CN112552482B - Bio-based phosphaphenanthrene biphenyl type epoxy resin as well as preparation method and application thereof - Google Patents

Bio-based phosphaphenanthrene biphenyl type epoxy resin as well as preparation method and application thereof Download PDF

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CN112552482B
CN112552482B CN202011345306.2A CN202011345306A CN112552482B CN 112552482 B CN112552482 B CN 112552482B CN 202011345306 A CN202011345306 A CN 202011345306A CN 112552482 B CN112552482 B CN 112552482B
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epoxy resin
phosphaphenanthrene
magnolol
dopo
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CN112552482A (en
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张笑晴
刘思慧
胡国梁
刘璟宏
雷彩红
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus

Abstract

The invention belongs to a flame-retardant epoxy treeThe technical field of resin, and discloses a bio-based phosphaphenanthrene biphenyl epoxy resin, a preparation method and application thereof. The molecular structural formula of the bio-based phosphaphenanthrene biphenyl type epoxy resin is as follows:
Figure DDA0002799716320000011
wherein X is
Figure DDA0002799716320000012
Or
Figure DDA0002799716320000013
Y is

Description

Bio-based phosphaphenanthrene biphenyl type epoxy resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of flame-retardant epoxy resins, and particularly relates to a bio-based phosphaphenanthrene biphenyl epoxy resin and a preparation method and application thereof.
Background
The epoxy resin is a high molecular polymer containing two or more than two epoxy groups in the molecule, and is mainly obtained by reacting phenol or alcohol compound containing hydroxyl with epichlorohydrin. Most of the epoxy resins currently in commercial use are bisphenol a type epoxy resins, and environmental pollution and toxicity problems are involved in the preparation and use processes, so that attempts have been made to prepare epoxy resins by using biomass materials instead of bisphenol a. However, both bisphenol a epoxy resin and bio-based epoxy resin have flame retardant properties that are difficult to satisfy for applications in the fields of electronics, aviation, and the like.
In order to achieve a good flame retardant effect, the addition of a halogen flame retardant to an epoxy resin tends to significantly reduce the flammability of the epoxy resin. However, these halogen-containing flame retardants release highly toxic gases during combustion, which is in conflict with sustainable and green chemistry. Therefore, halogen-free flame-retardant epoxy resin is more and more concerned by people, flame-retardant additives containing phosphorus, silicon and the like are more environment-friendly and show satisfactory flame-retardant effect, but the flame-retardant additives are poor in compatibility with matrix resin and can reduce the glass transition temperature and mechanical property of the material.
Magnolol is widely applied to Chinese herbal medicines and cosmetic raw materials, and is a low-toxicity biomass material. The magnolol has a high-rigidity biphenyl structure in a molecular structure, and two sides of the biphenyl have two reactive groups, namely phenolic hydroxyl and flexible allyl. Under appropriate reaction conditions, the allyl group can serve as a reaction site for introducing the DOPO functional group. Therefore, by reasonable molecular structure design and taking bio-based magnolol and DOPO as raw materials, the phosphaphenanthrene epoxy resins with different structures can be obtained, and phosphaphenanthrene materials with different phosphorus contents can be obtained.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the invention aims to provide a bio-based phosphaphenanthrene biphenyl type epoxy resin.
The invention also aims to provide a preparation method of the bio-based phosphaphenanthrene biphenyl type epoxy resin, which is used for preparing the bio-based phosphaphenanthrene biphenyl type epoxy resin P-EP-DOPO-n with different molecular weights by regulating and controlling the reaction parameters of the bio-based epoxy resin P-DBP-EP-n and DOPO.
The invention also aims to provide a preparation method of the bio-based phosphaphenanthrene biphenyl type epoxy resin, and the epoxy resin is used for preparing the bio-based phosphaphenanthrene biphenyl type epoxy resin P-DBP-DOPO-n with different phosphorus contents by regulating and controlling the reaction parameters of a bio-based magnolol epoxy monomer EDBP and a magnolol phosphaphenanthrene biphenyl type monomer DBP-DOPO-n.
The invention finally aims to provide the application of the bio-based phosphaphenanthrene biphenyl type epoxy resin.
The purpose of the invention is realized by the following technical scheme:
a bio-based phosphaphenanthrene biphenyl type epoxy resin has a molecular structural formula as follows:
Figure BDA0002799716310000021
wherein X is
Figure BDA0002799716310000022
Y is
Figure BDA0002799716310000023
n is an integer greater than or equal to zero.
Preferably, when both X and Y are
Figure BDA0002799716310000024
When the bio-based phosphaphenanthrene biphenyl type epoxy resin is abbreviated as P-EP-DOPO-n, the molecular structural formula of the bio-based phosphaphenanthrene biphenyl type epoxy resin is as follows:
Figure BDA0002799716310000025
the preparation method of the bio-based phosphaphenanthrene biphenyl type epoxy resin comprises the following specific steps:
s1, mixing magnolol, epoxy chloropropane and a catalyst, heating to 60-100 ℃ in a nitrogen atmosphere, dropwise adding an alkaline solution, heating to 80-150 ℃, reacting for 2-6 hours under an alkaline condition, stopping the reaction, and cooling to room temperature to obtain a bio-based magnolol epoxy resin P-DBP-EP-n;
s2, mixing the bio-based magnolol epoxy resin P-DBP-EP-n with DOPO, a photoinitiator and a solvent, placing the mixture under ultraviolet irradiation for reaction for 2-4 h, and removing excessive DOPO by using a chromatographic column through reaction liquid after the reaction is finished to prepare the P-EP-DOPO-n.
Preferably, the molar ratio of magnolol to epichlorohydrin in step S1 is controlled by the ratio of epoxy group to phenolic hydroxyl group, where epoxy group/phenolic hydroxyl group = 2-12; the catalyst is butyl triphenyl phosphonium bromide, benzyl triethyl ammonium chloride or tetrabutyl ammonium bromide; the catalyst is 0.1 to 0.5 weight percent of the total mass of magnolol and epichlorohydrin; the alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
Preferably, the molar ratio of DOPO to bio-based magnolol epoxy resin P-DBP-EP-n in step S2 is controlled by the ratio of phosphorus-hydrogen bond to allyl group, phosphorus-hydrogen bond/allyl group = 2-6; the photoinitiator is a photoinitiator 651, a photoinitiator 127 or a photoinitiator 369, and the dosage of the photoinitiator is 0.3 to 0.5 equivalent of that of P-DBP-EP-n; the volume ratio of the DOPO to the solvent is (1-2) g:1mL; the solvent is tetrahydrofuran or 1, 4-dioxane.
Preferably, when said X is
Figure BDA0002799716310000031
And Y is
Figure BDA0002799716310000032
The bio-based phosphaphenanthrene biphenyl type epoxy resin is abbreviated as P-DBP-DOPO-n, and the molecular structural formula of the bio-based phosphaphenanthrene biphenyl type epoxy resin is as follows:
Figure BDA0002799716310000033
the preparation method of the bio-based phosphaphenanthrene biphenyl type epoxy resin comprises the following specific steps:
s1, mixing magnolol, DOPO, a photoinitiator and a solvent, then placing the mixture under the irradiation of ultraviolet light for reaction for 2-4 h, and after the reaction is finished, enabling the reaction solution to pass through a chromatographic column to remove excessive DOPO, so as to prepare a magnolol phosphaphenanthrene biphenyl monomer DBP-DOPO;
s2, mixing magnolol, epoxy chloropropane and a catalyst, heating to 60-100 ℃ in a nitrogen atmosphere, dropwise adding an alkaline solution, heating to 80-150 ℃, reacting for 2-6 h under an alkaline condition, stopping the reaction, and cooling to room temperature to obtain a bio-based magnolol epoxy monomer EDBP;
s3, mixing the bio-based magnolol epoxy monomer EDBP, a magnolol phosphaphenanthrene biphenyl monomer DBP-DOPO and a catalyst, heating to 60-100 ℃, uniformly mixing, adding the catalyst, continuously heating to 80-150 ℃, reacting for 2-6 h, stopping the reaction, and cooling to room temperature to obtain the P-DBP-DOPO-n.
Preferably, the molar ratio of magnolol and DOPO in step S1 is controlled by the ratio of phosphorus-hydrogen bond to allyl group, with phosphorus-hydrogen bond/allyl group = 2-6; the photoinitiator is photoinitiator 651, photoinitiator 127 or photoinitiator 369, and the dosage of the photoinitiator is 0.3 to 0.5 equivalent of magnolol; the mass ratio of the DOPO to the solvent is (1-2) g:1mL; the solvent is tetrahydrofuran or 1, 4-dioxane.
Preferably, the molar ratio of magnolol to epichlorohydrin in step S2 is controlled by the ratio of epoxy group to phenolic hydroxyl group, and the ratio of epoxy group to phenolic hydroxyl group is 2-3; the catalyst is butyl triphenyl phosphonium bromide, benzyl triethyl ammonium chloride or tetrabutyl ammonium bromide; the catalyst is 0.1 to 0.5 weight percent of the total mass of magnolol and epoxy chloropropane; the alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
Preferably, the molar ratio of the bio-based magnolol epoxy monomer EDBP and magnolol phosphaphenanthrene biphenyl type monomer DBP-DOPO described in the step S3 is controlled by the ratio of epoxy group and phenolic hydroxyl group, and the ratio of epoxy group and phenolic hydroxyl group is 4-12; the catalyst is butyl triphenyl phosphonium bromide, benzyl triethyl ammonium chloride or tetrabutyl ammonium bromide, and the dosage of the catalyst is 0.1-0.5 wt% of the total mass of magnolol and epichlorohydrin.
The application of the bio-based phosphaphenanthrene biphenyl epoxy resin in the field of flame retardant preparation.
The bio-based phosphaphenanthrene biphenyl type epoxy resin provided by the invention has different molecular weights, n is an integer greater than or equal to zero, and the reaction route is shown as formula (1) and formula (2):
Figure BDA0002799716310000041
Figure BDA0002799716310000051
when n =0 in the P-DBP-EP-n, the ratio of epoxy group to phenolic hydroxyl group is 2-3, thus obtaining the bio-based magnolol epoxy monomer (EDBP), and when n is an integer larger than zero in the P-DBP-EP-n, the ratio of epoxy group to phenolic hydroxyl group is 4-12.
The bio-based phosphaphenanthrene biphenyl type epoxy resin provided by the invention has different phosphorus contents, n is an integer greater than zero, and the reaction route is shown as a formula (3) and a formula (4):
Figure BDA0002799716310000052
compared with the prior art, the invention has the following beneficial effects:
1. the high-rigidity biphenyl structure in the bio-based phosphaphenanthrene biphenyl type epoxy resin can improve the thermal stability of the polymer, and thermally-resistant carbon is formed in the combustion process, so that the flame retardance of the polymer is improved.
2. The invention respectively prepares the bio-based phosphaphenanthrene type epoxy resin with different molecular weights and the bio-based phosphaphenanthrene type epoxy resin with different phosphorus contents by a two-step method, the phosphaphenanthrene is proved to be an excellent flame retardant which is positioned at the end group of the epoxy resin, the activity is strong, and the excellent flame retardant effect is more easily achieved, thereby improving the flame retardant property of the epoxy resin.
3. The prepared bio-based phosphaphenanthrene biphenyl epoxy resin is an intrinsic flame-retardant epoxy resin, and compared with other epoxy resins, the cured bio-based phosphaphenanthrene biphenyl epoxy resin has better thermal stability, mechanical property and flame retardant property, and has important significance for promoting the development of high-performance bio-based flame-retardant epoxy resin.
4. The synthetic process of the bio-based phosphaphenanthrene biphenyl type epoxy resin is green and simple, is easy for large-scale production, and has great potential for wide application.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Adding 5g of magnolol (DBP), 6.9g of epoxy chloropropane and 0.06g of butyl triphenyl phosphine bromide into a reaction container, and then stirring at 60 ℃ until the three are uniformly mixed, wherein the molar ratio of the epoxy chloropropane to the magnolol is 4:1, epoxy group/phenolic hydroxyl group =2, and the mass of the catalyst butyl triphenyl phosphonium bromide is 0.5wt% of the total mass of magnolol and epichlorohydrin. Then, 40wt% aqueous sodium hydroxide solution was added dropwise to the mixture and the temperature was further raised to 80 ℃ to react for 3 hours, and then the reaction was stopped. Diluting the reaction solution with ethyl acetate, washing with deionized water for 3 times, extracting the organic layer, drying the organic layer with anhydrous sodium sulfate overnight, filtering, and rotary evaporating to remove solvent to obtain bio-based magnolol epoxy monomer, i.e. P-DBP-EP-0, abbreviated as EDBP.
Of EDBP 1 Characterization of HNMR results were: the absorption peaks were δ =7.09ppm, δ =6.90ppm, (hydrogen on benzene ring). δ =5.98ppm, δ =5.10ppm, δ =5.06ppm (three different hydrogens on the allyl group); δ =3.19ppm, δ =2.74ppm, δ =2.56ppm (different hydrogen in three on the epoxy group).
Example 2
Adding 5g of magnolol, 13.9g of epoxy chloropropane and 0.09g of butyl triphenyl phosphine bromide into a reaction container, and then stirring at 60 ℃ until the three are uniformly mixed, wherein the molar ratio of the epoxy chloropropane to the magnolol is 8:1, epoxy group/phenolic hydroxyl group =4, and the mass of the catalyst butyl triphenyl phosphonium bromide is 0.5wt% of the total mass of magnolol and epichlorohydrin. Then, 40wt% aqueous sodium hydroxide solution was added dropwise to the mixture and the temperature was further raised to 80 ℃ to react for 3 hours, and then the reaction was stopped. Diluting the reaction solution with ethyl acetate, adding deionized water, washing for 3 times, extracting an organic layer, drying the organic layer with anhydrous sodium sulfate overnight, filtering, and performing rotary evaporation to remove the solvent to obtain the bio-based magnolol epoxy resin, which is abbreviated as P-DBP-EP-n (n = 1).
Of P-DBP-EP-n (n = 1) 1 Characterization of HNMR results were: the absorption peaks were δ =7.08ppm, δ =6.92ppm, (hydrogen on benzene ring). δ =5.99ppm, δ =5.10ppm, δ =5.07ppm (three different hydrogens on the allyl group); δ =3.20ppm, δ =2.75ppm, δ =2.56ppm (three different hydrogens on the epoxy group).
Example 3
5g of P-DBP-EP-n (n = 1) of example 2, 6.17g of DOPO, 1.83g of the photoinitiator 651 and 31mL of tetrahydrofuran were charged in a reaction vessel, and then placed under 365nm ultraviolet irradiation for 4 hours. After the reaction is finished, the solvent is removed by rotary evaporation to obtain a yellow oily product. The product was further subjected to column chromatography to remove excessive DOPO and to obtain a bio-based phosphaphenanthrene biphenyl type epoxy resin, abbreviated as P-EP-DOPO-n (n = 1).
Of P-EP-DOPO-n (n = 1) 1 Characterization of HNMR results were: absorption peaks δ = 7.21-7.95 ppm (seven different hydrogens on DOPO); δ =7.00ppm, δ =6.93ppm,6.85ppm (hydrogen on the benzene ring); δ =3.16ppm, δ =2.69ppm, δ =2.51ppm (three different hydrogens on the epoxy group).
The phosphaphenanthrene epoxy resin prepared in this example had an epoxy value of 0.13g/mol and a phosphorus content of 8.21% by weight.
Example 4
5g of magnolol, 16.24g of DOPO, 4.81g of photoinitiator 651 and 81mL of tetrahydrofuran are added into a reaction vessel, and then the mixture is placed under the irradiation of 365nm ultraviolet light for reaction for 4 hours. After the reaction is finished, the tetrahydrofuran is removed by rotary evaporation, and a yellow oily product is obtained. Further passing the product through a chromatographic column to remove excessive DOPO, and obtaining magnolol phosphaphenanthrene biphenyl type monomer, which is abbreviated as DBP-DOPO.
Of DBP-DOPO 1 The characterization results of HNMR are: absorption peaks δ = 7.20-7.96 ppm (seven different hydrogens on DOPO); δ =7.03ppm, δ =6.90ppm,6.86ppm (hydrogen on the benzene ring).
Example 5
5g of bio-based magnolol epoxy monomer EDBP prepared in example 1 and 2.26g of magnolol phosphaphenanthrene biphenyl monomer DBP-DOPO prepared in example 4 are added into a reaction vessel and mixed, the mixture is heated to 60-100 ℃, after uniform mixing, 0.04g of butyl triphenyl phosphonium bromide is added, the temperature is continuously increased to 80-150 ℃, the reaction is stopped after 3 hours of reaction, and bio-based phosphaphenanthrene biphenyl epoxy resin (abbreviated as P-DBP-DOPO-n (n = 1) is obtained.
Of P-DBP-DOPO-1 1 Characterization of HNMR results were: absorption peak δ =7.23 to 7.95ppm (hydrogen on DOPO); δ =7.08ppm, δ =6.92ppm, δ =6.84ppm (hydrogen on the benzene ring). δ =5.98ppm, δ =5.10ppm, δ =5.06ppm (three different hydrogens on the allyl group).
The bio-based phosphaphenanthrene biphenyl type epoxy resin prepared in this example had an epoxy value of 0.14g/mol and a phosphorus content of 4.46wt%.
Example 6
100g of the bio-based phosphaphenanthrene biphenyl type epoxy resin P-EP-DOPO-1 of example 3 was added with 6.44g of curing agent diaminodiphenylmethane (DDM) and stirred uniformly, and vacuum defoamed at room temperature for 2 minutes. Pouring into a mould, and putting into an oven at the temperature of 80 ℃/2 hours +110 ℃/2 hours to obtain the DDM cured P-EP-DOPO-n (n = 1) epoxy resin, which is abbreviated as P-EP-DOPO-1/DDM.
Example 7
100g of the bio-based phosphaphenanthrene epoxy resin P-DBP-DOPO-1 prepared in example 5 was added with 6.93g of curing agent DDM, stirred uniformly, and vacuum defoamed at room temperature for 2 minutes. Pouring into a mould, and putting into an oven at 80 ℃/2 hours +110 ℃/2 hours to obtain the DDM cured P-DBP-DOPO-n (n = 1) epoxy resin, which is abbreviated as P-DBP-DOPO-1/DDM.
Comparative example 1
100g of bisphenol A epoxy resin monomer (E51) was added to 25.25g of curing agent DDM, and the mixture was stirred uniformly and vacuum-defoamed at room temperature for 2 minutes. Pouring into a mould, and putting into an oven at 80 ℃/2 hours +110 ℃/2 hours to obtain the DDM cured E51 epoxy resin, which is abbreviated as E51/DDM.
The glass transition temperature (Tg) was measured by dynamic thermo-mechanical analysis (DMA), defined by the tan delta peak temperature, and the specimen size was 30X 4X 2mm 3 (ii) a The UL94 vertical oxygen index adopts GB/T2408-2008 standard, and the size of the pattern is 120 multiplied by 13 multiplied by 3mm 3 (ii) a The limiting oxygen index adopts GB/T2406-2009, and the sample size is 80 multiplied by 6.5 multiplied by 3mm 3 Result inAs shown in table 1. As can be seen from Table 1, the bio-based phosphaphenanthrene biphenyl type cured epoxy resin P-EP-DOPO-n and P-DBP-DOPO-n contain a high-rigidity biphenyl structure, so that the glass transition temperature of the epoxy resin is obviously higher than that of E51/DDM. In addition, both the UL94 grade and the LOI are superior to those of E51, which indicates that the phosphaphenanthrene biphenyl type epoxy resin has better flame retardant property. The epoxy value of the phosphaphenanthrene epoxy resin prepared by the invention is 0.13-0.14 g/mol, the phosphorus content is 4-9 wt%, and the preferable phosphorus content is 4.5-8.2 wt%, which shows that the application of the bio-based phosphaphenanthrene biphenyl type epoxy resin under different occasions can be provided with flexibility by adjusting the molecular weight and the phosphorus content of the epoxy resin.
TABLE 1 Properties of Phosphaphenanthrene biphenyl type cured epoxy resins prepared in examples 6 to 7
Tg(℃) UL94 rating LOI(％)
E51/DDM 160 - 26
P-EP-DOPO-1/DDM 233 V-0 34
P-DBP-DOPO-1/DDM 235 V-1 30
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. The bio-based phosphaphenanthrene biphenyl type epoxy resin is characterized in that the molecular structural formula of the bio-based phosphaphenanthrene biphenyl type epoxy resin is as follows:
Figure FDA0003856589210000011
wherein X is
Figure FDA0003856589210000012
Y is
Figure FDA0003856589210000013
n is an integer greater than zero.
2. The bio-based phosphaphenanthrene biphenyl type epoxy resin according to claim 1, wherein when both of X and Y are selected from the group consisting of
Figure FDA0003856589210000014
Meanwhile, the bio-based phosphaphenanthrene biphenyl type epoxy resin is abbreviated as P-EP-DOPO-n, and the molecular structural formula of the bio-based phosphaphenanthrene biphenyl type epoxy resin is as follows:
Figure FDA0003856589210000015
3. the preparation method of bio-based phosphaphenanthrene biphenyl type epoxy resin according to claim 2, comprising the following specific steps:
s1, mixing magnolol, epoxy chloropropane and a catalyst, heating to 60-100 ℃ in a nitrogen atmosphere, dropwise adding an alkaline solution, heating to 80-150 ℃, reacting for 2-6 h under an alkaline condition, stopping the reaction, and cooling to room temperature to obtain bio-based magnolol epoxy resin P-DBP-EP-n;
s2, mixing the bio-based magnolol epoxy resin P-DBP-EP-n with DOPO, a photoinitiator and a solvent, placing the mixture under ultraviolet irradiation for reaction for 2-4 h, and removing excessive DOPO by using a chromatographic column through reaction liquid after the reaction is finished to prepare the P-EP-DOPO-n.
4. The method for preparing bio-based phosphaphenanthrene biphenyl type epoxy resin according to claim 3, wherein the molar ratio of magnolol to epichlorohydrin in step S1 is controlled by the ratio of epoxy group to phenolic hydroxyl group, epoxy group/phenolic hydroxyl group = 2-12; the catalyst is butyl triphenyl phosphonium bromide, benzyl triethyl ammonium chloride or tetrabutyl ammonium bromide; the catalyst is 0.1 to 0.5 weight percent of the total mass of magnolol and epichlorohydrin; the alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
5. The method for preparing bio-based phosphaphenanthrene biphenyl type epoxy resin according to claim 3, wherein the molar ratio of DOPO to bio-based magnolol epoxy resin P-DBP-EP-n in step S2 is controlled by the ratio of phosphorus hydrogen bond to allyl group, and phosphorus hydrogen bond/allyl group = 2-6; the photoinitiator is a photoinitiator 651, a photoinitiator 127 or a photoinitiator 369, and the dosage of the photoinitiator is 0.3 to 0.5 equivalent of that of P-DBP-EP-n; the volume ratio of the DOPO to the solvent is (1-2) g:1mL; the solvent is tetrahydrofuran or 1, 4-dioxane.
6. The bio-based phosphaphenanthrene biphenyl of claim 1A process for producing a type epoxy resin, characterized in that when X is
Figure FDA0003856589210000021
And Y is
Figure FDA0003856589210000022
The bio-based phosphaphenanthrene biphenyl type epoxy resin is abbreviated as P-DBP-DOPO-n, and comprises the following specific steps:
s1, mixing magnolol, DOPO, a photoinitiator and a solvent, then placing the mixture under the irradiation of ultraviolet light for reaction for 2-4 h, and after the reaction is finished, enabling the reaction solution to pass through a chromatographic column to remove excessive DOPO, so as to prepare a magnolol phosphaphenanthrene biphenyl monomer DBP-DOPO;
s2, mixing magnolol, epoxy chloropropane and a catalyst, heating to 60-100 ℃ in a nitrogen atmosphere, dropwise adding an alkaline solution, heating to 80-150 ℃, reacting for 2-6 h under an alkaline condition, stopping the reaction, and cooling to room temperature to obtain a bio-based magnolol epoxy monomer EDBP;
s3, mixing the bio-based magnolol epoxy monomer EDBP, a magnolol phosphaphenanthrene biphenyl monomer DBP-DOPO and a catalyst, heating to 60-100 ℃, uniformly mixing, adding the catalyst, continuously heating to 80-150 ℃, reacting for 2-6 h, stopping the reaction, and cooling to room temperature to obtain the P-DBP-DOPO-n.
7. The method for preparing bio-based phosphaphenanthrene biphenyl type epoxy resin according to claim 6, wherein the molar ratio of magnolol and DOPO in step S1 is controlled by the ratio of phosphorus-hydrogen bond to allyl group, and phosphorus-hydrogen bond/allyl group = 2-6; the photoinitiator is photoinitiator 651, photoinitiator 127 or photoinitiator 369, and the dosage of the photoinitiator is 0.3 to 0.5 equivalent of magnolol; the volume ratio of the DOPO to the solvent is (1-2) g:1mL; the solvent is tetrahydrofuran or 1, 4-dioxane;
the molar ratio of the magnolol to the epichlorohydrin in the step S2 is controlled by the ratio of the epoxy group to the phenolic hydroxyl group, and the ratio of the epoxy group to the phenolic hydroxyl group is 2-3; the catalyst is butyl triphenyl phosphonium bromide, benzyl triethyl ammonium chloride or tetrabutyl ammonium bromide; the catalyst is 0.1 to 0.5 weight percent of the total mass of magnolol and epoxy chloropropane; the alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
8. The method for preparing bio-based phosphaphenanthrene biphenyl type epoxy resin according to claim 6, wherein the molar ratio of bio-based magnolol epoxy monomer EDBP and magnolol phosphaphenanthrene biphenyl type monomer DBP-DOPO of step S3 is controlled by the ratio of epoxy group and phenolic hydroxyl group, the ratio of epoxy group and phenolic hydroxyl group is 4-12; the catalyst is butyl triphenyl phosphonium bromide, benzyl triethyl ammonium chloride or tetrabutyl ammonium bromide, and the dosage of the catalyst is 0.1-0.5 wt% of the total mass of magnolol and epichlorohydrin.
9. A DDM solidified bio-based phosphaphenanthrene biphenyl type epoxy resin, which is characterized in that the epoxy resin is prepared by adding the bio-based phosphaphenanthrene biphenyl type epoxy resin of claim 2 or 6 into a curing agent DDM, uniformly stirring, defoaming in vacuum for 2-4 minutes at normal temperature, and solidifying at 80-110 ℃.
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