resin, the condition of incomplete crosslinking can occur, and even the product performance is influenced by the defects of bubbles and the like; when bromine is used as a crosslinking group, the temperature is increased to more than 350 ℃ for debromination and crosslinking, the resin color is dark, and the conditions are harsh.
Disclosure of Invention
The invention aims to solve the problems of difficult crosslinking reaction, high cost, easy generation of defects and the like of the existing polyimide crosslinkable group, provides a diamine monomer with allyl groups on side groups and a crosslinkable polyetherimide polymer thereof, and controls the crosslinking degree of resin by adjusting the proportion of the allyl monomer.
In order to realize the purpose, the invention adopts the technical scheme that: an allyl-containing diamine monomer having pendant diallyl groups, the structural formula of which is as follows:
Figure BDA0003742996510000021
IUPAC is named 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl.
The invention also discloses a preparation method of the diamine monomer containing allyl, which comprises the following steps:
(1) taking 4,4 '-biphenol as a raw material, respectively adding a solvent, an alkali catalyst and a water-carrying agent, heating until the water-carrying agent is boiled, carrying out water until no water beads are generated in a water separator, evaporating the water-carrying agent, cooling the system to room temperature, adding 3-bromopropylene, heating to 80-100 ℃, reacting for 10-24 hours, pouring into deionized water, and filtering to obtain 4,4' -bis (4-allyloxy) biphenyl;
Figure BDA0003742996510000022
(2) pouring 4,4' -bis (4-allyloxy) biphenyl into a reaction container, introducing nitrogen for protection, stirring and heating to 180 ℃ and 200 ℃, melting the solid after the solid reaches a melting point, reacting for 0.5-2h, and obtaining 3,3' -diallyl-4, 4' -biphenyl diphenol after rearrangement;
Figure BDA0003742996510000031
(3) taking 3,3 '-diallyl-4, 4' -biphenol and 4-chloronitrobenzene as raw materials, adding a solvent, an alkali catalyst and a water-carrying agent, carrying out water carrying at the temperature of 120-150 ℃ for 1-5h, evaporating the water-carrying agent, heating to the temperature of 140-160 ℃ for reaction for 4-8h, pouring into deionized water for washing, and filtering to obtain 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl;
Figure BDA0003742996510000032
(4) adding 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl, a solvent and a catalyst into a reaction vessel, heating to 60-100 ℃, slowly dripping hydrazine hydrate, continuously reacting for 2-4h after dripping, cooling to room temperature, pouring into deionized water, filtering and drying to obtain the 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl.
Figure BDA0003742996510000033
Further, the solvent in the step (1) is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, the base catalyst in the step (1) is potassium carbonate and/or sodium carbonate, and the preferred base catalyst is potassium carbonate.
Further, the water-carrying agent in the step (1) is toluene and/or xylene.
Further, the molar ratio of the 4,4' -biphenol, the 3-bromopropylene, the alkali catalyst, the solvent and the water-carrying agent in the step (1) is 1: 2-2.2: 1-1.2: 1.5-2: 1-1.5, preferably 1: 2.1-2.2: 1.1-1.2: 1.6-1.8: 1-1.2.
Furthermore, the using amount of the solvent is 1.0-1.6 g/mL of the total mass of the 4,4' -biphenol and the 3-bromopropylene.
Further, the temperature in the step (1) is raised to 90-100 ℃ for reaction for 20-22 hours.
Further, pouring the deionized water into the step (1), wherein the ratio of the volume of the poured deionized water to the mass of the mixed solution is 50-100: 1.
Further, the temperature is raised to 190-.
Further, the temperature is slowly increased to 180-200 ℃ in 30-40min under the stirring condition of the step (2).
Further, the solvent in the step (3) is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, the alkali catalyst in the step (3) is potassium carbonate and/or sodium carbonate. The preferred base catalyst is potassium carbonate.
Further, the water-carrying agent in the step (3) is toluene and/or xylene.
Further, the molar ratio of the 4,4' -biphenol, the 4-chloronitrobenzene, the alkali catalyst, the solvent and the water-carrying agent in the step (3) is 1: 2-2.2: 1-1.2: 1.5-2: 1-1.5, preferably 1: 2.1-2.2: 1.1-1.2: 1.6-1.8: 1-1.2.
Further, the step (3) carries water for 1-2h at the temperature of 130-140 ℃.
Further, pouring deionized water into the step (3), wherein the ratio of the volume of the poured deionized water to the mass of the mixed solution is 50-100: 1.
Further, the solvent in the step (4) is one or more of ethanol, isopropanol and glycerol.
Further, the catalyst in the step (4) is palladium carbon and/or FeCl 3 。
Further, the molar ratio of the 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl to the 4-chloronitrobenzene in the step (4) to the catalyst to the solvent is 1: 2-2.2: 0.02-0.05: 2-3, preferably 1: 2.1-2.2: 0.03-0.05: 2.5-3.
Further, slowly dripping hydrazine hydrate in the step (4) within 0.5-1 h.
Further, the filtering and drying step in the step (4) is as follows: extracting with dichloromethane for three times; washing the organic layer with saturated salt solution, drying with anhydrous sodium sulfate, filtering, and evaporating the solvent to obtain a crude product; and (3) performing column chromatography separation and extraction by using petroleum ether/ethyl acetate ═ 3:1 as eluent to prepare the 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl.
Another object of the present invention is to disclose an allyl-containing cross-linkable polyetherimide polymer having the following structural formula (structural formula 2):
Figure BDA0003742996510000051
wherein: wherein n is the degree of polymerization and n is an integer;
R 1 comprises the following steps:
Figure BDA0003742996510000052
one of (1); r 2 Comprises the following steps:
Figure BDA0003742996510000053
Figure BDA0003742996510000054
one of (1);
another object of the present invention is to disclose a method for preparing allyl-containing crosslinkable polyetherimide polymer, comprising the steps of: diamine monomer [ at least containing 3,3' -diallyl-4, 4' -di (4-aminophenoxy) biphenyl ] and dianhydride monomer [ at least containing 4,4' - (hexafluoroisopropylidene) diphthalic anhydride ] are used as raw materials, adding m-cresol as solvent into a container with a mechanical stirring, nitrogen guide head and a condenser pipe, stirring at normal temperature for 8-12h to form viscous polyamic acid solution, adding catalyst into the solution to perform dehydration cyclization reaction, then reacting for 4-8h in an oil bath at 30-60 ℃, heating to 160-180 ℃ for reacting for 4-8h, cooling to room temperature, pouring the product into absolute ethyl alcohol, white floccule is obtained, filtered, washed by ethanol and distilled water, and dried in vacuum to obtain the allyl-containing cross-linkable polyetherimide polymer.
Further, the molar ratio of the diamine monomer to the dianhydride monomer is 0.96-1.04, preferably 1: 1.
Furthermore, the dosage of the m-cresol is 15-25% of the solid content of the mixed solution, and preferably 20-25%.
Further, the catalyst is used in an amount of 0.02 to 0.05 mole amount based on the diamine monomer and the dianhydride monomer.
Further, the catalyst is isoquinoline or a mixed solution of pyridine and acetic anhydride in a volume ratio of 1: 2-3.
Further, the absolute ethyl alcohol is used in the following amount of polymer settling agent: absolute ethanol 1 (g): 100-500 (mL).
Further, the vacuum drying condition is 80-100 ℃ and 10-24 h.
Further, when one diamine monomer is used, the diamine monomer is 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl; when two diamine monomers are used, one of them is 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl, and the other diamine monomer is one of p-phenylenediamine, m-phenylenediamine, diphenyldiamine, 9-bis (4-aminophenyl) fluorene, 4 '-diaminodiphenyl ether, 4' -isopropylamine, 4 '-diaminodiphenyl sulfone or 4,4' -diaminodiphenyl ketone.
Further, when one dianhydride monomer is used, the dianhydride monomer is 4,4'- (hexafluoroisopropylidene) diphthalic anhydride, when two dianhydride monomers are used, one dianhydride monomer is 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, and the other dianhydride monomer is one of terephthalic anhydride, biphenyl dianhydride, 4,4 '-diphenyl ether dianhydride, 4,4' - (4,4 '-isopropylidenediphenoxy) bis (phthalic anhydride), 3', 4,4 '-diphenylsulfone tetracarboxylic dianhydride, or 4,4' -carbonyldiphthalic anhydride.
Another object of the present invention is to disclose a cross-linked polyetherimide film prepared from the above cross-linkable polyetherimide polymer containing allyl groups.
The invention also discloses a preparation method of the crosslinked polyetherimide film, which comprises the following specific steps when thermal crosslinking is adopted: adding an allyl-containing cross-linkable polyetherimide polymer, a solvent, and a free radical initiator to a vessel; after stirring and dissolving, pouring into a polytetrafluoroethylene plate; drying the solvent in an oven, and taking out the transparent allyl-containing fluorinated polyetherimide film; and putting the obtained fluorinated polyetherimide film containing allyl into a vacuum oven, heating to 120-150 ℃, and preserving the heat for 4-8h to obtain the thermally crosslinked polyimide film.
Further, the solvent is one or more of chloroform, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, the free radical initiator is one or two of benzoyl peroxide and/or azobisisobutyronitrile.
Further, the allyl cross-linkable polyetherimide polymer, solvent, and free radical initiator are present in a molar ratio of 1: 10-20: 0.02 to 0.08, preferably 1: 15-20: 0.05-0.08.
The invention also discloses a preparation method of the cross-linked polyetherimide film, which comprises the following specific steps when photo-initiated cross-linking is adopted: adding an allyl-containing cross-linkable polyetherimide polymer, a solvent, and a photoinitiator to a vessel; stirring to dissolve, filtering the polymer solution with 0.45 μm needle filter, standing for 1-2 hr, and pouring into clean (10cm × 10 cm) polytetrafluoroethylene plate; drying in an oven at 60-80 ℃ for 24-48h until the solvent is completely evaporated, and cooling to room temperature to prepare a transparent allyl-containing polymer film; and (3) irradiating the obtained allyl-containing polymer film for 0.5h under an ultraviolet lamp to obtain the allyl-containing crosslinked polyetherimide film.
Further, the solvent is one or more of chloroform, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone (UV184), 2,4,6- (trimethylbenzoyl) diphenyl phosphorus oxide (TPO), ethyl 4-dimethylaminobenzoate (EDB) and tetraphenyl benzophenone (PBZ).
Further, the allyl-containing crosslinkable polyetherimide polymer, the photoinitiator and the solvent are in a molar ratio of 1: 0.02-0.05: 10-20, preferably 1: 0.03-0.05: 15-20.
The invention also discloses a preparation method of the cross-linked polyetherimide film, which comprises the following specific steps when silicon hydride cross-linking is adopted: adding an allyl-containing cross-linkable polyetherimide polymer, a solvent, a siloxane, and a catalyst to a vessel; stirring to dissolve, filtering the polymer solution with 0.45 μm needle filter, pouring into clean (10cm × 10 cm) polytetrafluoroethylene plate, standing at room temperature for 1-2h, transferring into 60-80 deg.C oven for 24-48h until the solvent is completely volatilized, and taking out to obtain the final product.
Further, the solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, the siloxane is hydrogen-terminated polydimethylsiloxane and/or polyhydrosilane.
Further, the catalyst is chloroplatinic acid.
Further, the allyl-containing cross-linkable polyetherimide polymer, the solvent, the siloxane, and the catalyst are present in a molar ratio of 1: 10-20: 5-30: 0.01 to 0.05, preferably 1: 15-20: 10-20: 0.02-0.05.
The invention also discloses a preparation method of the cross-linked polyetherimide membrane, which comprises the following specific steps when the mercapto cross-linking is adopted: adding the allyl-containing cross-linkable polyetherimide polymer, a solvent, a mercapto cross-linking agent and a catalyst into a container under the protection of nitrogen; stirring to dissolve, filtering the polymer solution with 0.45 μm needle filter, pouring into clean (10cm × 10 cm) polytetrafluoroethylene plate, and vacuum oven at 60-80 deg.C; and keeping the temperature for 24-48h until the solvent is completely volatilized, and taking out the film to obtain the sulfydryl crosslinked fluorinated polyetherimide film.
Further, the solvent is one or more of N, N '-dimethylformamide, N, N' -dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, the mercapto crosslinking agent is one or more of dimercaptoalcohol or mercapto-terminated polyethylene glycol.
Further, the catalyst is one or more of dimethylolpropionic acid, tetramethylammonium hydroxide, triethylamine and DBU.
Further, the polyetherimide, the solvent, the mercapto crosslinking agent and the catalyst have a molar ratio of 1: 10-20: 0.05-0.1: 0.01 to 0.05, preferably 1: 15-20: 0.05-0.08: 0.02-0.05.
Compared with the prior art, the allyl-containing diamine monomer, the cross-linkable polyetherimide polymer, the cross-linked polyetherimide film and the preparation method thereof have the following advantages:
1) the preparation method of the invention can obtain the diamine monomer containing allyl by only one step, has simple process, mild reaction and easy control, and the raw materials and the reagents are easy to obtain, the cost is lower, and the industrial production is easy.
2) The allyl-containing cross-linkable polyetherimide polymer prepared by the method has the advantages of large molecular weight and narrow molecular weight distribution, and the preparation method has the advantages of short preparation period, high equipment utilization rate, uniform product molecular weight and lower cost. The invention provides a one-step method for preparing cross-linkable polyetherimide with allyl on a side chain, so that cross-linkable groups are introduced into a main polymer chain.
3) The allyl-containing crosslinkable polyetherimide film has the excellent comprehensive properties of no color, high transparency, high mechanical strength, good thermal stability and the like, and the preparation method has the advantages of mild and rapid crosslinking reaction, easily obtained reaction reagents, low cost and various crosslinking modes. The allyl groups can be crosslinked by a variety of crosslinking means, such as photo-initiated, thermally-initiated, hydrosilyl or mercapto crosslinking. And the crosslinking degree of the polymer can be regulated and controlled by adjusting the proportion of the crosslinking monomer, so that the thermal stability and the mechanical property of the polymer are improved, and the requirements of different fields are met.
4) The series of polymers can be dissolved in a common solvent before crosslinking, have good processability, and are insoluble after crosslinking, so that the glass transition temperature and the thermal stability of the polymers are greatly improved. Meanwhile, no small molecules escape in the cross-linking process, and defects are not easy to generate. The crosslinking degree of the polyetherimide material is regulated and controlled by adjusting the proportion of the allyl-containing monomer, so that the application range of the polyimide resin in different fields is greatly widened.
Drawings
FIG. 1 is an IR spectrum of a diamine monomer, 3 '-diallyl-4, 4' -bis (4-aminophenoxy) Biphenyl (BADA), prepared in example 2 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of diamine monomer 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) Biphenyl (BADA) prepared in example 2 of the present invention;
FIG. 3 is an infrared spectrum of allyl group-containing uncrosslinked polyimide prepared in example 9 of the present invention and a 2 wt% photoinitiator added film cured for 0.5h under ultraviolet light;
FIG. 4 is a TGA spectrum of allyl-containing crosslinkable polyetherimine prepared in example 4 of the present invention before crosslinking.
Detailed Description
The invention is further illustrated by the following examples:
example 1
This example provides a 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl prepared as follows: 1.86g (0.01mol) of 4,4' -biphenol, 5mL of DMMF, 1.66g (0.012mol) of potassium carbonate and 5mL of toluene were charged into a 100mL three-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer, respectively. Heating to boil the water-carrying agent, carrying water until no water beads are generated in the water separator, steaming out the water-carrying agent, cooling the system to room temperature, adding 2.88g (0.024mol) of 3-bromopropylene, heating to 80-100 ℃, reacting for 24 hours, pouring into deionized water, and filtering to obtain 4,4' -bis (4-allyloxy) biphenyl.
Adding 4,4' -bis (4-allyloxy) biphenyl into a three-neck flask, introducing nitrogen for protection, slowly heating to 180 ℃ and 200 ℃ under stirring, reacting for 1h, and obtaining 3,3' -diallyl-4, 4' -biphenol after rearrangement;
2.66g (0.01mol) of the rearranged product 3,3 '-diallyl-4, 4' -biphenol, 3.465(0.022mol) 4-chloronitrobenzene and 1.66g of potassium carbonate are weighed and added into a 100mL three-neck flask with a mechanical stirring, reflux condenser and thermometer, and simultaneously added with 5mL of DMF10mL solvent and toluene as a water-carrying agent. Introducing nitrogen, carrying water for 2h when the temperature reaches 140 ℃, and discharging the water carrying agent after no water beads are generated in the water separator. The temperature of the reaction mixed solution is increased to 160 ℃, and the reaction is carried out for 6 hours. And pouring the mixed solution into 300mL of deionized water to obtain a khaki precipitate, filtering, washing with deionized water for three times, and drying in a vacuum oven to obtain the 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl with the yield of about 85%.
5.08g (0.01mol) of 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl was charged into a 100mL three-vial flask, 7g (0.0125mol) of iron powder was added, and 60mL of a mixed solvent (V) Deionized water \V Ethanol 1\1), under nitrogen, heated to reflux. 2mL of dilute hydrochloric acid was slowly added dropwise to the three-necked flask. After the dropwise addition of HCl was complete, the reaction was continued for 2 h. And (3) filtering the product while the product is hot, adjusting the pH of the filtrate to 8 by using a 10% sodium hydroxide solution, precipitating a solid, filtering, recrystallizing a filter cake by using ethanol water, and placing the filter cake in a vacuum oven at 60 ℃ to obtain the 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl with the yield of 76%.
Example 2
This example provides a 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl prepared as follows: 1.86g (0.01mol) of 4,4' -biphenol, 5mL of DMMF, 1.66g (0.012mol) of potassium carbonate and 5mL of toluene were charged into a 100mL three-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer, respectively. Heating until the water-carrying agent is boiled, carrying water until no water beads are generated in the water separator, steaming out the water-carrying agent, cooling the system to room temperature, adding 2.88g (0.024mol) of 3-bromopropylene, reacting for 48h at 60 ℃, pouring into deionized water, and filtering to obtain 4,4' -bis (4-allyloxy) biphenyl.
Adding 4,4' -bis (4-allyloxy) biphenyl into a three-neck flask, introducing nitrogen for protection, slowly heating to 180 ℃ and 200 ℃ under stirring, reacting for 1h, and obtaining 3,3' -diallyl-4, 4' -biphenol after rearrangement;
2.66g (0.01mol) of the rearranged product 3,3 '-diallyl-4, 4' -biphenol, 3.465(0.022mol) 4-chloronitrobenzene and 1.66g of potassium carbonate are weighed and added into a 100mL three-neck flask with a mechanical stirring, reflux condenser and thermometer, and simultaneously added with 5mL of DMF10mL solvent and toluene as a water-carrying agent. Introducing nitrogen, carrying water for 2h when the temperature reaches 140 ℃, and discharging the water carrying agent after no water beads are generated in the water separator. The temperature of the reaction mixed solution is increased to 160 ℃, and the reaction is carried out for 6 hours. And pouring the mixed solution into 300mL of deionized water to obtain a khaki precipitate, filtering, washing with deionized water for three times, and drying in a vacuum oven to obtain the 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl with the yield of about 85%.
5.08g (0.01mol) of 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl were charged into a 100mL three-vial flask, and 0.1g of palladium on carbon and 60mL of absolute ethanol were added, and the mixture was heated to reflux under nitrogen. 15mL of hydrazine hydrate was slowly added dropwise to the three-necked flask. After the addition of hydrazine hydrate was completed, the reaction was continued for 2 h. The product was filtered hot, cooled and poured into deionized water to precipitate a pale yellow solid. Filtering, recrystallizing the yellow filter cake with ethanol water, and placing in a vacuum oven at 60 ℃ to obtain the 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl. The yield was 86%, and the infrared spectrum and the hydrogen nuclear magnetic spectrum of the sample were shown in FIG. 1 and FIG. 2, respectively.
Example 3
This example provides a 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl prepared as follows: 1.86g (0.01mol) of 4,4' -biphenol, 5mL of DMMF, 1.66g (0.012mol) of potassium carbonate and 5mL of toluene were charged into a 100mL three-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer, respectively. Heating to boil the water-carrying agent, carrying water until no water beads are generated in the water separator, steaming out the water-carrying agent, cooling the system to room temperature, adding 2.88g (0.024mol) of 3-bromopropylene, heating to 80-100 ℃, reacting for 24 hours, pouring into deionized water, and filtering to obtain 4,4' -bis (4-allyloxy) biphenyl.
Adding 4,4' -bis (4-allyloxy) biphenyl into a three-neck flask, introducing nitrogen for protection, slowly heating to 180 ℃ and 200 ℃ under stirring, reacting for 1h, and obtaining 3,3' -diallyl-4, 4' -biphenol after rearrangement;
2.66g (0.01mol) of the rearranged product 3,3 '-diallyl-4, 4' -biphenol, 3.465(0.022mol) 4-chloronitrobenzene and 1.66g of potassium carbonate are weighed into a 100mL three-neck flask with a mechanical stirring, reflux condenser and thermometer, and simultaneously 5mL of DMF10mL and toluene as a water-carrying agent are added. Introducing nitrogen, carrying water for 2h when the temperature reaches 140 ℃, and discharging the water carrying agent after no water beads are generated in the water separator. The temperature of the reaction mixed solution is increased to 160 ℃, and the reaction is carried out for 6 hours. And pouring the mixed solution into 300mL of deionized water to obtain a khaki precipitate, filtering, washing with deionized water for three times, and drying in a vacuum oven to obtain the 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl with the yield of about 85%.
5.08g (0.01mol) of 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl was charged in a 100mL three-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer, respectively, and 0.2g of FeCl was added 3 A spoon of activated carbon was added with 60mL of absolute ethanol and heated to reflux under nitrogen. 15mL of hydrazine hydrate was slowly added dropwise to the three-necked flask. After the addition of hydrazine hydrate was completed, the reaction was continued for 2 h. The product was filtered hot, cooled and poured into deionized water to precipitate a pale yellow solid. Filtering, recrystallizing the yellow filter cake with ethanol water, and placing in a vacuum oven at 60 ℃ to obtain the 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl with the yield of 82%.
Example 4
This example provides an allyl-containing polyetherimide homopolymer prepared as follows: 2.24g (0.005mol) of 3,3' -diallyl-4, 4' -bis (4-aminophenoxy) biphenyl were weighed out, charged into a 100mL three-necked flask equipped with a reflux condenser and a thermometer with mechanical stirring under nitrogen atmosphere, 18mL of m-cresol was charged, and after completely dissolving, 2.22g (0.005mol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride was reacted with the resulting mixture. After the addition was complete, the mixture was mechanically stirred at room temperature for 1h to form a viscous polyamic acid solution. Adding 0.2mL of isoquinoline into the mixed solution, heating to 80 ℃, continuing to react for 1h, and then heating to 180 ℃ to react for 10 h. After cooling, the polymer solution was poured into 200mL of absolute ethanol with stirring to obtain a polymer in the form of a thin strip. The obtained product is filtered, washed by distilled durene water and ethanol for three times respectively, and dried in a vacuum oven at 100 ℃ for 24 hours to obtain the polyether imide homopolymer containing allyl, wherein the yield is 95%.
The thermogravimetry curve of the prepared allyl-containing polyetherimide homopolymer in nitrogen is shown in fig. 4, and the temperature of 5% of the thermogravimetry is 490 ℃, which shows that the polymer has excellent thermal stability.
Example 5
This example provides an allyl-containing polyetherimide homopolymer prepared as follows: 1.12g (0.0025mol) of 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl and 0.5g (0.0025mol) of 4,4 '-diaminophenyl ether were weighed into a 100mL three-necked flask with mechanical stirring, reflux condenser and thermometer under nitrogen protection, 15mL of m-cresol was added, and after complete dissolution, 2.22g (0.005mol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride was reacted with it. After the addition was complete, the mixture was mechanically stirred at room temperature for 1h to form a viscous polyamic acid solution. Adding 0.2mL of isoquinoline into the mixed solution, heating to 80 ℃, continuing to react for 1h, and then heating to 180 ℃ to react for 10 h. After cooling, the polymer solution was poured into 200mL of absolute ethanol with stirring to obtain a polymer in the form of a thin strip. The mixture was filtered, washed three times with distilled durene water and ethanol, and dried in a vacuum oven at 100 ℃ for 24h to obtain a polyetherimide copolymer with 50% allyl content, with a yield of 96%.
Example 6
This example provides an allyl-containing polyetherimide homopolymer prepared by the following method: 2.24g (0.005mol) of 3,3' -diallyl-4, 4' -bis (4-aminophenoxy) biphenyl were weighed out, charged into a 100mL three-necked flask with a mechanical stirrer, reflux condenser and thermometer under nitrogen atmosphere, 18mL of m-cresol was charged, and after completely dissolving, 2.22g (0.005mol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride was added. After the addition was complete, the mixture was mechanically stirred at room temperature for 24h to form a viscous polyamic acid solution. And adding 0.2mL of pyridine and 0.4mL of acetic anhydride into the mixed solution, continuously reacting for 8h in an oil bath at the temperature of 60 ℃, pouring into absolute ethyl alcohol to obtain white floccules, filtering, washing with distilled water and ethanol for three times respectively, and drying in a vacuum oven at 100 ℃ for 24h to obtain the allyl-containing polyetherimide homopolymer with the yield of 96%.
Example 7
This example provides an allyl-containing polyetherimide homopolymer prepared as follows: 1.12g (0.0025mol) of 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl and 0.5g (0.0025mol) of 4,4 '-diaminophenyl ether were weighed into a 100mL three-necked flask with mechanical stirring, reflux condenser and thermometer under nitrogen protection, 15mL of m-cresol was added, and after complete dissolution, 2.22g (0.005mol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride was added. After the addition was complete, the mixture was mechanically stirred at room temperature for 24h to form a viscous polyamic acid solution. Then 0.2mL pyridine and 0.4mL acetic anhydride are added into the mixed solution, the mixture is continuously reacted for 8 hours in an oil bath at the temperature of 60 ℃, poured into absolute ethyl alcohol, white floccule appears, filtered and washed with distilled pomegranate water and ethyl alcohol for three times respectively. Drying in a vacuum oven at 100 ℃ for 24h gave a polyetherimide copolymer of 50% allyl content in 95% yield.
Example 8
This example discloses a cross-linked polyetherimide film prepared by the following steps: 0.3g of allyl-containing polyetherimide homopolymer was weighed into a 50mL single-neck flask and 10mL of N, N' -dimethylformamide (DMAc). After the dissolution by stirring, the polymer solution was filtered through a 0.45 μm syringe filter, left to stand for 2 hours, and poured into a clean 10cm × 10 cm-sized polytetrafluoroethylene plate. Drying in an oven at 60 deg.C for 24 hr until the solvent is evaporated, and cooling to room temperature. A small amount of deionized water was dropped on the tetrafluoro plate, and the transparent allyl group-containing fluorinated polyether imide film was taken out.
And (3) putting the obtained fluorinated polyetherimide film containing allyl into a vacuum oven, heating to 180 ℃, and preserving the temperature for 6 hours to obtain the thermally crosslinked polyimide film.
Example 9
This example discloses a cross-linked polyetherimide film prepared by the following steps: 0.3g of allyl-containing polyetherimide homopolymer was weighed into a 50mL single-neck flask, 10mL of N, N' -dimethylformamide (DMAc), and 2% of photoinitiator (1-hydroxycyclohexyl phenyl ketone) was added. After the dissolution by stirring, the polymer solution was filtered through a 0.45 μm syringe filter, left to stand for 2 hours, and poured into a clean 10cm × 10 cm-sized polytetrafluoroethylene plate. Drying in an oven at 60 deg.C for 24 hr until the solvent is evaporated, and cooling to room temperature. A small amount of deionized water was dropped on the tetrafluoro plate, and the transparent allyl group-containing fluorinated polyether imide film was taken out.
And (3) irradiating the obtained fluorinated polyetherimide film containing allyl under an ultraviolet lamp for 0.5h to obtain the crosslinked polyetherimide film. The IR spectrum is shown in FIG. 3.
Example 10
This example discloses a cross-linked polyetherimide film prepared by the following steps: 0.3g of allyl-containing polyetherimide homopolymer was weighed into a 50mL three-necked flask, 10mL of N, N' -dimethylformamide (DMAc), 0.01g of hydrogen-terminated polydimethylsiloxane and 1mg of chloroplatinic acid catalyst were added. Stirring to dissolve, filtering the polymer solution with 0.45 μm needle filter, pouring into clean 10cm × 10cm polytetrafluoroethylene plate, standing at room temperature for 2h, transferring into 60 deg.C oven for 24h until the solvent is completely volatilized, and taking out to obtain silicon hydride crosslinked polyetherimide film.
Example 11
This example discloses a cross-linked polyetherimide film prepared by the following steps: 0.3g of allyl-containing polyetherimide homopolymer was weighed into a 50mL three-necked flask under nitrogen, 10mL of N, N' -dimethylformamide (DMAc), 0.06g of 1, 2-ethanedithiol and 1mg of dimethylolpropionic acid (DMPA). After dissolution with stirring, the polymer solution was filtered through a 0.45 μm syringe filter and poured quickly into a clean 10cm x 10cm teflon plate and placed in a vacuum oven at 60 ℃. And keeping the temperature for 24h until the solvent is completely volatilized, and taking out the film to obtain the sulfydryl crosslinked fluorinated polyetherimide film.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. An allyl-containing diamine monomer characterized by having pendant diallyl groups and the formula:
Figure FDA0003742996500000011
2. a preparation method of an allyl-containing diamine monomer is characterized by comprising the following steps:
(1) taking 4,4 '-biphenyl diphenol as a raw material, respectively adding a solvent, an alkali catalyst and a water-carrying agent, heating until the water-carrying agent is boiled, steaming out the water-carrying agent after no water beads are generated in a water separator, cooling a system to room temperature, adding 3-bromopropylene, heating to 80-100 ℃, reacting for 10-24 hours, pouring into deionized water, and filtering to obtain 4,4' -bis (4-allyloxy) biphenyl;
(2) pouring 4,4' -bis (4-allyloxy) biphenyl into a reaction vessel, introducing nitrogen for protection, stirring, heating to 180 ℃ and 200 ℃, melting after the solid reaches a melting point, reacting for 0.5-2h, and rearranging to obtain 3,3' -diallyl-4, 4' -biphenol;
(3) taking 3,3 '-diallyl-4, 4' -biphenol and 4-chloronitrobenzene as raw materials, adding a solvent, an alkali catalyst and a water-carrying agent, carrying out water carrying at the temperature of 120-150 ℃ for 1-5h, evaporating the water-carrying agent, heating to the temperature of 140-160 ℃ for reaction for 4-8h, pouring into deionized water for washing, and filtering to obtain 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl;
(4) adding 3,3 '-diallyl-4, 4' -bis (4-nitrophenoxy) biphenyl, a solvent and a catalyst into a reaction vessel, heating to 60-100 ℃, slowly dripping hydrazine hydrate, continuously reacting for 2-4h after dripping, cooling to room temperature, pouring into deionized water, filtering and drying to obtain the 3,3 '-diallyl-4, 4' -bis (4-aminophenoxy) biphenyl.
3. The method for preparing allyl-containing diamine monomer according to claim 2, wherein the molar ratio of 4,4' -biphenol, 3-bromopropene, alkali catalyst, solvent and water-carrying agent in step (1) is 1: 2-2.2: 1-1.2: 1.5-2: 1-1.5.
4. An allyl-containing crosslinkable polyetherimide polymer characterized by the structural formula:
Figure FDA0003742996500000012
Figure FDA0003742996500000021
wherein: wherein n is the degree of polymerization and n is an integer;
R 1 comprises the following steps:
Figure FDA0003742996500000022
Figure FDA0003742996500000023
one of (1);
R 2 comprises the following steps:
Figure FDA0003742996500000024
Figure FDA0003742996500000025
one kind of (1).
5. A method for preparing the allyl-containing cross-linkable polyetherimide polymer of claim 4, comprising the steps of: taking the allyl-containing diamine monomer and dianhydride monomer as the raw materials in claim 1, taking m-cresol as a solvent, adding into a container with a mechanical stirrer, a nitrogen guide head and a condenser tube, stirring at normal temperature for 8-12h to form a viscous polyamic acid solution, adding a catalyst into the solution to perform a dehydration cyclization reaction, reacting in an oil bath at 30-60 ℃ for 4-8h, heating to 160-180 ℃ for reaction for 4-8h, cooling to room temperature, pouring the product into absolute ethyl alcohol to obtain white floccule, filtering, washing with ethyl alcohol and distilled water, and performing vacuum drying to obtain the allyl-containing crosslinkable polyetherimide polymer.
6. A crosslinked polyetherimide film prepared from the allyl-containing crosslinkable polyetherimide polymer of claim 4.
7. A preparation method of a cross-linked polyetherimide membrane is characterized by comprising the following specific steps when thermal cross-linking is adopted: adding an allyl-containing cross-linkable polyetherimide polymer, a solvent, and a free radical initiator to a vessel; after stirring and dissolving, pouring into a polytetrafluoroethylene plate; drying the solvent in an oven, and taking out the transparent allyl-containing fluorinated polyetherimide film; and putting the obtained fluorinated polyetherimide film containing allyl into a vacuum oven, heating to 120-150 ℃, and preserving the heat for 4-8h to obtain the thermally crosslinked polyimide film.
8. The invention discloses a preparation method of a cross-linked polyetherimide film, which is characterized in that the other purpose of the invention also discloses a preparation method of the cross-linked polyetherimide film, and the method adopts the specific steps of photo-initiated cross-linking: adding an allyl-containing cross-linkable polyetherimide polymer, a solvent, and a photoinitiator to a vessel; after stirring and dissolving, filtering the polymer solution by using a needle filter, standing for 1-2h, and pouring into a clean polytetrafluoroethylene plate; drying in an oven at 60-80 ℃ for 24-48h until the solvent is completely evaporated, and cooling to room temperature to prepare a transparent allyl-containing polymer film; and (3) irradiating the obtained allyl-containing polymer film for 0.5h under an ultraviolet lamp to obtain the allyl-containing crosslinked polyetherimide film.
9. The invention discloses a preparation method of a cross-linked polyetherimide membrane, which is characterized in that the other purpose of the invention also discloses a preparation method of the cross-linked polyetherimide membrane, and the method adopts silicon hydride cross-linking to specifically comprise the following steps: adding an allyl-containing cross-linkable polyetherimide polymer, a solvent, a siloxane, and a catalyst to a vessel; after stirring and dissolving, filtering the polymer solution by using a needle filter, pouring the polymer solution into a clean polytetrafluoroethylene plate, standing the polytetrafluoroethylene plate for 1 to 2 hours at room temperature, transferring the polytetrafluoroethylene plate into a 60 to 80 ℃ oven for 24 to 48 hours until the solvent is completely volatilized, and taking out the polyetherimide film crosslinked by silicon hydride.
10. A preparation method of a cross-linked polyetherimide membrane is characterized by comprising the following specific steps when mercapto cross-linking is adopted: adding the allyl-containing cross-linkable polyetherimide polymer, a solvent, a mercapto cross-linking agent and a catalyst into a container under the protection of nitrogen; after stirring and dissolving, filtering the polymer solution by using a needle filter, quickly pouring the polymer solution into a clean polytetrafluoroethylene plate, and placing the polytetrafluoroethylene plate in a vacuum oven at the temperature of 60-80 ℃; and keeping the temperature for 24-48h until the solvent is completely volatilized, and taking out the film to obtain the sulfydryl crosslinked fluorinated polyetherimide film.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113527683A (en) * 2021-08-10 2021-10-22 宁波博雅聚力新材料科技有限公司 Polyimide and polyimide film using the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0317944A2 (en) * 1987-11-24 1989-05-31 Hoechst Celanese Corporation Polymers prepared from 4,4'-bis-(2-(amino (halo) phenoxyphenyl) hexafluoroisopropyl) diphenyl ether
CN102108120A (en) * 2011-01-19 2011-06-29 吉林大学 Allyl-group-containing cross-linked poly(aryl ether sulfone) polymer and preparation method thereof
CN107162922A (en) * 2017-05-24 2017-09-15 吉林大学 A kind of diamine monomer of polyimides containing pi-allyl and its polyimide polymer and preparation method
CN111607088A (en) * 2020-06-01 2020-09-01 素水能源科技（上海）有限公司 Self-crosslinking sulfonated polyimide copolymer, proton exchange membrane and preparation method thereof
CN113511980A (en) * 2021-07-10 2021-10-19 南昌大学 Aromatic polyimide with main chain containing benzonorbornene structure and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0317944A2 (en) * 1987-11-24 1989-05-31 Hoechst Celanese Corporation Polymers prepared from 4,4'-bis-(2-(amino (halo) phenoxyphenyl) hexafluoroisopropyl) diphenyl ether
CN102108120A (en) * 2011-01-19 2011-06-29 吉林大学 Allyl-group-containing cross-linked poly(aryl ether sulfone) polymer and preparation method thereof
CN107162922A (en) * 2017-05-24 2017-09-15 吉林大学 A kind of diamine monomer of polyimides containing pi-allyl and its polyimide polymer and preparation method
CN111607088A (en) * 2020-06-01 2020-09-01 素水能源科技（上海）有限公司 Self-crosslinking sulfonated polyimide copolymer, proton exchange membrane and preparation method thereof
CN113511980A (en) * 2021-07-10 2021-10-19 南昌大学 Aromatic polyimide with main chain containing benzonorbornene structure and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘金刚 等: "新型烯丙基芳香二胺的合成及其固化特性研究", 《热固性树脂》, vol. 21, no. 3, pages 5 - 8 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113527683A (en) * 2021-08-10 2021-10-22 宁波博雅聚力新材料科技有限公司 Polyimide and polyimide film using the same
CN113527683B (en) * 2021-08-10 2023-09-29 宁波博雅聚力新材料科技有限公司 Polyimide and polyimide film using the same

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