Biomass furyl phthalonitrile monomer, preparation method thereof and resin composition

Abstract

The invention discloses a biomass furyl phthalonitrile monomer. The biomass furyl phthalonitrile monomer has a structure as shown in a formula 1. According to the biomass furyl phthalonitrile monomer provided by the invention, biomass furyl phthalonitrile resin can be prepared in a thermocuring manner; the raw material of the biomass furyl phthalonitrile monomer is a bio-based source, and the aromatic structure and strong polarity of the biomass furyl phthalonitrile monomer well maintain the thermal properties and mechanical properties of a resin system, so that the adhesive ability of the resin to an adhesive matrix and a reinforcement is improved; and the overall strength of a high-performance adhesive and a resin-based composite material can be improved.

Description

Technical Field

[0001] This application relates to the technical field of polymer materials, and particularly relates to a biomass furanyl phthalonitrile monomer, a preparation method thereof, and a resin composition. Background Art

[0002] Under the background of the development of the manufacturing industry towards high-end, intelligent, and green directions and the "dual carbon" development strategy, bio-based polymer materials have emerged as the times require.

[0003] As a thermosetting polymer material, phthalonitrile resin has the characteristics of high heat resistance, low moisture absorption, good flame retardancy, and dimensional stability due to its multi-aromatic ring structure and the presence of heteroatoms. It is the only thermosetting polymer that can meet the US Navy flammability standard (MIL-STD-2031), and occupies an important position in polymer materials for extreme environments such as aerospace. In recent years, the military manufacturing industry has also put forward the concept of green and sustainable development, and a series of policies and regulatory documents have been issued. For example, the "Development Outline of Green Aviation Manufacturing Industry" jointly issued by the Ministry of Industry and Information Technology and other four departments clearly states that developing green aviation manufacturing is an inevitable requirement for addressing climate change and achieving the sustainable development of the aviation industry, an important direction for the new round of aviation science and technology revolution and industrial transformation, and a major strategic measure to enhance the future competitiveness of the aviation manufacturing industry. However, the phthalonitrile resin in the existing technology has poor wettability to reinforcing fibers, and it is difficult to maintain its thermal and mechanical properties.

[0004] Therefore, developing a monomer containing phthalonitrile groups for synthesizing phthalonitrile resin to improve the wettability, thermal properties, and mechanical properties of the resin is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, this application provides a biomass furanyl phthalonitrile monomer. The monomer raw material is not only of bio-based origin, but also the aromatic structure it possesses enables the thermal and mechanical properties of the resin system to be well maintained. For high-performance adhesives and advanced composites, this strong polar furan ring structure is beneficial to improving the bonding force of the adhesive to the bonding substrate and the interfacial interaction between the resin and the reinforcement, which is conducive to enhancing the overall strength of the resin matrix composite.

[0006] As a bio-based platform compound, 2,5-furandicarboxylic acid can be derived into a variety of bio-based furan monomers, such as furandicarboxylic acid, furandimethanol, furandiamine, and furandicarbonyl chloride, etc., laying a foundation for the preparation of bio-based polymer materials. The furan ring belongs to a rigid aromatic structure. Compared with the petroleum-based benzene ring structure, the thermal and mechanical properties of the synthesized polymer will be well maintained, and its strong polarity will endow the polymer with some special properties.

[0007] The present application provides a biomass furanyl phthalonitrile monomer having the structure of Formula 1:

[0008]

[0009] Wherein, R 1 is selected from

[0010] R 2 is selected from an aryl group.

[0011] In some specific implementation manners, the R 2 is selected from

[0012] Wherein, n is an integer from 1 to 6, and R 3 , R 4 are each independently selected from an alkyl group of C 1 to C 6 or a substituted alkyl group of C 1 to C 6 , and R 5 is selected from

[0013] Wherein, m, o, p are each independently 0, 1, 2; and X is selected from N, O, S.

[0014] In some specific implementation manners, the biomass furanyl phthalonitrile monomer has the structures shown in Formulas 2 to 6; 2 is selected from

[0015]

[0016] In some specific implementation manners, the biomass furanyl phthalonitrile monomer has the structures shown in Formulas 2 to 6;

[0017]

[0018] The present application also provides a preparation method of the above-mentioned biomass furanyl phthalonitrile monomer, including:

[0019] Subjecting a biomass furanyl difluoride monomer of Formula 7, a diphenol monomer of Formula 8 and a nitro phthalonitrile monomer of Formula 9 to a nucleophilic substitution reaction to obtain the biomass furanyl phthalonitrile monomer;

[0020]

[0021] In some specific implementation manners, the temperature of the nucleophilic substitution reaction is from 40°C to 160°C, and can be 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C. The time of the nucleophilic substitution reaction is from 10 h to 24 h, and can be 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 18 h, 20 h, 21 h, 22 h, 23 h, 24 h.

[0022] In this application, first, a biomass furanyl difluoride monomer, a diphenol monomer, a solvent, an azeotropic dehydrating agent, and a catalyst are mixed to carry out the azeotropic dehydration stage in the nucleophilic substitution reaction. In some specific implementation manners, the molar ratio of the biomass furanyl difluoride monomer to the diphenol monomer is 1:(1.8 - 2.5), preferably 1:2. In some specific implementation manners, the temperature of the azeotropic dehydration stage is from 100°C to 160°C, and the time of the azeotropic dehydration stage is from 5 h to 12 h. In some specific implementation manners, the solvent includes but is not limited to one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, or diphenyl sulfone. This application has no special requirements for the selection of the solvent, and the total concentration of the reaction monomers is from 10 wt% to 30 wt%. In some specific implementation manners, the azeotropic dehydrating agent includes but is not limited to one or more of benzene, toluene, xylene, or cyclohexane. This application has no special requirements for the selection of the azeotropic dehydrating agent. In some specific implementation manners, the catalyst includes but is not limited to one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, or potassium hydroxide. This application has no special requirements for the selection of the catalyst.

[0023] In some specific implementation manners, the biomass furanyl difluoride monomer is selected from

[0024]

[0025] In some specific implementation manners, the preparation method of the biomass furanyl difluoride monomer includes: reacting furan dicarbonyl chloride, fluorobenzene, and a Lewis acid catalyst in a first solvent to obtain the biomass furanyl difluoride monomer. In some specific implementation manners, the reaction is carried out in an ice-water bath. In some specific implementation manners, after the reaction is stopped, the system is cooled to room temperature, poured into a second solvent, a solid is precipitated, filtered, dried, and recrystallized to obtain the biomass furanyl difluoride monomer. In some specific implementation manners, the first solvent includes but is not limited to one or more of dichloromethane, tetrachloroethane, tetrahydrofuran, or toluene. This application has no special requirements for the selection of the first solvent. In some specific implementation manners, the Lewis acid catalyst includes but is not limited to aluminum chloride (AlCl 3)、Niobium pentachloride (NbCl 5 )、Iron(III) chloride (FeCl 3 )、Tin(IV) chloride (SnCl 4 )、Titanium(IV) chloride (TiCl 4 ) or Zinc chloride (ZnCl 2 ), and the present application has no special requirements for the selection of the Lewis acid catalyst. In some specific implementation manners, the temperature of the reaction is 30 °C to 100 °C, and the time of the reaction is 2 h to 24 h. In some specific implementation manners, the second solvent includes, but is not limited to, one or more of methanol, ethanol, chloroform, or ether, and the present application has no special requirements for the selection of the second solvent. In some specific implementation manners, the recrystallization system is one or more of N,N-dimethylformamide, chlorobenzene, xylene, toluene, acetonitrile, ethanol, tetrahydrofuran, chloroform, ethyl acetate, cyclohexane, methyl ethyl ketone, acetone, or petroleum ether, and the present application has no special requirements for the selection of the recrystallization system.

[0026] In some specific implementation manners, the diphenol monomer is selected from

[0027] In some specific implementation manners,

[0028] The preparation method of

[0029] comprises: 3 Reacting furandicarbonyl chloride, anisole with a Lewis acid catalyst in a first solvent, adding a reducing agent for reduction to obtain a diphenol monomer. In some specific implementation manners, the first solvent includes, but is not limited to, one or more of dichloromethane, tetrachloroethane, tetrahydrofuran, or toluene, and the present application has no special requirements for the selection of the first solvent. In some specific implementation manners, the Lewis acid catalyst includes, but is not limited to, aluminum chloride (AlCl 5 ), niobium pentachloride (NbCl 3 ), iron(III) chloride (FeCl 4 ), tin(IV) chloride (SnCl 4 ), titanium(IV) chloride (TiCl 2) one or more of them, and there are no special requirements for the selection of the Lewis acid catalyst in this application. In some specific implementation manners, the temperature of the reaction is 30°C to 100°C, and the time of the reaction is 2 h to 24 h. In some specific implementation manners, the reaction is carried out in an ice-water bath. In some specific implementation manners, after the reaction is stopped, the system is cooled to room temperature, poured into a second solvent, a solid is precipitated, filtered and dried, and then a reducing agent is added for reduction. In some specific implementation manners, the second solvent includes, but is not limited to, one or more of methanol, ethanol, chloroform or ether, and there are no special requirements for the selection of the second solvent in this application. In some specific implementation manners, furan dicarbonyl chloride, anisole and the Lewis acid catalyst react in a first solvent to obtain dimethyl ether, and the dimethyl ether is reduced with a reducing agent under a third solvent to obtain a diphenol monomer. In some specific implementation manners, the reducing agent includes, but is not limited to, one or more of concentrated hydroiodic acid, trimethylsilyl iodide or boron tribromide, and there are no special requirements for the selection of the reducing agent in this application. In some specific implementation manners, the molar ratio of the reducing agent to dimethyl ether is 5:1 to 50:1. In some specific implementation manners, the time of the reaction is 2 h to 48 h.

[0030] This application then adds nitro-phthalonitrile monomer to carry out a stabilization reaction in the nucleophilic substitution reaction. In some specific implementation manners, the molar ratio of the biomass furanyl diphenol monomer to the nitro-phthalonitrile monomer is 1:(1.8 - 2.5), preferably 1:2. In some specific implementation manners, the temperature of the stabilization reaction is 40°C to 120°C, and the time of the stabilization reaction is 5 h to 12 h.

[0031] In some specific implementation manners, the nitro-phthalonitrile monomer is selected from

[0032] This application then cools the system to room temperature and precipitates a powdery solid in a sodium hydroxide solution, and a biomass furanyl phthalonitrile monomer is obtained after purification and drying.

[0033] This application also provides a biomass furanyl phthalonitrile resin composition, which includes, by mass: 90 parts to 99 parts of biomass furanyl phthalonitrile monomer and 1 part to 10 parts of a thermal curing accelerator.

[0034] The biomass furanyl phthalonitrile resin composition described in this application includes the above-mentioned biomass furanyl phthalonitrile monomer or the biomass furanyl phthalonitrile monomer prepared by the above-mentioned preparation method. The mass fraction of the biomass furanyl phthalonitrile monomer is 90 parts to 99 parts, and can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts.

[0035] The biomass furanyl phthalonitrile resin composition described in this application includes a curing accelerator. In some specific implementation manners, the curing accelerator includes, but is not limited to, one or more of 4,4-diaminodiphenyl ether, 4,4-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 4,4-diaminodiphenyl methane, or bis(4-(4-aminophenoxy)phenyl)sulfone. This application has no special requirements for the selection of the curing accelerator. The mass fraction of the curing accelerator is 1 part to 10 parts, and it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts.

[0036] This application also provides a preparation method for a biomass furanyl phthalonitrile resin, including:

[0037] Thermally curing the biomass furanyl phthalonitrile monomer and the curing accelerator to obtain the biomass furanyl phthalonitrile resin.

[0038] In some specific implementation manners, the temperature of the thermal curing is 250°C to 400°C, and it can be 250°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, or 400°C. The time of the thermal curing is 3h to 10h, and it can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h. The thermal curing is carried out in the presence of the curing accelerator, and the curing accelerator includes, but is not limited to, one or more of 4,4-diaminodiphenyl ether, 4,4-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 4,4-diaminodiphenyl methane, or bis(4-(4-aminophenoxy)phenyl)sulfone. This application has no special requirements for the selection of the curing accelerator.

[0039] The biomass furanyl phthalonitrile monomer provided by this application can be used to prepare the biomass furanyl phthalonitrile resin by thermal curing. Not only is the raw material of the biomass furanyl phthalonitrile monomer of biological origin, but the aromatic structure it possesses also enables the thermal and mechanical properties of the resin system to be well maintained, which is beneficial to improving the wettability of the resin to the reinforcing fiber and conducive to enhancing the overall strength of the resin matrix composite. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 1H NMR spectrum of 2,5-bis(4-fluorobenzoyl)furan provided in Example 1 of this application;

[0041] Figure 2 1H NMR spectrum of 2,5-bis(4-hydroxybenzoyl)furan provided in Example 2 of this application;

[0042] Figure 31H NMR spectrum of the biomass furanyl phthalonitrile monomer provided in Example 3 of the present application;

[0043] Figure 4 1H NMR spectrum of the biomass furanyl phthalonitrile monomer provided in Example 4 of the present application;

[0044] Figure 5 1H NMR spectrum of the biomass furanyl phthalonitrile monomer provided in Example 5 of the present application;

[0045] Figure 6 1H NMR spectrum of the biomass furanyl phthalonitrile monomer provided in Example 6 of the present application. Detailed implementation manners

[0046] It should be understood that the expression "one or more of..." individually includes each of the objects recited after the expression and various different combinations of two or more of the recited objects, unless otherwise understood from the context and usage. The expression "and / or" in combination with three or more recited objects should be understood to have the same meaning, unless otherwise understood from the context.

[0047] The terms "comprising", "having" or "containing", including the use of their grammatical synonyms, should generally be understood as open and non-limiting, for example, not excluding other unrecited elements or steps, unless specifically stated otherwise or understood from the context.

[0048] It should be understood that as long as the present application is still operable, the order of steps or the order of performing certain actions is not important. In addition, two or more steps or actions can be performed simultaneously.

[0049] The use of any and all examples or exemplary language in this document, such as "for example" or "including", is only intended to better illustrate the present application and does not limit the scope of the present application unless a claim is made. No language in this specification should be construed as indicating that any unclaimed element is essential for the practice of the present application.

[0050] In addition, the numerical ranges and parameters used to define the present application are approximate values. The relevant values in the specific embodiments have been presented as precisely as possible herein. However, any value inherently and inevitably contains standard deviations due to individual testing methods. Therefore, unless otherwise clearly stated, it should be understood that all ranges, quantities, values and percentages used in this disclosure are modified by "about". Herein, "about" generally means that the actual value is within plus or minus 10%, 5%, 1% or 0.5% of a specific value or range.

[0051] The present application provides a biomass furanyl phthalonitrile monomer having the structure of Formula 1;

[0052]

[0053] Among them, R 1 is selected from

[0054] R 2 is selected from aryl groups.

[0055] The biomass furanyl phthalonitrile monomer provided by this application can prepare a biomass furanyl phthalonitrile resin by means of thermal curing; not only is the raw material of the biomass furanyl phthalonitrile monomer from a bio-based source, but the aromatic structure it itself has also enables the thermal and mechanical properties of the resin system to be well maintained, which is conducive to improving the wettability of the resin to reinforcing fibers and is beneficial to the improvement of the overall strength of the resin matrix composite.

[0056] The following further elaborates this application in conjunction with embodiments. The protection scope of this application is not limited by the following embodiments.

[0057] Example 1

[0058] This example provides a furanyl difluoride monomer 2,5-bis(4-fluorobenzoyl)furan.

[0059]

[0060] The preparation method of the 2,5-bis(4-fluorobenzoyl)furan includes:

[0061] Add 2,5-furandicarboxylic acid FDCC (173.06 g) and fluorobenzene (259.50 g) into a three-necked flask equipped with a nitrogen inlet and a tail gas treatment device. After complete dissolution, transfer the system to an ice-water bath and slowly add AlCl 3 (336.01 g). After the system stabilizes, remove the ice bath and gradually heat up to 70 °C and reflux for more than 12 h. After stopping the reaction, cool the system to room temperature and then pour it into a methanol solution. Filter out the precipitate and dry it, and perform recrystallization with toluene and n-hexane to obtain a pale yellow crystal. Perform NMR testing on the obtained 2,5-bis(4-fluorobenzoyl)furan, and use nuclear magnetic resonance spectroscopy to characterize the chemical structure of the synthesized monomer. The deuterated reagent is dimethyl sulfoxide-d6, and the obtained 1H NMR spectrum is as shown in Figure 1 shown.

[0062] Example 2

[0063] This example provides a diphenol monomer 2,5-bis(4-hydroxybenzoyl)furan.

[0064]

[0065] The preparation method of 2,5-bis(4-hydroxybenzoyl)furan includes:

[0066] Add FDCC (173.06 g) and anisole (291.60 g) into a three-necked flask equipped with a nitrogen inlet and a tail gas treatment device. After complete dissolution, transfer the system to an ice-water bath, and slowly add AlCl 3 (336.01 g). After the system stabilizes, remove the ice bath, gradually heat up to 50 °C, and reflux for more than 12 h. After stopping the reaction, cool the system to room temperature, and then pour it into a methanol solution. Filter out the precipitate and dry it to obtain light pink solid 2,5-bis(4-methoxybenzoyl)furan. Take 10 mmol of 2,5-bis(4-methoxybenzoyl)furan and dissolve it in 100 mL of dichloromethane (DCM). Cool the system temperature to minus 40 °C, and slowly add a DCM solution of 1 M boron tribromide to the system. After the addition is complete, maintain at minus 40 °C for 2 h, then restore the reaction to room temperature and continue the reaction at room temperature for 24 h. After the reaction is completed, quench the reaction with water, extract with ethyl acetate, and obtain white solid 2,5-bis(4-hydroxybenzoyl)furan by column chromatography. Perform NMR testing on the obtained 2,5-bis(4-hydroxybenzoyl)furan, and the obtained 1H NMR spectrum is as Figure 2 shown.

[0067] Example 3

[0068] This example provides a biomass furanyl phthalonitrile monomer.

[0069]

[0070] The preparation method of the biomass furanyl phthalonitrile monomer includes:

[0071] Add bisphenol A (11.98 g), 2,5-bis(4-fluorobenzoyl)furan (10.93 g) provided in Example 1, potassium carbonate (14.51 g), N,N-dimethylacetamide (108 g) and toluene (36 g) into a three-necked flask equipped with a nitrogen vent. After ventilation for 30 min, heat up the oil bath to 170 °C, and the system temperature is 136 °C. At this time, it is an azeotropic dehydration process. After 8 h, distill out toluene, cool the reaction system to room temperature, add 4-nitrophthalonitrile (13.33 g), heat up the system to 85 °C, and continue the reaction for 10 h. Then cool the system to room temperature and precipitate powder solid in sodium hydroxide solution. After purification and drying, the final product is obtained. Perform NMR testing on the obtained biomass furanyl phthalonitrile monomer, and the obtained 1H NMR spectrum is as Figure 3 shown.

[0072] Example 4

[0073] This embodiment provides a biomass furanyl phthalonitrile monomer.

[0074]

[0075] The preparation method of the biomass furanyl phthalonitrile monomer includes:

[0076] Add bisphenol AF (17.65 g), 2,5-bis(4-fluorobenzoyl)furan (10.93 g) provided in Example 1, potassium carbonate (14.51 g), N,N-dimethylacetamide (126 g) and toluene (42 g) into a three-necked flask equipped with a nitrogen inlet. After aerating for 30 min, raise the oil bath temperature to 170 °C. The system temperature is 136 °C. At this time, it is an azeotropic dehydration process. After 8 h, distill out toluene. Cool the reaction system to room temperature, add 4-nitrophthalonitrile (13.33 g), raise the system temperature to 85 °C, and continue to react for 10 h. Then cool the system to room temperature and precipitate powdery solid in sodium hydroxide solution. After purification and drying, the final product is obtained. Nuclear magnetic resonance test is carried out on the obtained biomass furanyl phthalonitrile monomer, and the obtained nuclear magnetic resonance hydrogen spectrum is as Figure 4 shown.

[0077] Example 5

[0078] This embodiment provides a biomass furanyl phthalonitrile monomer.

[0079]

[0080] The preparation method of the biomass furanyl phthalonitrile monomer includes:

[0081] Add resorcinol (5.78 g), 2,5-bis(4-fluorobenzoyl)furan (10.93 g) provided in Example 1, potassium carbonate (14.51 g), N,N-dimethylacetamide (90 g) and toluene (30 g) into a three-necked flask equipped with a nitrogen inlet. After aerating for 30 min, raise the oil bath temperature to 170 °C. The system temperature is 136 °C. At this time, it is an azeotropic dehydration process. After 8 h, distill out toluene. Cool the reaction system to room temperature, add 4-nitrophthalonitrile (13.33 g), raise the system temperature to 85 °C, and continue to react for 10 h. Then cool the system to room temperature and precipitate powdery solid in sodium hydroxide solution. After purification and drying, the final product is obtained. Nuclear magnetic resonance test is carried out on the obtained biomass furanyl phthalonitrile monomer, and the obtained nuclear magnetic resonance hydrogen spectrum is as Figure 5 shown.

[0082] Example 6

[0083] This embodiment provides a biomass furanyl phthalonitrile monomer.

[0084]

[0085] The preparation method of the biomass furanyl phthalonitrile monomer includes:

[0086] Add biphenol (9.78 g), 2,5-bis(4-fluorobenzoyl)furan (10.93 g) provided in Example 1, potassium carbonate (14.51 g), N,N-dimethylacetamide (102 g) and toluene (34 g) into a three-necked flask equipped with a nitrogen inlet. After aeration for 30 min, raise the oil bath temperature to 170 °C, and the system temperature is 136 °C. At this time, it is the azeotropic dehydration process. After 8 h, distill out toluene. Cool the reaction system to room temperature, add 4-nitrophthalonitrile (13.33 g), raise the system temperature to 85 °C, and continue the reaction for 10 h. Then cool the system to room temperature and precipitate powdery solid in sodium hydroxide solution. After purification and drying, the final product is obtained. The obtained biomass furanyl phthalonitrile monomer was subjected to NMR test, and the obtained 1H NMR spectrum is as Figure 6 shown.

[0087] Example 7

[0088] This example provides a biomass furanyl phthalonitrile resin.

[0089] The preparation method of the biomass furanyl phthalonitrile resin includes:

[0090] The biomass furanyl phthalonitrile monomer provided in Example 3 is mixed with solid powder of bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) and then hot-pressed to preform a tensile spline. The mold uses a self-made mold, and the size is the 1BA type small spline in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature is 150 °C, the pre-pressing pressure is 5 MPa, for three cycles, 3 min each time, the holding pressure is 15 MPa, and the time is 5 min. The preformed spline is placed in a high-temperature oven for thermal curing to obtain the final resin sample. The curing program uses a gradient heating program, and the temperatures are 250 °C, 300 °C, 350 °C, 370 °C respectively, and the time interval is 2 h.

[0091] Example 8

[0092] This example provides a biomass furanyl phthalonitrile resin.

[0093] The preparation method of the biomass furanyl phthalonitrile resin includes:

[0094] The biomass furanyl phthalonitrile monomer provided in Example 4 was mixed with solid powder of bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) and then hot-pressed and preformed into tensile splines. A self-made mold was used, and the size was the 1BA small spline in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature was 150 °C, the pre-pressing pressure was 5 MPa, with three cycles, 3 min for each cycle, the holding pressure was 15 MPa, and the time was 5 min. The preformed splines were placed in a high-temperature oven for thermal curing to obtain the final resin sample. The curing program used a gradient heating program, with temperatures of 250 °C, 300 °C, 350 °C, and 370 °C respectively, and the time interval was 2 h.

[0095] Example 9

[0096] This example provides a biomass furanyl phthalonitrile resin.

[0097] The preparation method of the biomass furanyl phthalonitrile resin includes:

[0098] The biomass furanyl phthalonitrile monomer provided in Example 5 was mixed with solid powder of bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) and then hot-pressed and preformed into tensile splines. A self-made mold was used, and the size was the 1BA small spline in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature was 150 °C, the pre-pressing pressure was 5 MPa, with three cycles, 3 min for each cycle, the holding pressure was 15 MPa, and the time was 5 min. The preformed splines were placed in a high-temperature oven for thermal curing to obtain the final resin sample. The curing program used a gradient heating program, with temperatures of 250 °C, 300 °C, 350 °C, and 370 °C respectively, and the time interval was 2 h.

[0099] Example 10

[0100] This example provides a biomass furanyl phthalonitrile resin.

[0101] The preparation method of the biomass furanyl phthalonitrile resin includes:

[0102] The biomass furanyl phthalonitrile monomer provided in Example 6 was mixed with bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) solid powder and then hot-pressed and preformed into tensile splines. A self-made mold was used, and the size was the 1BA type small spline in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature was 150 °C, the pre-pressing pressure was 5 MPa, with three cycles, 3 min each time, the holding pressure was 15 MPa, and the time was 5 min. The preformed splines were placed in a high-temperature oven for thermal curing to obtain the final resin sample. The curing program used a gradient heating program, with temperatures of 250 °C, 300 °C, 350 °C, and 370 °C respectively, and the time interval was 2 h. The biomass furanyl phthalonitrile monomer provided in Example 6 was mixed with bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) solid powder and then hot-pressed and preformed into tensile splines. A self-made mold was used, and the size was the 1BA type small spline in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature was 150 °C, the pre-pressing pressure was 5 MPa, with three cycles, 3 min each time, the holding pressure was 15 MPa, and the time was 5 min. The preformed splines were placed in a high-temperature oven for thermal curing to obtain the final resin sample. The curing program used a gradient heating program, with temperatures of 250 °C, 300 °C, 350 °C, and 370 °C respectively, and the time interval was 2 h.

[0103] Comparative Example 1

[0104] This comparative example provides a petroleum-based phthalonitrile monomer, and the preparation method includes:

[0105] Bisphenol A (11.98 g), 4,4'-difluorobenzophenone (7.637 g), potassium carbonate (14.51 g), N,N-dimethylacetamide (99 g) and toluene (33 g) were added to a three-necked flask equipped with a nitrogen inlet. After aeration for 30 min, the oil bath was heated to 170 °C, and the system temperature was 136 °C. At this time, it was an azeotropic dehydration process. After 8 h, toluene was distilled off. The reaction system was cooled to room temperature, and 4-nitrophthalonitrile (13.33 g) was added. The system was heated to 85 °C and reacted for 10 h. Then the system was cooled to room temperature and precipitated as a powdery solid in a sodium hydroxide solution. After purification and drying, the final product was obtained.

[0106] This comparative example also provides a petroleum-based phthalonitrile resin, and the preparation method includes:

[0107] The above petroleum-based phthalonitrile monomer was mixed with solid powder of bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) and then hot-pressed to preform tensile specimens. A self-made mold was used, and the size was the 1BA small specimen in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature was 150 °C, the pre-pressing pressure was 5 MPa, with three cycles, 3 min for each cycle, the holding pressure was 15 MPa, and the time was 5 min. The preformed specimens were placed in a high-temperature oven for thermal curing to obtain the final resin samples. The curing program used a gradient heating program, with temperatures of 250 °C, 300 °C, 350 °C, and 370 °C respectively, and the time interval was 2 h.

[0108] Comparative Example 2

[0109] This comparative example provides a petroleum-based phthalonitrile monomer, and the preparation method includes:

[0110] Bisphenol AF (17.65 g), 4,4'-difluorobenzophenone (7.637 g), potassium carbonate (14.51 g), N,N-dimethylacetamide (116 g), and toluene (38 g) were added to a three-necked flask equipped with a nitrogen inlet. After aeration for 30 min, the oil bath was heated to 170 °C, and the system temperature was 136 °C. At this time, it was an azeotropic dehydration process. After 8 h, toluene was distilled off. The reaction system was cooled to room temperature, 4-nitrophthalonitrile (13.33 g) was added, the system was heated to 85 °C, and after reacting for 10 h, the system was cooled to room temperature and powdered solid was precipitated in sodium hydroxide solution. After purification and drying, the final product was obtained.

[0111] This comparative example also provides a petroleum-based phthalonitrile resin, and the preparation method includes:

[0112] The above petroleum-based phthalonitrile monomer was mixed with solid powder of bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) and then hot-pressed to preform tensile specimens. A self-made mold was used, and the size was the 1BA small specimen in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature was 150 °C, the pre-pressing pressure was 5 MPa, with three cycles, 3 min for each cycle, the holding pressure was 15 MPa, and the time was 5 min. The preformed specimens were placed in a high-temperature oven for thermal curing to obtain the final resin samples. The curing program used a gradient heating program, with temperatures of 250 °C, 300 °C, 350 °C, and 370 °C respectively, and the time interval was 2 h.

[0113] Comparative Example 3

[0114] This comparative example provides a petroleum-based phthalonitrile monomer, and the preparation method includes:

[0115] In a three-necked flask equipped with a nitrogen inlet, add resorcinol (5.78 g), 4,4'-difluorobenzophenone (7.64 g), potassium carbonate (14.51 g), N,N-dimethylacetamide (81 g) and toluene (27 g). After aerating for 30 min, raise the oil bath temperature to 170 °C. The system temperature is 136 °C. At this time, it is an azeotropic dehydration process. After 8 h, distill out toluene. Cool the reaction system to room temperature, add 4-nitrophthalonitrile (13.33 g), raise the system temperature to 85 °C, and continue the reaction for 10 h. Then cool the system to room temperature and precipitate powdery solid in sodium hydroxide solution. After purification and drying, the final product is obtained.

[0116] This comparative example also provides a petroleum-based phthalonitrile resin, and the preparation method includes:

[0117] The above-mentioned petroleum-based phthalonitrile monomer is mixed with bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) solid powder and then hot-pressed and preformed into tensile splines. The mold uses a self-made mold, and the size is the 1BA small spline in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature is 150 °C, the pre-pressing pressure is 5 MPa, for three cycles, 3 min each time, the holding pressure is 15 MPa, and the time is 5 min. The preformed splines are placed in a high-temperature oven for thermal curing to obtain the final resin sample. The curing program uses a gradient heating program, and the temperatures are 250 °C, 300 °C, 350 °C, 370 °C respectively, and the time interval is 2 h

[0118] Comparative Example 4

[0119] This comparative example provides a petroleum-based phthalonitrile monomer, and the preparation method includes:

[0120] In a three-necked flask equipped with a nitrogen inlet, add biphenol (9.78 g), 4,4'-difluorobenzophenone (7.64 g), potassium carbonate (14.51 g), N,N-dimethylacetamide (93 g) and toluene (31 g). After aerating for 30 min, raise the oil bath temperature to 170 °C. The system temperature is 136 °C. At this time, it is an azeotropic dehydration process. After 8 h, distill out toluene. Cool the reaction system to room temperature, add 4-nitrophthalonitrile (13.33 g), raise the system temperature to 85 °C, and continue the reaction for 10 h. Then cool the system to room temperature and precipitate powdery solid in sodium hydroxide solution. After purification and drying, the final product is obtained.

[0121] This comparative example also provides a petroleum-based phthalonitrile resin, and the preparation method includes:

[0122] The above-mentioned petroleum-based phthalonitrile monomer was mixed with bis(4-(4-aminophenoxy)phenyl)sulfone (mass fraction 5 wt%) solid powder, and then hot-pressed and preformed into tensile specimens. The mold used was a self-made mold with dimensions of the 1BA small specimen in GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics". The hot-pressing temperature was 150 °C, the pre-pressing pressure was 5 MPa, and it was cycled three times, 3 minutes each time. The holding pressure was 15 MPa and the time was 5 minutes. The preformed specimens were placed in a high-temperature oven for thermal curing to obtain the final resin samples. The curing procedure used a gradient heating program with temperatures of 250 °C, 300 °C, 350 °C, and 370 °C, and the time intervals were 2 hours.

[0123] Performance tests were carried out on the biomass furan-based phthalonitrile resins obtained in Examples 7-10 and the petroleum-based phthalonitrile resins obtained in Comparative Examples 1-4. The test methods are as follows:

[0124] Characterization of thermal stability: Thermogravimetric analysis was used to characterize the thermal stability of the prepared polymers. The test temperature range was 30-800 °C, the heating rate was 10 °C / min, and the air atmosphere was used;

[0125] Characterization of tensile properties: The mechanical properties were tested in accordance with GB / T 1040.1-2018 "Determination of Tensile Properties of Plastics", and the test specimens used were 1BA small specimens;

[0126] Characterization of adhesion properties: The adhesion properties were tested in accordance with GB / T 7124-2008 "Determination of Tensile Shear Strength - Rigid-to-Rigid Materials".

[0127] The test results are shown in Tables 1-3.

[0128] Table 1

[0129] 5% Thermal decomposition temperature (air atmosphere) Example 7 491 Example 8 488 Example 9 493 Example 10 497 Comparative Example 1 495 Comparative Example 2 493 Comparative Example 3 499 Comparative Example 4 501

[0130] Table 2

[0131] Tensile strength (MPa) Elongation at break (%) Example 7 56.5 3.22 Example 8 55.3 2.90 Example 9 60.3 3.16 Example 10 58.2 3.33 Comparative Example 1 48.3 2.96 Comparative Example 2 52.3 3.01 Comparative Example 3 51.5 3.06 Comparative Example 4 50.2 2.99

[0132] Table 3

[0133] Adhesive strength (MPa) Example 7 8.99 Example 8 8.74 Example 9 8.33 Example 10 8.41 Comparative Example 1 6.34 Comparative Example 2 6.31 Comparative Example 3 6.02 Comparative Example 4 6.16

[0134] According to the data in Table 1 and Table 2, it can be concluded that the biomass furanyl phthalonitrile resin provided in the embodiments of the present application has thermal stability and tensile strength comparable to those of the petroleum-based phthalonitrile resin in the comparative example. This is because the furan ring and the benzene ring belong to the aromatic ring structure, and their stability is comparable to that of the benzene ring. Therefore, the thermal stability and tensile properties of the phthalonitrile resin will not deteriorate due to the introduction of the furan ring. According to the data in Table 3, it can be concluded that the biomass furanyl phthalonitrile resin provided in the embodiments of the present application is significantly superior to the petroleum-based phthalonitrile resin in the comparative example in terms of bonding strength. This is because the polarity of the furan ring is larger than that of the benzene ring, resulting in a greater interaction force with the bonding matrix and showing a higher bonding strength.

[0135] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present application, according to the technical solution and its application concept of the present application, makes equivalent substitutions or changes, and should be covered by the protection scope of the present application.

Claims

1. A biomass furanyl phthalonitrile monomer, characterized in that: Having the structure of Formula 1; Wherein R1 is selected from R2 is selected from aromatic groups.

2. The biomass furanyl phthalonitrile monomer according to claim 1, characterized in that The R2 is selected from wherein n is an integer from 1 to 6, R3 and R4 are each independently selected from a C1 to C6 alkyl group or a substituted C1 to C6 alkyl group, and R5 is selected from wherein m, o, and p are each independently 0, 1, or 2; and X is selected from N, O, and S.

3. The biomass furanyl phthalonitrile monomer according to claim 1, characterized in that: The R2 is selected from 4. The biomass furanyl phthalonitrile monomer according to claim 1, characterized in that: Having structures as shown in Formulas 2 to 6; 5. A method for preparing a biomass furanylphthalonitrile monomer according to any one of claims 1 to 4, characterized in that: include: A biomass furanyl difluoro monomer of formula 7, a diphenol monomer of formula 8 and a nitrophthalonitrile monomer of formula 9 are subjected to a nucleophilic substitution reaction to obtain a biomass furanyl phthalonitrile monomer; 6. The preparation method according to claim 5, characterized in that: The biomass furanyl difluoro monomer is selected from The diphenol monomer is selected from The nitrophthalonitrile monomer is selected from 7. The preparation method according to claim 5, characterized in that: The molar ratio of the biomass furanyl difluoro monomer to the diphenol monomer is 1:(1.8-2.5); the molar ratio of the biomass furanyl difluoro monomer to the nitrophthalonitrile monomer is 1:(1.8-2.5).

8. The preparation method according to claim 5, characterized in that: The temperature of the nucleophilic substitution reaction is 40° C. to 160° C., and the time of the nucleophilic substitution reaction is 10 h to 24 h.

9. A biomass furanyl phthalonitrile resin composition, characterized in that: The invention comprises, by weight, 90 to 99 parts of biomass furanyl phthalonitrile monomer and 1 to 10 parts of thermal curing accelerator.

10. A method for preparing a biomass furanyl phthalonitrile resin, characterized in that: include: The biomass furanyl phthalonitrile monomer and a curing accelerator are thermally cured to obtain a biomass furanyl phthalonitrile resin.

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