CN115010613A - A kind of allyl-containing diamine monomer, cross-linkable polyetherimide polymer, cross-linked polyetherimide film and preparation method thereof - Google Patents

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

A kind of allyl-containing diamine monomer, cross-linkable polyetherimide polymer, cross-linked polyetherimide film and preparation method thereof

technical field

The invention relates to polymer material technology, in particular to an allyl-containing diamine monomer, a cross-linkable polyetherimide polymer, a cross-linked polyetherimide film and a preparation method thereof.

Background technique

Polyimide is a high-performance engineering material with excellent performance. It has excellent high temperature resistance, mechanical properties, radiation resistance, dielectric properties and solvent resistance. It has been widely used in aerospace, military, electronics and other fields. However, due to the conjugated semi-trapezoid molecular chain structure composed of aromatic heterocycles in most polyimide molecules, the molecular chain has high rigidity and the molecular chain is difficult to rotate, resulting in poor solubility of polyimide in organic solvents. , the phenomenon of non-melting or non-softening occurs under thermal processing, which limits the application range of polyimide. Therefore, reducing its rigidity and improving its solubility and processability while maintaining its excellent heat resistance has become a hot spot in the research of high-performance polyimide.

It is an effective method to improve the processability of polyimide by introducing cross-linkable groups. These cross-linking groups do not react before molding, but cause cross-linking reaction during or after molding, forming insoluble Infusible three-dimensional polymer network. This not only ensures the excellent solubility and processability of polyimide, but also has more excellent thermal properties after molding.

There are two main ways to introduce cross-linking groups in polyimide, one is to introduce at the end of the polymer chain, such as maleic anhydride, norbornene or alkynyl end capping groups. The polyimide end-capped with maleic anhydride, the resin after cross-linking is brittle; the polyimide end-capped with norbornene anhydride forms an aliphatic chain structure after cross-linking, the thermal stability is decreased, and the alkynyl end-capped group After the group is cross-linked, a benzene ring is formed, which makes up for the shortcomings of the above two groups and is the most commonly used cross-linking group at present. high and difficult to use on a large scale. The other is the introduction of side groups in the polymer chain, such as carboxyl, bromine, etc. Carboxyl group as cross-linking group needs to add a third small molecule diol or diamine as cross-linking agent. Since the cross-linking reaction is in the resin after molding, incomplete cross-linking will occur, and even defects such as bubbles will appear. Affect the performance of the product; when bromine is used as the cross-linking group, the temperature needs to be raised to above 350 ℃ to debrominate and cross-linking occurs, the color of the resin becomes darker, and the conditions are harsh.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a side group-containing allyl diamine monomer and its cross-linking reaction in view of the problems of difficult cross-linking reaction, high cost, and easy occurrence of defects in the existing polyimide cross-linkable groups. Linking polyetherimide polymers, the crosslinking degree of the resin is controlled by adjusting the proportion of allyl monomers. This method has various crosslinking methods due to the introduction of allyl groups into the polymer, such as thermal crosslinking, light curing Cross-linking, sulfhydryl click cross-linking or silicon-hydrogen reagent cross-linking, these cross-linking methods have fast reaction and high efficiency, and no small molecules escape during curing, which greatly broadens the needs of polyimide resins in different fields.

In order to achieve the above object, the technical scheme adopted in the present invention is: a diamine monomer containing an allyl group, and its side group contains a bisallyl group, and the structural formula is as follows:

IUPAC named 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl.

Another object of the present invention also discloses a preparation method of an allyl-containing diamine monomer, comprising the following steps:

(1) Take 4,4'-biphenol as raw material, add solvent, alkali catalyst and water-carrying agent respectively, heat up to boiling with water-carrying agent, bring water to the water separator until no water droplets are produced, steam out the water-carrying agent Aqueous agent, after the system is lowered to room temperature, add 3-bromopropene, heat up to 80-100 ° C and react for 10-24 hours, pour into deionized water, and filter to obtain 4,4'-bis(4-allyloxy) bicarbonate. benzene;

(2) Pour 4,4'-bis(4-allyloxy)biphenyl into the reaction vessel, protect it with nitrogen, and stir to warm to 180-200°C, melt when the solid reaches the melting point, and react for 0.5-2h , 3,3'-diallyl-4,4'-biphenol is obtained after rearrangement;

(3) Using 3,3'-diallyl-4,4'-biphenol and 4-chloronitrobenzene as raw materials, adding solvent, alkali catalyst and water-carrying agent, and carrying water at 120-150 ° C After 1-5h, the water agent was evaporated, the temperature was raised to 140-160°C for 4-8h, poured into deionized water for washing, and filtered to obtain 3,3'-diallyl-4,4'-bis(4). - nitrophenoxy)biphenyl;

(4) 3,3'-diallyl-4,4'-bis(4-nitrophenoxy)biphenyl, solvent and catalyst were added to the reaction vessel, heated to 60-100°C and slowly dripped Add hydrazine hydrate, continue to react for 2-4h after dripping, cool to room temperature, pour into deionized water, filter and dry to obtain 3,3'-diallyl-4,4'-bis(4-aminobenzene) oxy) biphenyl.

Further, the solvent described in step (1) is one or more of N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone. kind.

Further, the alkali catalyst described in step (1) is potassium carbonate and/or sodium carbonate, and the preferred alkali catalyst is potassium carbonate.

Further, the water-carrying agent described in step (1) is toluene and/or xylene.

Further, in step (1), the molar ratio of 4,4'-biphenol, 3-bromopropene, alkali catalyst, solvent and water-carrying agent 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 amount of the solvent is 1.0-1.6 g/mL of the total mass of 4,4'-biphenol and 3-bromopropene.

Further, in step (1), the temperature is raised to 90-100° C. to react for 20-22 hours.

Further, step (1) is poured into deionized water, and the ratio of the volume of the poured deionized water to the mass of the mixed solution is 50-100:1.

Further, in step (2), the temperature is raised to 190-200° C. under stirring condition, and the solid is melted after reaching the melting point, and the reaction is carried out for 1-1.5 h.

Further, step (2) is slowly heated to 180-200° C. in 30-40 min under stirring condition.

Further, the solvent described in step (3) is one or more of N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone. kind.

Further, the alkali catalyst described in step (3) is potassium carbonate and/or sodium carbonate. The preferred base catalyst is potassium carbonate.

Further, the water-carrying agent described in step (3) is toluene and/or xylene.

Further, the molar ratio of 4,4'-biphenol, 4-chloronitrobenzene, alkali catalyst, solvent and water-carrying agent in step (3) is 1:2～2.2:1～1.2:1.5～2 : 1 to 1.5, preferably 1: 2.1 to 2.2: 1.1 to 1.2: 1.6 to 1.8: 1 to 1.2.

Further, in step (3), water is carried at 130-140° C. for 1-2 hours.

Further, step (3) is poured into deionized water, and the ratio of the volume of the poured deionized water to the mass of the mixed solution is 50-100:1.

Further, the solvent described in step (4) is one or more of ethanol, isopropanol and glycerol.

Further, the catalyst in step (4) is palladium carbon and/or FeCl ₃ .

Further, the molar ratio of 3,3'-diallyl-4,4'-bis(4-nitrophenoxy)biphenyl, 4-chloronitrobenzene, catalyst and solvent described in step (4) 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, the hydrazine hydrate is slowly dripped in in step (4), and the dripping is completed within 0.5-1 h.

Further, the step (4) filtration drying step is as follows: extract three times with dichloromethane; the organic layer is washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent is evaporated to obtain a crude product; with petroleum ether/ethyl acetate =3:1 is the eluent, which is separated and extracted by column chromatography to prepare 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl.

Another object of the present invention also discloses a cross-linkable polyetherimide polymer containing an allyl group, and the structural formula (structural formula 2) is as follows:

Among them: where n is the degree of polymerization, and n is an integer;

R1 is _:

中的一种； R₂为：

one of _; R2 is:

中的一种；

one of the

Another object of the present invention also discloses a preparation method of an allyl-containing crosslinkable polyetherimide polymer, comprising the following steps: using a diamine monomer [at least a 3,3'-diallyl group] -4,4'-bis(4-aminophenoxy)biphenyl] and dianhydride monomers [at least containing 4,4'-(hexafluoroisopropylidene)diphthalic anhydride] as raw materials, Using m-cresol as a solvent, add it into a container with mechanical stirring, a nitrogen leader and a condenser, stir at room temperature for 8-12 hours to form a viscous polyamic acid solution, and then add a catalyst to the above solution to carry out dehydration cyclization reaction, Then react in 30-60℃ oil bath for 4-8h, heat up to 160-180℃ and react for 4-8h, then drop to room temperature, pour the product into absolute ethanol to get white flocs, filter with ethanol and distilled water Washed and dried in vacuo to obtain an allyl-containing crosslinkable polyetherimide polymer.

Further, the molar ratio of the diamine monomer to the dianhydride monomer is 0.96-1.04, preferably 1:1.

Further, the dosage of the m-cresol is 15%-25% of the solid content of the mixed liquid, preferably 20-25%.

Further, the dosage of the catalyst is 0.02-0.05 of the molar amount of 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 to 3.

Further, the consumption of the absolute ethanol is polymer sedimentation agent: absolute ethanol 1 (g): 100-500 (mL).

Further, the vacuum drying conditions are 80-100° C., 10-24 h.

Further, when using a diamine monomer, the diamine monomer is 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl; when using In the case of two diamine monomers, one of which is 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl and the other is p-phenylene Diamine, m-phenylenediamine, biphenylenediamine, 9,9-bis(4-aminophenyl)fluorene, 4,4'-diaminodiphenyl ether, 4,4'-isopropylamine, One of 4,4'-diaminodiphenylsulfone or 4,4'-diaminobenzophenone.

Further, when using one dianhydride monomer, the dianhydride monomer is 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and when using two dianhydride monomers, One of them is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and the other dianhydride monomer is terephthalic anhydride, biphthalic anhydride, 4,4'-biphenyl ether Dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 3,3',4,4'-diphenylsulfonetetracarboxylic acid One of acid anhydride or 4,4'-carbonyl diphthalic anhydride.

Another object of the present invention also discloses a cross-linked polyetherimide film, which is prepared by using the above-mentioned allyl-containing cross-linkable polyetherimide polymer.

Another object of the present invention also discloses a method for preparing a cross-linked polyetherimide film. When thermal cross-linking is adopted, the specific steps are: mixing an allyl-containing cross-linkable polyetherimide polymer, a solvent and The free radical initiator is added into the container; after stirring and dissolving, it is poured into a polytetrafluoroethylene plate; the solvent is dried in an oven, and the transparent allyl-containing fluoropolyetherimide film is taken out; The allyl fluoropolyetherimide film is put into a vacuum oven, the temperature is raised to 120-150° C., and the temperature is maintained for 4-8 hours to obtain a thermally cross-linked polyimide film.

Further, the solvent is one or more of chloroform, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.

Further, the free radical initiator is one or both of benzoyl peroxide and/or azobisisobutyronitrile.

Further, the molar ratio of the allyl crosslinkable polyetherimide polymer, the solvent and the free radical initiator is 1:10-20:0.02-0.08, preferably 1:15-20:0.05-0.08 .

Another object of the present invention also discloses a method for preparing a cross-linked polyetherimide film. The specific steps when the cross-linking is initiated by light are as follows: an allyl-containing cross-linkable polyetherimide polymer, a solvent and photoinitiator were added to the container; after stirring and dissolving, the polymer solution was filtered with a 0.45 μm syringe filter, and after standing for 1-2 hours, poured into a clean (10cm×10cm size) polytetrafluoroethylene plate; Dry in an oven at 60-80°C for 24h-48h until the solvent evaporates and then drop to room temperature to prepare a transparent allyl-containing polymer film; place the obtained allyl-containing polymer film under a UV lamp After irradiating for 0.5h, an allyl-containing cross-linked polyetherimide film is obtained.

Further, the solvent is one or more of chloroform, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.

Further, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone (UV184), 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO), 4-dimethylamino One or more of ethyl benzoate (EDB) and tetraphenylbenzophenone (PBZ).

Further, the molar ratio of the allyl-containing crosslinkable polyetherimide polymer, the photoinitiator and the solvent is 1:0.02-0.05:10-20, preferably 1:0.03-0.05:15-20 .

Another object of the present invention also discloses a method for preparing a cross-linked polyetherimide film. The specific steps when using silicon-hydrogen cross-linking are: mixing an allyl-containing cross-linkable polyetherimide polymer, a solvent , siloxane and catalyst were added to the container; after stirring and dissolving, the polymer solution was filtered with a 0.45 μm syringe filter, poured into a clean (10cm×10cm size) PTFE plate, and placed at room temperature for 1- 2h, transfer to a 60-80°C oven for 24-48h until the solvent evaporates, and take out to obtain a polyetherimide film cross-linked by silicon hydrogen.

Further, the solvent is one or more of N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.

Further, the siloxane is hydrogen-terminated polydimethylsiloxane and/or polysiloxane.

Further, the catalyst is chloroplatinic acid.

Further, the molar ratio of the allyl-containing crosslinkable polyetherimide polymer, solvent, siloxane and catalyst is 1:10-20:5-30:0.01-0.05, preferably 1:15- 20:10～20:0.02-0.05.

Another object of the present invention also discloses a method for preparing a cross-linked polyetherimide film. The specific steps when using mercapto cross-linking are as follows: cross-linkable polyetherimide polymer containing allyl group, solvent, The thiol crosslinking agent and catalyst were added to the container under nitrogen protection; after stirring and dissolving, the polymer solution was filtered with a 0.45 μm syringe filter, and quickly poured into a clean (10cm×10cm size) PTFE plate, Place in a 60-80° C. vacuum oven; keep the temperature for 24-48 hours until the solvent evaporates, and take out the thiol-crosslinked fluoropolyetherimide 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 dimercapto alcohol or mercapto-terminated polyethylene glycol.

Further, the catalyst is one or more of dimethylolpropionic acid, tetramethylammonium hydroxide, triethylamine and DBU.

Further, the molar ratio of the polyetherimide, solvent, mercapto crosslinking agent and catalyst is 1: 10-20: 0.05-0.1: 0.01-0.05, preferably 1: 15-20: 0.05-0.08: 0.02 -0.05.

The allyl-containing diamine monomer, the cross-linkable polyetherimide polymer, the cross-linked polyetherimide film and the preparation method thereof of the present invention have the following advantages compared with the prior art:

1) The present invention only needs one step to obtain the allyl-containing diamine monomer, and the preparation method is not only simple in process, mild in reaction, and easy to control, but also the raw materials and reagents are easily obtained, the cost is low, and the industrial production is easy.

2) The allyl-containing crosslinkable polyetherimide polymer prepared by the present invention has large molecular weight and narrow molecular weight distribution, and the preparation method not only has short preparation period, high equipment utilization, but also has uniform product molecular weight and lower cost. The present invention prepares the cross-linkable polyetherimide with an allyl group in the side chain by a "one-step method", thereby introducing the cross-linkable group into the polymer main chain.

3) The allyl-containing cross-linkable polyetherimide film of the present invention has excellent comprehensive properties such as colorless, high transparency, high mechanical strength and good thermal stability. Easy to obtain, low cost, and various cross-linking methods. The allyl group can be cross-linked by various cross-linking methods, such as photo-induced cross-linking, thermal-induced cross-linking, silicon-hydrogen cross-linking or mercapto-based cross-linking. And by adjusting the ratio of crosslinking monomers, the degree of crosslinking of the polymer can be regulated, the thermal stability and mechanical properties of the polymer can be improved, and the needs of different fields can be met.

4) This series of polymers are soluble in common solvents before cross-linking and have good processability, but are insoluble after cross-linking, which greatly improves the glass transition temperature and thermal stability of the polymers. At the same time, no small molecules escape during the cross-linking process, and defects are not easily generated. By adjusting the proportion of allyl-containing monomers, the cross-linking degree of the polyetherimide material can be regulated, which greatly broadens the use range of polyimide resins in different fields.

Description of drawings

Fig. 1 is the infrared spectrum of diamine monomer 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl (BADA) prepared in Example 2 of the present invention;

Fig. 2 is the hydrogen nuclear magnetic resonance 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 the infrared spectrogram of the allyl-containing uncrosslinked polyimide prepared in Example 9 of the present invention and the photoinitiator film added with 2wt% and cured under ultraviolet light for 0.5h;

4 is a TGA spectrum of the allyl-containing crosslinkable polyetherimine prepared in Example 4 of the present invention before crosslinking.

Detailed ways

Below in conjunction with embodiment, the present invention is further described:

Example 1

This embodiment provides a 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl, and the preparation method is as follows: 1.86g (0.01mol) 4,4 '-Biphenol, 5mL DMF, 1.66g (0.012mol) potassium carbonate and 5mL toluene were added to a 100mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer, respectively. Heat up to boiling with water agent, bring water until no water droplets are produced in the water separator, steam with water agent, after the system is lowered to room temperature, add 2.88g (0.024mol) 3-bromopropene, heat up to 80-100 ℃ The reaction was carried out for 24 hours, poured into deionized water, and filtered to obtain 4,4'-bis(4-allyloxy)biphenyl.

Put all 4,4'-bis(4-allyloxy)biphenyl into the three-necked flask, pass nitrogen protection, slowly heat up to 180-200°C with stirring, react for 1h, and get 3,3'- diallyl-4,4'-biphenol;

Weigh the above rearranged product 2.66g (0.01mol) 3,3'-diallyl-4,4'-biphenol, 3.465 (0.022mol) 4-chloronitrobenzene, 1.66g potassium carbonate, A 100mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer was added, and at the same time, 10mL of solvent DMF and 5mL of toluene with water were added. Pass nitrogen, when the temperature reaches 140 ℃, carry water for 2 hours, and release the water-carrying agent after no water droplets are produced in the water separator. The temperature of the reaction mixture was increased to 160 °C, and the reaction was performed for 6 h. Pour the mixed solution into 300 mL of deionized water to obtain a khaki-yellow precipitate, filter, wash three times with deionized water, and dry in a vacuum oven to obtain 3,3'-diallyl-4,4'-bismuth (4-Nitrophenoxy)biphenyl in about 85% yield.

Add 5.08g (0.01mol) 3,3'-diallyl-4,4'-bis(4-nitrophenoxy)biphenyl to three 100mL bottles, add 7g (0.0125mol) iron powder, and then Add 60 mL of mixed solvent (V _{deionized water} \V _ethanol =1\1), under nitrogen, heat to reflux. 2 mL of dilute hydrochloric acid was slowly added dropwise to the three-necked flask. After the dropwise addition of HCl, the reaction was continued for 2 h. The product was filtered while hot, the filtrate was adjusted to pH 8 with 10% sodium hydroxide solution, after the solid was precipitated, filtered, the filter cake was recrystallized with ethanolic water, and placed in a vacuum oven at 60°C to obtain 3,3'-bis Allyl-4,4'-bis(4-aminophenoxy)biphenyl, 76% yield.

Example 2

This embodiment provides a 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl, and the preparation method is as follows: 1.86g (0.01mol) 4,4 '-Biphenol, 5mL DMF, 1.66g (0.012mol) potassium carbonate and 5mL toluene were added to a 100mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer, respectively. The temperature was raised to boiling with the water agent, and after the water was added to the water separator, no water beads were produced, and the water agent was distilled off. After the system was lowered to room temperature, 2.88g (0.024mol) of 3-bromopropene was added, and the reaction was carried out at 60 °C for 48h. Pour into deionized water and filter to obtain 4,4'-bis(4-allyloxy)biphenyl.

Put all 4,4'-bis(4-allyloxy)biphenyl into the three-necked flask, pass nitrogen protection, slowly heat up to 180-200°C with stirring, react for 1h, and get 3,3'- diallyl-4,4'-biphenol;

Weigh the above rearranged product 2.66g (0.01mol) 3,3'-diallyl-4,4'-biphenol, 3.465 (0.022mol) 4-chloronitrobenzene, 1.66g potassium carbonate, A 100mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer was added, and at the same time, 10mL of solvent DMF and 5mL of toluene with water were added. Pass nitrogen, when the temperature reaches 140 ℃, carry water for 2 hours, and release the water-carrying agent after no water droplets are produced in the water separator. The temperature of the reaction mixture was increased to 160 °C, and the reaction was performed for 6 h. Pour the mixed solution into 300 mL of deionized water to obtain a khaki-yellow precipitate, filter, wash three times with deionized water, and dry in a vacuum oven to obtain 3,3'-diallyl-4,4'-bismuth (4-Nitrophenoxy)biphenyl in about 85% yield.

Add 5.08g (0.01mol) 3,3'-diallyl-4,4'-bis(4-nitrophenoxy)biphenyl to 100mL three bottles, add 0.1g palladium carbon, 60mL absolute ethanol , under nitrogen, heated to reflux. 15mL of hydrazine hydrate was slowly added dropwise to the three-necked flask. After the dropwise addition of hydrazine hydrate, the reaction was continued for 2 h. The product was filtered while hot, poured into deionized water after cooling, and a pale yellow solid was precipitated. Filtration, the yellow filter cake was recrystallized from ethanol water, and placed in a vacuum oven at 60°C to obtain 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl. The yield is 86%, the infrared spectrum of the tested sample is shown in Figure 1, and the hydrogen nuclear magnetic spectrum is shown in Figure 2.

Example 3

This embodiment provides a 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl, and the preparation method is as follows: 1.86g (0.01mol) 4,4 '-Biphenol, 5mL DMF, 1.66g (0.012mol) potassium carbonate and 5mL toluene were added to a 100mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer, respectively. Heat up to boiling with water agent, bring water until no water droplets are produced in the water separator, steam with water agent, after the system is lowered to room temperature, add 2.88g (0.024mol) 3-bromopropene, heat up to 80-100 ℃ The reaction was carried out for 24 hours, poured into deionized water, and filtered to obtain 4,4'-bis(4-allyloxy)biphenyl.

Put all 4,4'-bis(4-allyloxy)biphenyl into the three-necked flask, pass nitrogen protection, slowly heat up to 180-200°C with stirring, react for 1h, and get 3,3'- diallyl-4,4'-biphenol;

Weigh the above rearranged product 2.66g (0.01mol) 3,3'-diallyl-4,4'-biphenol, 3.465 (0.022mol) 4-chloronitrobenzene, 1.66g potassium carbonate, A 100mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer was added, and at the same time, 10mL of solvent DMF and 5mL of toluene with water were added. Pass nitrogen, when the temperature reaches 140 ℃, carry water for 2 hours, and release the water-carrying agent after no water droplets are produced in the water separator. The temperature of the reaction mixture was increased to 160 °C, and the reaction was performed for 6 h. Pour the mixed solution into 300 mL of deionized water to obtain a khaki-yellow precipitate, filter, wash three times with deionized water, and dry in a vacuum oven to obtain 3,3'-diallyl-4,4'-bismuth (4-Nitrophenoxy)biphenyl in about 85% yield.

5.08g (0.01mol) of 3,3'-diallyl-4,4'-bis(4-nitrophenoxy)biphenyl was added to three 100mL ports with mechanical stirring, reflux condenser and thermometer respectively. In the flask, add 0.2 g FeCl ₃ , a spoonful of activated carbon, and then add 60 mL of absolute ethanol, and heat to reflux under nitrogen. 15 mL of hydrazine hydrate was slowly added dropwise to the three-necked flask. After the dropwise addition of hydrazine hydrate, the reaction was continued for 2 h. The product was filtered while hot, poured into deionized water after cooling, and a pale yellow solid was precipitated. Filtration, the yellow filter cake was recrystallized from ethanol water, and placed in a vacuum oven at 60 °C to obtain 3,3'-diallyl-4,4'-bis(4-aminophenoxy)biphenyl, which was The rate was 82%.

Example 4

This embodiment provides an allyl-containing polyetherimide homopolymer, the preparation method of which is as follows: weigh 2.24g (0.005mol) of 3,3'-diallyl-4,4'-di (4-aminophenoxy)biphenyl, under nitrogen protection, was added to a 100 mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer, 18 mL of m-cresol was added, and after it was completely dissolved, 2.22 g (0.005 mol) 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and. After the addition was completed, the mixture was mechanically stirred at room temperature for 1 h to form a viscous polyamide solution. 0.2 mL of isoquinoline was added to the mixture, the temperature was raised to 80 °C, the reaction was continued for 1 h, and then the temperature was raised to 180 °C for 10 h. After cooling, the polymer solution was poured into 200 mL of anhydrous ethanol with stirring to obtain a thin polymer. After filtering, it was washed three times with distilled water and ethanol each, and dried in a vacuum oven at 100° C. for 24 hours to obtain an allyl-containing polyetherimide homopolymer with a yield of 95%.

Figure 4 shows the thermal weight loss curve of the prepared allyl-containing polyetherimide homopolymer in nitrogen, and the 5% thermal weight loss temperature is 490°C, which shows that the polymer has excellent thermal stability.

Example 5

This embodiment provides an allyl-containing polyetherimide homopolymer, and the preparation method is as follows: Weigh 1.12g (0.0025mol) of 3,3'-diallyl-4,4'-di (4-aminophenoxy)biphenyl, 0.5g (0.0025mol) 4,4'-diaminophenyl ether, under nitrogen protection, was added to a 100mL three-necked flask with mechanical stirring, reflux condenser and thermometer , 15 mL of m-cresol was added, and after it was completely dissolved, 2.22 g (0.005 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride was added to the solution. After the addition was completed, the mixture was mechanically stirred at room temperature for 1 h to form a viscous polyamide solution. 0.2 mL of isoquinoline was added to the mixture, the temperature was raised to 80 °C, the reaction was continued for 1 h, and then the temperature was raised to 180 °C for 10 h. After cooling, the polymer solution was poured into 200 mL of anhydrous ethanol with stirring to obtain a thin polymer. After filtration, it was washed three times with distilled water and ethanol each, and dried in a vacuum oven at 100° C. for 24 hours to obtain a polyetherimide copolymer with 50% allyl content in a yield of 96%.

Example 6

This embodiment provides an allyl-containing polyetherimide homopolymer, the preparation method of which is as follows: weigh 2.24g (0.005mol) of 3,3'-diallyl-4,4'-di (4-aminophenoxy)biphenyl, under nitrogen protection, was added to a 100 mL three-necked flask with mechanical stirring, a reflux condenser and a thermometer, 18 mL of m-cresol was added, and after it was completely dissolved, 2.22 g (0.005 mol) 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. After the addition, the mixture was mechanically stirred at room temperature for 24h to form a viscous polyamic acid solution. Then add 0.2 mL of pyridine and 0.4 mL of acetic anhydride to the mixture, continue the reaction for 8 hours at 60 °C in an oil bath, pour it into absolute ethanol, and white flocs appear, which are filtered and evaporated. The pomegranate water and ethanol were washed three times each, and dried in a vacuum oven at 100° C. for 24 hours to obtain an allyl-containing polyetherimide homopolymer with a yield of 96%.

Example 7

This embodiment provides an allyl-containing polyetherimide homopolymer, and the preparation method is as follows: Weigh 1.12g (0.0025mol) of 3,3'-diallyl-4,4'-di (4-aminophenoxy)biphenyl, 0.5g (0.0025mol) 4,4'-diaminophenyl ether, under nitrogen protection, was added to a 100mL three-necked flask with mechanical stirring, reflux condenser and thermometer , 15 mL of m-cresol was added, and after it was completely dissolved, 2.22 g (0.005 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride was added. After the addition, the mixture was mechanically stirred at room temperature for 24h to form a viscous polyamic acid solution. Add 0.2 mL of pyridine and 0.4 mL of acetic anhydride to the mixture, continue the reaction in an oil bath at 60°C for 8 h, pour it into absolute ethanol, and white flocs appear, which are filtered and evaporated. The pomegranate water and ethanol were washed three times each. After drying in a vacuum oven at 100° C. for 24 hours, a polyetherimide copolymer with an allyl content of 50% was obtained, and the yield was 95%.

Example 8

This embodiment discloses a cross-linked polyetherimide film, the preparation method of which is as follows: weigh 0.3 g of polyetherimide homopolymer containing allyl groups and add it into a 50 mL single-neck bottle; Methylformamide (DMAc) 10 mL. After stirring and dissolving, the polymer solution was filtered with a 0.45 μm syringe filter, and after standing for 2 h, it was poured into a clean 10 cm × 10 cm Teflon plate. Dry in an oven at 60°C for 24h until the solvent evaporates and then drop to room temperature. A small amount of deionized water was dropped on the tetrafluoro plate, and the transparent allyl-containing fluoropolyetherimide film was taken out.

The obtained allyl-containing fluoropolyetherimide film was put into a vacuum oven, the temperature was raised to 180°C, and the temperature was maintained for 6 h to obtain a thermally cross-linked polyimide film.

Example 9

This embodiment discloses a cross-linked polyetherimide film, the preparation method of which is as follows: weigh 0.3 g of polyetherimide homopolymer containing allyl groups and add it into a 50 mL single-neck bottle; Methylformamide (DMAc) 10mL, add 2% photoinitiator (1-hydroxycyclohexyl phenyl ketone). After stirring and dissolving, the polymer solution was filtered with a 0.45 μm syringe filter, and after standing for 2 h, it was poured into a clean 10cm×10cm PTFE plate. Dry in an oven at 60°C for 24h until the solvent evaporates and then drop to room temperature. A small amount of deionized water was dropped on the tetrafluoro plate, and the transparent allyl-containing fluoropolyetherimide film was taken out.

The obtained allyl-containing fluoropolyetherimide film is irradiated under an ultraviolet lamp for 0.5 h to obtain a cross-linked polyetherimide film. The infrared spectrum is shown in Figure 3.

Example 10

This embodiment discloses a cross-linked polyetherimide film, the preparation method of which is as follows: Weigh 0.3 g of an allyl-containing polyetherimide homopolymer, add it into a 50 mL three-necked bottle, N,N'- 10 mL of dimethylformamide (DMAc) was added with 0.01 g of hydrogen-terminated polydimethylsiloxane and 1 mg of chloroplatinic acid catalyst. After stirring and dissolving, filter the polymer solution with a 0.45 μm syringe filter, pour it into a clean 10cm×10cm PTFE plate, place it at room temperature for 2 hours, transfer it to a 60°C oven for 24 hours until the solvent evaporates, take out A silicon-hydrogen cross-linked, polyetherimide film was obtained.

Example 11

This embodiment discloses a cross-linked polyetherimide film, the preparation method of which is as follows: Weigh 0.3 g of an allyl-containing polyetherimide homopolymer, put it into a 50 mL three-necked bottle under nitrogen protection, and add N , N'-dimethylformamide (DMAc) 10mL, add 0.06g 1,2-ethanedithiol and 1mg dimethylolpropionic acid (DMPA). After stirring and dissolving, the polymer solution was filtered with a 0.45 μm syringe filter, quickly poured into a clean 10cm×10cm teflon plate, and placed in a 60°C vacuum oven. Incubate for 24h until the solvent evaporates, and then take out the thiol-crosslinked fluoropolyetherimide film.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (10)

1. An allyl-containing diamine monomer characterized by having pendant diallyl groups and the formula:

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:

wherein: wherein n is the degree of polymerization and n is an integer;

R ₁ comprises the following steps:

one of (1);

R ₂ comprises the following steps:

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.

Images