CN115703873B - Method for continuously preparing main chain type benzoxazine derivative - Google Patents
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Abstract
The invention discloses a method for continuously preparing main chain type benzoxazine derivatives, which comprises the following steps: the formaldehyde aqueous solution enters from the liquid inlet of the first sample injection pump, the amine compound solution enters from the liquid inlet of the second sample injection pump, then the amine compound solution is converged through the three-way valve, the phenol compound solution enters through the liquid inlet of the third sample injection pump, then the phenol compound solution enters into the micro-channel reaction tube through the three-way valve and the converged solution together through the liquid inlet of the micro-channel reaction tube, the reaction is carried out in the micro-channel reaction tube, the reaction liquid after the reaction is completed enters into the back pressure valve through the liquid inlet of the back pressure valve, the solvent is removed from the liquid coming out from the liquid outlet of the back pressure valve, and the main chain type benzoxazine derivative is obtained through vacuum drying; the invention has simple equipment, convenient operation, short reaction time, high molecular weight of the product, continuous production and industrial application.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for continuously preparing main chain benzoxazine derivatives.
Background
The benzoxazine is a benzo six-membered heterocyclic compound containing oxygen atoms and nitrogen atoms, which is obtained by one-step reaction of phenolic compounds, amine compounds and formaldehyde, and is polymerized into the benzoxazine by heating and autocatalysis, and the polymer has a plurality of unique advantages and mainly comprises (1) almost zero volume change rate in the curing process, (2) flexible molecular design, (3) no catalyst and no byproduct generation in the curing process, (4) high glass transition temperature, (5) high heat resistance, (6) low water absorption rate, (7) low dielectric constant, (8) low surface free energy and the like. Based on the characteristics, the polybenzoxazine resin has been widely applied to the fields of high-temperature resistance, electric insulation, halogen-free flame retardance, aerospace ablation resistance, electronic packaging and the like. However, the problems of low polymer crosslinking density, poor flexibility and the like caused by the strong rigidity of the benzoxazine molecule and the hydrogen bond structure in the benzoxazine crosslinking network further influence the performance of each aspect of the polymer. Therefore, the main chain type benzoxazine synthesized by taking diamine and dihydric phenol as raw materials becomes an optimal scheme for breaking through the defects of the traditional benzoxazine.
The patent application with publication number of CN112142935A reports a preparation method of quaternary ammonium group-containing main chain benzoxazine, successfully prepares a polybenzoxazine film with good flexibility, and proposes application of the polybenzoxazine film in a fuel cell of an anion exchange membrane. The patent application with publication number of CN110818868A adopts a monoamine end-capping method to prepare main chain benzoxazine copolymer resin, obtains excellent thermal performance and toughness on the basis of keeping high crosslinking density of the main chain benzoxazine resin, and has extremely low dielectric constant (2.0-3.0) and dielectric loss (0.003-0.013) at ultrahigh frequency (10 GHz). Patent application publication No. CN110894274A discloses bio-based main chain benzoxazine based on daidzein, and the obtained material not only has good corrosion resistance, but also has excellent intrinsic antibacterial and algicidal capabilities. However, the traditional batch kettle type method is mainly adopted in the current benzoxazine synthesis, the reaction time is long, and the reaction time is preferably more than 3-24 hours; the batch feeding is needed, the working procedure is complex, and the safety is uncontrollable; large equipment volume, difficult industrial amplification, high industrial production cost and the like.
In view of the above, a simple, low-cost and continuous synthesis method of a main chain benzoxazine derivative is an urgent technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a method for continuously preparing main chain benzoxazine derivatives, which aims to solve the technical problems of complex process, long reaction time, potential safety hazard and the like in the existing preparation technology.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a method for continuously preparing main chain benzoxazine derivatives, which comprises the following steps:
the formaldehyde aqueous solution enters from the liquid inlet of the first sample injection pump, the amine compound solution enters from the liquid inlet of the second sample injection pump, then the amine compound solution is converged through the three-way valve, the phenol compound solution enters from the liquid inlet of the third sample injection pump, then the solution enters into the micro-channel reaction tube through the liquid inlet of the micro-channel reaction tube together with the converged solution through the three-way valve, the flow rates of the first sample injection pump, the second sample injection pump and the third sample injection pump are all controlled to be 0.05-20 mL/min, the reaction temperature is 60-140 ℃ and the residence time is 1-180 minutes, the pressure of the reaction system is normal pressure to 5.0MPa, the molar ratio of the phenol compound, the amine compound and formaldehyde in the reaction system is 1 (1-1.2) (4-5.0) (the solution is prepared after stoichiometric calculation, the proportion in the final round is controlled according to the solution concentration and the flow rate), the reaction solution after the complete reaction enters into the back pressure valve through the liquid inlet of the back pressure valve, the solution out of the liquid outlet of the back pressure valve is subjected to vacuum drying, and the main chain type benzoxazine derivative is obtained;
the device used by the method for continuously preparing the main chain benzoxazine derivative comprises a first sample injection pump, a second sample injection pump, a third sample injection pump, a micro-channel reaction tube and a back pressure valve, wherein a liquid inlet and a liquid outlet are formed in the first sample injection pump, a liquid inlet and a liquid outlet are formed in the second sample injection pump, a liquid inlet and a liquid outlet are formed in the third sample injection pump, the liquid outlet of the first sample injection pump is communicated with the liquid outlet of the second sample injection pump through a three-way valve, and then the liquid outlet of the first sample injection pump is respectively connected with the liquid outlet of the third sample injection pump and the liquid inlet of the micro-channel reaction tube through the three-way valve, the liquid outlet of the micro-channel reaction tube is connected with the liquid inlet of the back pressure valve for controlling pressure, and the liquid outlet is formed in the back pressure valve.
The phenolic compound is at least one selected from bisphenol A, bisphenol B, bisphenol F, bisphenol S, bisphenol AF, 4 '-dihydroxydiphenyl ether and 4,4' -dihydroxydiphenyl ketone.
The amine compound is at least one selected from 4,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl ether, 2-bis (4-aminophenyl) propane, 4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl ketone and 2, 2-bis (4-aminophenyl) hexafluoropropane.
The microchannel reaction tube is a stainless steel hollow tube with spiral openings at two ends, the inner diameter of the tube is 0.5-5 mm, and the length of the tube is 0.5-40 m.
The preparation method of the amine compound solution comprises the following steps: and (3) dissolving the amine compound in a solvent to obtain an amine compound solution with the concentration of 0.1mol/ml to the saturated concentration.
The preparation method of the phenolic compound solution comprises the following steps: the phenolic compound is dissolved in a solvent to obtain a phenolic compound solution with the concentration of 0.1mol/ml to the saturation concentration.
The formaldehyde solution is a commercial formaldehyde aqueous solution.
The solvent is at least one of methanol, ethanol, 2-propanol, acetone, toluene, xylene, chloroform, dioxane and tetrahydrofuran.
Weight average molecular weight M of the main chain type benzoxazine derivative w 9000 to 40000.
The molecular weight distribution (PDI) of the main chain type benzoxazine derivative is 1-9.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
in the traditional benzoxazine synthesis, different reactant ratios have great influence on the structure of a product, the product can be mutually converted among various compounds such as Bz, mannich alkali, phenol Mannich bridge dimer and the like, the selectivity of a target product is low, the reaction is generally stopped when the benzoxazine content in a system is highest after more than 5 hours of reaction is needed, and the product is purified by post-treatment modes such as acid washing, alkali washing and the like, so that the problem is more prominent in a complex reaction system of diamine and dihydric phenol. Meanwhile, the traditional batch kettle type reactor has obvious problems of local proportion mismatch and overheating, and causes the problems of long reaction time, multiple side reactions and the like. Compared with the existing intermittent preparation process, the main chain type benzoxazine derivative is prepared through the micro-channel reaction tube, the equipment is simpler, the operation is convenient, the safety is high, the characteristics of high micro-channel heating efficiency, uniform reactant heating and no back mixing are utilized, continuous output and uninterrupted amplified production can be carried out, the reaction time can be obviously shortened, the uniformity of the molecular weight of the main chain type benzoxazine derivative is improved, the flux is high, and the stability of the performance of the subsequent application product is better.
The reactor has the advantages of small size, high heat exchange efficiency and accurate temperature control; the reactant mixing and reaction efficiency is high, and the reaction time is short; the operation is convenient, the residence time of reactants can be accurately controlled, the molecular weight of the product is high, and the molecular weight distribution is adjustable; the device can be continuously produced, and is beneficial to industrial application.
Drawings
FIG. 1 is a process flow diagram of a method for continuously preparing main chain benzoxazine derivatives in an embodiment of the present invention.
Wherein, 1 is first advance kind pump, 2 is the second advance kind pump, 3 is the third advance kind pump, 4 is microchannel reaction tube, 5 is the backpressure valve.
FIG. 2 is a reaction equation for continuously preparing main chain benzoxazine derivatives in example 1 of the present invention.
FIG. 3 is a schematic representation of the preparation of a main chain benzoxazine derivative based on 4,4' -diaminodiphenylmethane and bisphenol A in example 1 of the present invention 1 H NMR nuclear magnetic spectrum.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The process flow chart of the method for continuously preparing the main chain type benzoxazine derivative in the embodiment of the invention is shown in fig. 1, and fig. 1 is the process flow chart of the method for continuously preparing the main chain type benzoxazine derivative in the embodiment of the invention. The device used in the method for continuously preparing the main chain benzoxazine derivative comprises a first sample injection pump 1, a second sample injection pump 2, a third sample injection pump 3, a micro-channel reaction tube 4 and a back pressure valve 5, wherein a liquid inlet and a liquid outlet are formed in the first sample injection pump 1, a liquid inlet and a liquid outlet are formed in the second sample injection pump 2, a liquid inlet and a liquid outlet are formed in the third sample injection pump 3, the liquid outlet of the first sample injection pump 1 is communicated with the liquid outlet of the second sample injection pump 2 through a three-way valve, and then is respectively connected with the liquid outlet of the third sample injection pump 3 and the liquid inlet of the micro-channel reaction tube 4 through the three-way valve, the liquid outlet of the micro-channel reaction tube 4 is connected with the liquid inlet of the back pressure valve 5 for controlling pressure, and the liquid outlet is formed in the back pressure valve 5.
Example 1
A method for continuously preparing main chain benzoxazine derivatives comprises the following steps:
4,4' -diaminodiphenyl methane was dissolved in a toluene-ethanol mixed solvent (toluene to ethanol volume ratio: 8:3) to obtain an amine compound solution having a concentration of 0.75 mol/L.
Bisphenol A was dissolved in a toluene-ethanol mixed solvent (volume ratio of toluene to ethanol: 12:7) to obtain a phenol compound solution having a concentration of 0.48 mol/L.
Introducing commercial formaldehyde aqueous solution (with the concentration of 35% -40%) into the sample injection device from the liquid inlet of the first sample injection pump 1, introducing amine compound solution into the sample injection device from the liquid inlet of the second sample injection pump 2, converging the solution through a three-way valve, introducing phenol compound solution into the sample injection device through the liquid inlet of the third sample injection pump 3, and introducing the solution into the microchannel reaction tube 4 through the liquid inlet of the microchannel reaction tube 4 together with the converged solution through the three-way valve, wherein the microchannel reaction tube is a stainless steel hollow tube with spiral openings at two ends, the inner diameter of the tube is 2mm, and the length of the tube is 8m; the flow rate of the first sample injection pump 1 is controlled to be 2mL/min, the flow rate of the second sample injection pump 2 is controlled to be 7mL/min, the flow rate of the third sample injection pump 3 is controlled to be 11mL/min, the reaction temperature is 100 ℃ and the residence time is 5 minutes in the microchannel reaction tube 4, the pressure of the reaction system is 3MPa, the molar ratio of phenolic compounds, amine compounds and formaldehyde in the reaction system is 1:1:4.5, the reaction liquid after the reaction is completed enters the back pressure valve 5 through the liquid inlet of the back pressure valve 5, the solvent is removed from the liquid outlet of the back pressure valve 5, the product is dried in vacuum at 80 ℃ for 24 hours, and the main chain benzoxazine derivative is obtained, and the product yield is 85%.
The reaction equation is shown in fig. 2, and fig. 2 is a reaction equation for continuously preparing the main chain benzoxazine derivative in the embodiment 1 of the present invention. The nuclear magnetic pattern of the product is shown in FIG. 3, FIG. 3 is a diagram showing the preparation of main chain type benzoxazine derivative based on 4,4' -diaminodiphenylmethane and bisphenol A in example 1 of the present invention 1 H NMR nuclear magnetic spectrum. 1 H NMR(400MHz,Chloroform-d,ppm)δ6.8-7.3(ArH),5.24(O-CH 2 -N),4.49(C-CH 2 -N),3.77(Ar-CH 2 -Ar),1.54(Ar-C-(CH 3 ) 2 )。
Example 2
A method for continuously preparing main chain benzoxazine derivatives comprises the following steps:
4,4' -diaminodiphenyl ether was dissolved in ethanol to obtain an amine compound solution having a concentration of 0.83 mol/L.
Bisphenol S was dissolved in ethanol to obtain a phenol compound solution having a concentration of 0.47 mol/L.
Introducing commercial formaldehyde aqueous solution (with the concentration of 35% -40%) into the sample injection device from the liquid inlet of the first sample injection pump 1, introducing amine compound solution into the sample injection device from the liquid inlet of the second sample injection pump 2, converging the solution through a three-way valve, introducing phenol compound solution into the sample injection device through the liquid inlet of the third sample injection pump 3, and introducing the solution into the microchannel reaction tube 4 through the liquid inlet of the microchannel reaction tube 4 together with the converged solution through the three-way valve, wherein the microchannel reaction tube is a stainless steel hollow tube with spiral openings at two ends, the inner diameter of the tube is 1mm, and the length of the tube is 32m; the flow rate of the first sample injection pump 1 is controlled to be 0.3mL/min, the flow rate of the second sample injection pump 2 is controlled to be 1.2mL/min, the flow rate of the third sample injection pump 3 is controlled to be 1.9mL/min, the reaction is carried out in the micro-channel reaction tube 4, the reaction temperature is 130 ℃, the residence time is 30 minutes, the pressure of the reaction system is 5MPa, the mole ratio of phenolic compounds, amine compounds and formaldehyde in the reaction system is 1:1.1:4, the reaction liquid after the reaction is completed enters the back pressure valve 5 through the liquid inlet of the back pressure valve 5, the solvent is removed from the liquid coming out from the liquid outlet of the back pressure valve 5, and the main chain benzoxazine derivative is obtained through vacuum drying for 24 hours at 60 ℃, and the product yield is 90%. 1 H NMR(400MHz,DMSO-d,ppm)δ6.8-7.8(ArH),4.86(O-CH 2 -N),3.98(C-CH 2 -N)。
Example 3
A method for continuously preparing main chain benzoxazine derivatives comprises the following steps:
4,4' -diaminodiphenyl sulfone was dissolved in chloroform to obtain an amine compound solution having a concentration of 3.75 mol/L.
Bisphenol F was dissolved in chloroform to obtain a phenol compound solution having a concentration of 2.27 mol/L.
Introducing commercial formaldehyde aqueous solution (with the concentration of 35% -40%) into the micro-channel reaction tube 4 through the liquid inlet of the micro-channel reaction tube 4 together with the mixed solution, introducing amine compound solution into the micro-channel reaction tube 4 through the liquid inlet of the micro-channel reaction tube 4, wherein the amine compound solution is introduced into the micro-channel reaction tube 4 through the liquid inlet of the third sample pump 3, and then the three-way valve is used for converging the amine compound solutionThe stainless steel hollow pipe with openings at two ends in a spiral shape has the inner diameter of 3.5mm and the length of 15m; the flow rate of the first sample injection pump 1 is controlled to be 3.6mL/min, the flow rate of the second sample injection pump 2 is controlled to be 2.3mL/min, the flow rate of the third sample injection pump 3 is controlled to be 3.8mL/min, the reaction is carried out in the micro-channel reaction tube 4, the reaction temperature is 60 ℃, the residence time is 60 minutes, the pressure of the reaction system is 5MPa, the mole ratio of phenolic compounds, amine compounds and formaldehyde in the reaction system is 1:1:5, the reaction liquid after the reaction is completely enters the back pressure valve 5 through the liquid inlet of the back pressure valve 5, the solvent is removed from the liquid outlet of the back pressure valve 5, the reaction liquid is dried in vacuum for 24 hours at 40 ℃, and the main chain benzoxazine derivative is obtained, and the product yield is 80%. 1 H NMR(400MHz,Chloroform-d,ppm)δ6.8-7.3(ArH),5.53(O-CH 2 -N),4.62(C-CH 2 -N),3.78(Ar-CH 2 -Ar)。
Molecular weight of the Main chain benzoxazine derivatives prepared in examples 1 to 3 Using gel permeation chromatography Agilent PL-GPC50, tetrahydrofuran as Mobile phase solvent, flow Rate 1.0mL/min, weight average molecular weight M of the Main chain benzoxazine derivatives was tested w And molecular weight distribution (PDI), as shown in table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Weight average molecular weight M w | 10339 | 9591 | 33880 |
| PDI | 3.34 | 4.38 | 8.04 |
From the data in Table 1, it is shown that the invention successfully prepares the main chain benzoxazine derivative with high molecular weight.
Taking the structure of example 3 as an example, a repeat unit having a molecular weight of about 500 may be referred to as a monomer having a molecular weight of 500, a dimer having a factor of 2, a trimer having a factor of 3, and a high molecular weight having a factor of 4 or more, that is, 2000 or more. The smaller the PDI, the narrower the molecular weight distribution, the theoretically not lower than 1, infinitely close to 1, and when 1, all the molecular weights are consistent, the larger the PDI difference of the invention, the molecular weight distribution can be controlled by the reaction condition, and the products with different molecular weights and distributions can be prepared according to the actual requirements.
Comparative example 1
The patent application with publication number CN112142935A adopts an intermittent method to synthesize main chain benzoxazine, the reaction time is 3-24 hours, the post-treatment requires multiple times of washing by multiple solvents, and continuous production cannot be realized.
Comparative example 2
The patent application with publication number CN110818868A adopts an intermittent method to synthesize main chain benzoxazine, reaction takes 6-48 hours, post-treatment requires methanol solution to precipitate a product and standing for 24 hours for separating liquid, and continuous production cannot be realized.
Comparative example 3
The patent application with publication number CN110894274A adopts an intermittent method to synthesize main chain benzoxazine, the reaction raw materials are stirred for 0.5 to 4 hours at the temperature of 25 to 60 ℃ and then react for 3 to 30 hours, and continuous production cannot be realized.
The comparison shows that the method can realize continuous production of main chain benzoxazine, has short reaction time, simple and high post-treatment process, high product molecular weight (more than 18 repeating units), and can control the product molecular weight and distribution by regulating and controlling process conditions.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (7)
1. The method for continuously preparing the main chain type benzoxazine derivative is characterized by comprising the following steps of:
the formaldehyde aqueous solution enters from the liquid inlet of the first sample injection pump, the amine compound solution enters from the liquid inlet of the second sample injection pump, then the amine compound solution is converged through the three-way valve, the phenol compound solution enters through the liquid inlet of the third sample injection pump, then the mixed solution enters into the micro-channel reaction tube through the liquid inlet of the micro-channel reaction tube together with the converged solution through the three-way valve, the flow rates of the first sample injection pump, the second sample injection pump and the third sample injection pump are all controlled to be 0.05-20 mL/min, the reaction temperature is 60-140 ℃ and the residence time is 1-180 minutes, the pressure of the reaction system is normal pressure to 5.0MPa, the molar ratio of the phenol compound, the amine compound and formaldehyde in the reaction system is 1 (1-1.2): (4-5.0), the reaction solution after the reaction is completely enters into the back pressure valve through the liquid inlet of the back pressure valve, the solvent is removed from the liquid outlet of the back pressure valve, and the main chain type benzoxazine derivative is obtained through vacuum drying;
the device used by the method for continuously preparing the main chain benzoxazine derivative comprises a first sample injection pump, a second sample injection pump, a third sample injection pump, a micro-channel reaction tube and a back pressure valve, wherein the first sample injection pump is provided with a liquid inlet and a liquid outlet, the second sample injection pump is provided with the liquid inlet and the liquid outlet, the third sample injection pump is provided with the liquid inlet and the liquid outlet, the liquid outlet of the first sample injection pump is communicated with the liquid outlet of the second sample injection pump through a three-way valve, and then is respectively connected with the liquid outlet of the third sample injection pump and the liquid inlet of the micro-channel reaction tube through the three-way valve, the liquid outlet of the micro-channel reaction tube is connected with the liquid inlet of the back pressure valve for controlling pressure, and the back pressure valve is provided with the liquid outlet;
the phenolic compound is at least one selected from bisphenol A, bisphenol B, bisphenol F, bisphenol S, bisphenol AF, 4 '-dihydroxydiphenyl ether and 4,4' -dihydroxydiphenyl ketone;
the amine compound is at least one selected from 4,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl ether, 2-bis (4-aminophenyl) propane, 4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl ketone and 2, 2-bis (4-aminophenyl) hexafluoropropane.
2. The method for continuously preparing the main chain benzoxazine derivative according to claim 1, wherein the microchannel reaction tube is a stainless steel hollow tube with spiral openings at two ends, the inner diameter of the tube is 0.5-5 mm, and the length of the tube is 0.5-40 m.
3. The method for continuously preparing the main chain type benzoxazine derivative according to claim 1, wherein the preparation method of the amine compound solution comprises the following steps: and (3) dissolving the amine compound in a solvent to obtain an amine compound solution with the concentration of 0.1mol/ml to the saturated concentration.
4. The method for continuously preparing the main chain type benzoxazine derivative according to claim 1, wherein the preparation method of the phenolic compound solution comprises the following steps: the phenolic compound is dissolved in a solvent to obtain a phenolic compound solution with the concentration of 0.1mol/ml to the saturation concentration.
5. The method for continuously producing a main chain benzoxazine derivative according to claim 1, wherein the solvent is at least one of methanol, ethanol, 2-propanol, acetone, toluene, xylene, chloroform, dioxane, and tetrahydrofuran.
6. The method for continuously preparing main chain type benzoxazine derivatives according to claim 1, wherein the weight average molecular weight M of the main chain type benzoxazine derivatives w 9000 to 40000.
7. The method for continuously preparing the main chain type benzoxazine derivatives according to claim 1, wherein the molecular weight distribution of the main chain type benzoxazine derivatives is 1-9.
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