CN107011499B - Epoxy resin composition containing vanillin-based phosphorus-containing flame retardant and its application - Google Patents

Abstract

The invention discloses a kind of composition epoxy resins of phosphonium flame retardant of aldehyde radical containing vanilla comprising epoxy resin, curing agent, curing accelerator, main flame retardant and flame retardant etc., the flame retardant are selected from vanilla aldehyde radical phosphonium flame retardant.The invention also discloses the applications of the composition epoxy resin, such as the purposes of the composition epoxy resin or its solidfied material as fire proofing.Composition epoxy resin of the invention is when solidification is as fire proofing application; compared with existing expansion type flame-retarding epoxy systems; not only flame retardant property and mechanical property are more excellent; it is simultaneously raw material because flame retardant therein is using the vanillic aldehyde of sustainability, there are the double effects for economizing on resources and protecting environment.

Description

Epoxy resin composition containing vanillin-based phosphorus-containing flame retardant and its application

technical field

The invention relates to an epoxy resin composition, in particular to an epoxy resin composition containing the formulation of the vanillin-based phosphorus-containing flame retardant and its application, such as the use as a flame-retardant material, belonging to the technical field of polymer materials .

Background technique

Epoxy resin has excellent mechanical properties, high temperature resistance, corrosion resistance, adhesion and electrical insulation, and is widely used in automobiles, construction, electronics, aviation and other fields. Flammability is a common problem of epoxy resins and even most polymer materials. In order to achieve the purpose of flame retardancy, the current common method is to introduce flame retardants into the epoxy resin system. With the EU's two major environmental directives on flame retardants, "West Electrical and Electronic Equipment Directive, WEEE" (effective in March 2003) and "Restriction of With the promulgation of Hazardous Substances Directive, RoHS), traditional flame retardant systems such as halogens have been greatly restricted. The flame retardant industry is under pressure to switch to flame retardants that are considered more environmentally friendly. Intumescent flame retardants have developed rapidly due to their many advantages such as environmental protection, low toxicity, and smoke suppression. However, the current intumescent flame retardants are composed of acid source, carbon source and gas source. To achieve ideal flame retardancy, a large amount is added, which will inevitably lead to the decline of other properties. Therefore, improving the efficiency of intumescent flame retardants and reducing the addition amount is a way for intumescent flame retardants to be widely used.

Phosphorus-containing compounds based on Schiff bases have a very good carbon-forming effect and contain nitrogen, which can act as a gas source. However, the existing phosphorus-containing compounds are usually made from petrochemical products, and often The process is complex. With the depletion of petroleum resources, finding sustainable, high-quality and cheap petroleum substitutes is the key to the existence and development of the polymer industry. Bio-based materials use renewable resources as the main raw materials. While reducing the consumption of petrochemical products, they also reduce the environmental pollution during the production of petroleum-based raw materials. It is an important development direction of current polymer materials. The industry has been eager to develop bio-based functional organic materials that have excellent flame retardant properties and are easy to prepare.

Contents of the invention

The main purpose of the present invention is to provide an epoxy resin composition containing a vanillin-based phosphorus-containing flame retardant and its application, so as to overcome the deficiencies in the prior art.

In order to realize the aforementioned object of the invention, the technical solutions adopted in the present invention include:

An embodiment of the present invention provides an epoxy resin composition containing a vanillin-based phosphorus-containing flame retardant, which comprises the following components calculated in parts by weight: 100 parts of epoxy resin, 5 to 150 parts of curing agent, curing Accelerator 0-6 parts, main flame retardant 3-15 parts and flame-retardant auxiliary agent 0.5-10 parts; wherein, the flame-retardant auxiliary agent adopts vanillin-based phosphorus-containing flame retardant.

Further, the vanillin-based phosphorus-containing flame retardant additive has a structure shown in any one of formulas (1) to (4):

where _R1 is

R ₂ is a straight-chain alkane or aromatic hydrocarbon or alicyclic alkane structure with 2-20 carbon atoms, 0≤n≤10.

The embodiment of the present invention also provides a cured product of the epoxy resin composition containing the vanillin-based phosphorus-containing flame retardant.

Preferably, the flame retardancy of the cured product is not lower than UL-94V0, the bending strength is above 90 MPa, and the glass transition temperature is above 100°C.

The embodiment of the present invention also provides a method for preparing the cured product, comprising: uniformly mixing the components of the epoxy resin composition containing the vanillin-based phosphorus-containing flame retardant, and performing thermal curing to form The cured product.

The embodiment of the present invention also provides the use of the epoxy resin composition containing vanillin-based phosphorus-containing flame retardant or its cured product in preparing flame-retardant materials.

Compared with the prior art, the advantages of the present invention at least include:

1) The vanillin-based phosphorus-containing flame retardant provided by the present invention is prepared from the platform compound vanillin, which is the second largest natural renewable resource of lignin, as a raw material. It has a very good char-forming effect and can be used as a gas source To achieve a good effect of intumescent carbon layer, and synergize with the acid source commonly used in intumescent flame retardants, on the premise of achieving effective flame retardancy, it can greatly reduce the amount of flame retardants added, which can alleviate the oil crisis and reduce CO ₂ It has a certain positive effect on the discharge aspect; and its preparation method is simple, the raw materials are easy to obtain, and the implementation is convenient, which is conducive to reducing costs in actual production and has strong practicability;

2) In the present invention, the vanillin-based phosphorus-containing compound is combined with an acid source commonly used in intumescent flame retardants to jointly modify the epoxy resin. Compared with the traditional intumescent flame-retardant epoxy system, the obtained epoxy resin composition , the mechanical properties and flame retardant properties are more excellent, and the sustainable vanillin is used as the raw material, which has the dual effects of saving resources and protecting the environment; its cured product is composed of epoxy-based silicone hybrids, epoxy resins, lignin It is compounded with curing agent and curing accelerator, and there is a synergistic effect between each component, especially between epoxy-based organosilicon hybrids, epoxy resin, and lignin, which has a strong synergistic effect and flame retardant Good, and at the same time, due to the small amount of flame retardant added, the thermal and mechanical properties are also excellent.

Detailed ways

In view of the deficiencies in the prior art, the inventor of this case has been able to propose the technical solution of the present invention after long-term research and extensive practice. The technical solution, its implementation process and principles will be further explained as follows.

One aspect of the embodiments of the present invention provides a vanillin-based phosphorus-containing flame retardant, which has a structure shown in any one of the following formulas (1) to (4):

where _R1 includes Either of the structures shown,

R ₂ includes straight-chain alkanes or aromatic hydrocarbons or alicyclic alkanes with 2 to 20 carbon atoms, 0≤n≤10.

The vanillin-based phosphorus-containing flame retardant described in the foregoing embodiments of the present invention can be prepared by known methods in the industry.

For example, a method for preparing the vanillin-based phosphorus-containing flame retardant provided in the embodiment of the present invention includes: uniformly mixing vanillin, diamine compound, phosphorus-containing compound, catalyst and organic solvent, and then After reacting for 0.5-48 hours, vanillin-based phosphorus-containing bisphenols are obtained, and the vanillin-based phosphorus-containing bisphenols have the structure shown in formula (1) or formula (2);

where _R1 includes

R ₂ includes straight-chain alkanes or aromatic hydrocarbons or alicyclic alkanes with 2 to 20 carbon atoms.

Further, the preparation method may further include: uniformly mixing the vanillin-based phosphorus-containing bisphenol, epichlorohydrin and alkaline substances, and then reacting at 20-120° C. for 0.2-48 hours to obtain the vanillin-based phosphorus-containing bisphenol An epoxy compound, the vanillin-based phosphorus-containing epoxy compound has a structure shown in formula (3) or formula (4);

where _R1 includes

R ₂ includes linear alkanes or aromatic hydrocarbons or alicyclic alkanes with 2 to 20 or more carbon atoms, 0≤n≤10.

As one of the preferred embodiments, the mass ratio of vanillin, diamine compound, phosphorus-containing compound, catalyst and organic solvent is 100: (15-100): (20-300): (0-15): (50 ~500).

As one of the preferred embodiments, the mass ratio of the vanillin-based phosphorus-containing bisphenol, epichlorohydrin and alkaline substance is 100:(20-500):(30-300).

As one of the preferred embodiments, the diamine compound includes p-phenylenediamine, m-phenylenediamine, p-cyclohexanediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexyl Any one or a combination of two or more of methane, ethylenediamine, 1,6-hexanediamine, and 1,3-propylenediamine, but not limited thereto.

Preferably, the phosphorus-containing compound includes diethyl phosphite, dimethyl phosphite, dipropyl phosphite, diphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -Any one or a combination of two or more of the 10-oxides, but not limited thereto.

Preferably, the catalyst includes any one or a combination of two or more of aluminum chloride, zinc chloride, ferric chloride, boron trifluoride, niobium pentachloride and antimony pentafluoride, but is not limited thereto.

Preferably, the organic solvent includes any one or a combination of two or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, alcohols, ethers and aromatic hydrocarbon solvents; preferred , the alcohol solvent includes ethanol; preferably, the ether solvent includes tetrahydrofuran and/or dioxane; preferably, the aromatic hydrocarbon solvent includes toluene, but they are not limited thereto.

Preferably, the alkaline substance includes tetramethylammonium chloride, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, hexadecyltrimethylammonium bromide ammonium, dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, hexamethylenetetramine, sodium hydroxide, sodium carbonate, lithium hydroxide, potassium hydroxide and potassium carbonate At least one or an aqueous solution of at least one, but not limited thereto.

Another aspect of the embodiments of the present invention provides an epoxy resin composition containing a vanillin-based phosphorus-containing flame retardant, which comprises the following components calculated in parts by weight: 100 parts of epoxy resin, 5-5 parts of curing agent 150 parts, 0-6 parts of curing accelerator, 3-15 parts of main flame retardant, and 0.5-10 parts of flame-retardant auxiliary; agent.

Further, the epoxy resin includes any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and novolak epoxy resin Or a combination of two or more, but not limited thereto.

Further, the curing agent can be selected from various suitable epoxy curing agents known in the industry, and the amount of the epoxy curing agent can be determined according to the type of epoxy curing agent used, which is known by those skilled in the art Known, for example, reference can be made to "Epoxy Curing Agents and Additives" (Chemical Industry Press, published on September 1, 2011, ISBN: 9787122110275). For example, the curing agent may be selected from any one or a combination of two or more of amine curing agents, acid anhydride curing agents and phenolic resins, but is not limited thereto. For example, the amine curing agent can be preferably selected from any one or more than two of diethylenetriamine, 4,4'-diaminodiphenylmethane, amidoamine, polyamide, polyetheramine and dicyandiamide combination, but not limited to this. For example, the acid anhydride curing agent may be preferably selected from any one or a combination of two or more of methyl hexahydrophthalic anhydride, itaconic anhydride, and tung oil anhydride, but is not limited thereto.

Further, the curing accelerator can also be selected from various types known in the industry. For example, the curing accelerator may be selected from any one or a combination of two or more of tertiary amines, quaternary ammonium salts, organic bases and Lewis acids, but is not limited thereto. For example, the curing accelerator can be preferably selected from any one of 2-methylimidazole, tetrabutylammonium bromide, 2,4,6-tris(dimethylaminomethyl)phenol, boron trifluoride or A combination of two or more, but not limited thereto.

Further, the main flame retardant includes any one or a combination of two or more of ammonium polyphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium pyrophosphate, but is not limited thereto.

Another aspect of the embodiments of the present invention also provides a cured product of the epoxy resin composition containing the vanillin-based phosphorus-containing flame retardant. The cured product not only has excellent flame retardancy, but also has excellent comprehensive properties including high glass transition temperature, bending strength and the like. For example, the flame retardancy of the cured product is not lower than UL-94V0, the bending strength is above 90MPa, and the glass transition temperature is above 100°C.

Another aspect of the embodiment of the present invention also provides the preparation method of the cured product, comprising: uniformly mixing the components of the epoxy resin composition containing the vanillin-based phosphorus-containing flame retardant, and heating cured to form the cured product.

As one of the preferred embodiments, the preparation method specifically includes: mixing 100 parts of epoxy resin, 5-150 parts of curing agent, 0-6 parts of curing accelerator, 3-15 parts of main flame retardant, 0.5-10 parts of vanilla The aldehyde-based phosphorus-containing flame retardant is mixed evenly, and then cured at 50-90°C for 0.5-10 hours, at 90-150°C for 0.5-10 hours, and at 150-200°C for 0-10 hours to obtain the cured product.

The embodiment of the present invention also provides the use of the epoxy resin composition containing vanillin-based phosphorus-containing flame retardant or its cured product in preparing flame-retardant materials.

The technical solutions of the present invention will be further explained below in conjunction with several embodiments, but the implementation manners of the present invention are not limited thereto.

Example 1:

(1) React 100g of vanillin, 36g of p-phenylenediamine, and 500mL of ethanol at 40°C for 1 hour, then add 2.5g of zinc chloride and 72g of dimethyl phosphite, heat up to 80°C and react for 3 hours, petroleum ether precipitates, After washing with ethanol, the vanillin-based phosphorus-containing bisphenol represented by the following formula (5) was obtained. According to the proton peak on the benzene ring of the vanillin structure, 6.7-7.1ppm represents the proton peak on the benzene ring of the vanillin structure in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent), and 6.5ppm represents the The proton peak on the benzene ring of the phenylenediamine structure, and 3.8ppm is the proton peak on the methyl group of the vanillin structure.

(2) Mix 100g of bisphenol-A epoxy resin (E-51), 15g of ammonium polyphosphate and 0.5g of vanillin-based phosphorus-containing bisphenol synthesized in step (1) using a ball mill, and then add 4,4' - 25 g of diaminodiphenylmethane, stirred and mixed evenly, firstly cured at 90°C for 2 hours, then at 150°C for 2 hours, and finally at 180°C for 2 hours to obtain a cured flame retardant epoxy resin.

After testing, the flame retardant performance of the flame retardant epoxy resin cured product obtained in this embodiment reaches UL-94V0 (measured by standard ASTMD3801-00, the same below), and the bending strength is 140MPa (the bending strength is measured by the universal material testing machine , the sample is a cuboid, the size is 60×10×3.5mm ³ , the span is 48mm, the test speed is 2mm/min, the same below), and the glass transition temperature (Tg) is 165°C (after the sample is solidified, it is ground into Powder, tested by differential scanning calorimeter, N ₂ atmosphere, heating rate is 20°C/min, the same below).

Comparative example 1: substantially the same as step (2) of embodiment 1, but do not add the vanillin base phosphorus-containing bisphenol synthesized in ammonium polyphosphate and embodiment 1, but bisphenol A type epoxy resin (E- 51) 100g, 25g of 4,4'-diaminodiphenylmethane, stir and mix evenly, first cure at 90°C for 2 hours, then at 150°C for 2 hours, and finally at 180°C for 2 hours to obtain the ring Cured epoxy resin. The flame retardancy of the cured epoxy resin reaches UL-94 gradeless, the bending strength is 142MPa, and the Tg is 162°C.

Comparative example 2: basically the same as step (2) of Example 1, but do not add ammonium polyphosphate, but bisphenol A type epoxy resin (E-51) 100g, the vanillin group phosphorus-containing compound synthesized in Example 1 15.5g of bisphenol, mixed evenly with a ball mill; then add 25g of 4,4'-diaminodiphenylmethane, stir and mix evenly, first cure at 90°C for 2 hours, then at 150°C for 2 hours, and finally at 180°C Cured for 2 hours to obtain cured epoxy resin. The flame retardant performance of the cured epoxy resin reaches UL-94 gradeless, the bending strength is 145MPa, and the Tg is 168°C.

Comparative Example 3: It is basically the same as step (2) of Example 1, but instead of adding the vanillin-based phosphorus-containing bisphenol synthesized in Example 1, 100 g of bisphenol A epoxy resin (E-51), poly 15.5g of ammonium phosphate, mixed evenly with a ball mill; then add 25g of 4,4'-diaminodiphenylmethane, stir and mix evenly, first cure at 90°C for 2 hours, then at 150°C for 2 hours, and finally at 180°C Cured for 2 hours to obtain cured epoxy resin. The flame retardancy of the cured epoxy resin reaches UL-94 gradeless, the bending strength is 138MPa, and the Tg is 163°C.

Comparing Example 1 with Comparative Examples 1-3, it can be seen that the flame-retardant performance of the cured flame-retardant epoxy resin obtained by adopting the technical solution of the present invention is greatly improved, and the bending strength and glass transition temperature are maintained.

Example 2:

(1) React 100g of vanillin, 36g of p-cyclohexanediamine, and 500mL of ethanol at 40°C for 1 hour, then add 2.5g of zinc chloride and 154g of diphenyl phosphite, raise the temperature to 90°C for 2 hours, and precipitate petroleum ether , after washing with ethanol, obtain the vanillin-based phosphorus-containing bisphenol shown in the following formula (6). According to the hydrogen nuclear magnetic resonance spectrogram of this vanillin-based phosphorus-containing bisphenol, it can be seen that in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent), 6.6-7.4ppm represents the proton on the benzene ring of diphenyl phosphite and vanillin structure Peak, 2.6ppm represents the proton peak on the carbon connected to the imine group on the alicyclic ring, 1.2-1.8ppm is the chemical shift of the proton on the methylene of the 1,4-cyclohexanediamine structure, and 3.7ppm is the methyl group of the vanillin structure proton peak on the .

(2) Mix 100 g of glycidylamine type epoxy resin (AG80), 10 g of ammonium phosphate, 3 g of ammonium polyphosphate and 1 g of vanillin-based phosphorus-containing bisphenol synthesized in step (1) using a ball mill; then add polyether Amine (D230, provided by Aladdin) 70g, stirred and mixed evenly, first cured at 70°C for 4 hours, and then cured at 150°C for 3 hours to obtain a cured flame retardant epoxy resin. After testing, the flame retardancy of the cured flame retardant epoxy resin obtained in this example reaches UL-94V0, the bending strength is 125MPa, and the Tg is 115°C.

Example 3:

(1) React 100g of vanillin, 65g of 4,4'-diaminodiphenylmethane, and 500mL of ethanol at 40°C for 1 hour, then add 45g of diethyl phosphite, heat up to 90°C for 2 hours, petroleum ether precipitates, After washing with ethanol, the vanillin-based phosphorus-containing bisphenol represented by the following formula (7) was obtained. According to the hydrogen nuclear magnetic resonance spectrum of the vanillin-based phosphorus-containing bisphenol, it can be known that 6.7-7.3ppm represents 4,4'-diaminodiphenylmethane and vanillin in ¹ H nuclear magnetic resonance (d6-DMSO is the solvent). The proton peak on the structural benzene ring, 1.3ppm is the proton peak on the structural methyl group of diethyl phosphite, and 3.5ppm is the chemical shift of the proton on the structural methylene group of 4,4'-diaminodiphenylmethane, 3.7ppm It is the proton peak on the methyl group of the vanillin structure.

(2) Bisphenol A type epoxy resin (E-54, provided by Bluestar Chemical New Material Co., Ltd.) 80g, bisphenol A type epoxy resin (E-20, provided by Bluestar Chemical New Material Co., Ltd.) 20g, diammonium hydrogen phosphate 11g and the vanillin-based phosphorus-containing bisphenol 2g synthesized in step (1), utilize a ball mill to mix uniformly; add dicyandiamide 50g and boron trifluoride (BF3) 1g again, stir and mix uniformly, Curing at 60°C for 8 hours, then curing at 100°C for 4 hours, and finally curing at 150°C for 10 hours to obtain a cured flame retardant epoxy resin. After testing, the flame retardant performance of the cured flame retardant epoxy resin obtained in this example reached UL-94V0, the bending strength was 129 MPa, and the Tg was 155°C.

Comparative Example 4: It is basically the same as step (2) of Example 3, but the vanillin-based phosphorus-containing bisphenol synthesized in Example 3 is not added. The flame retardancy of the obtained cured epoxy resin was UL-94-V0 gradeless, the bending strength was 126MPa, and the Tg was 150°C.

Comparative example 5: basically the same as step (2) of embodiment 3, but do not add diammonium hydrogen phosphate. The flame retardancy of the obtained cured epoxy resin was UL-94-V0 gradeless, the bending strength was 130 MPa, and the Tg was 165°C.

Example 4:

(1) React 100g of vanillin, 65g of 4,4'-diaminodicyclohexylmethane, and 500mL of ethanol at 40°C for 1 hour, then add 2.5g of aluminum chloride and 9,10-dihydro-9-oxa- 142g of 10-phosphaphenanthrene-10-oxide, heated up to 90°C for 2 hours, precipitated with petroleum ether and washed with ethanol to obtain the vanillin-based phosphorus-containing bisphenol shown in the following formula (8), and then mixed with 300g epoxy chloride Propane and 10g of cetyltrimethylammonium bromide were reacted at 80°C for 2 hours, then 100g of 40% NaOH aqueous solution was added, reacted at 50°C for 2 hours, washed with water, and distilled to obtain the vanillin shown in the following formula (9): Phosphorus-based epoxy compound, the epoxy value is 0.195. According to the hydrogen nuclear magnetic resonance spectrum of this vanillin-based phosphorus-containing epoxy compound, it can be seen that in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent), 6.7-8.3ppm represents 9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide and the proton peak on the benzene ring of the vanillin structure, 2.3～3.5ppm represents the characteristic chemical shift of the proton on the epoxy group and the proton peak connected to the imine group on the aliphatic ring, 1.1～ 1.8ppm is the chemical shift of other protons in the 4,4'-diaminodicyclohexylmethane structure except the proton on the methylene group connected to the imine group, and 3.7ppm is the proton peak in the methyl group of the vanillin structure.

(2) Vanillin-based phosphorus-containing epoxy compound 6g synthesized in glycidyl ester type epoxy resin (diglycidyl phthalate) 100g, ammonium dihydrogen phosphate 9g and step (1), utilize ball mill to mix uniformly Add 20g of diethylenetriamine, 5g of tungoleic anhydride and 2g of tetrabutylammonium bromide, stir and mix evenly, first cure at 50°C for 10 hours, then at 90°C for 1 hour, and then at 160°C for 1 hour Hours, the flame retardant epoxy resin cured product is obtained. After testing, the UL-94V0 of the cured flame-retardant epoxy resin obtained in this example has a flexural strength of 130 MPa and a Tg of 170°C.

Example 5:

(1) React 100g of vanillin, 36g of m-phenylenediamine, and 500mL of ethanol at 40°C for 1 hour, then add 2.5g of zinc chloride and 154g of diphenyl phosphite, raise the temperature to 90°C for 2 hours, and precipitate petroleum ether, After washing with ethanol, obtain the vanillin-based phosphorus-containing bisphenol shown in the following formula (10), then react with 40 g of epichlorohydrin and 10 g of cetyltrimethylammonium bromide at 80° C. for 2 hours, and then add 40% 100 g of NaOH aqueous solution was reacted at 50° C. for 2 hours, washed with water, and distilled to obtain a vanillin-based phosphorus-containing epoxy compound shown in the following formula (11), with an epoxy value of 0.036. According to the hydrogen nuclear magnetic resonance spectrogram of this vanillin-based phosphorus-containing epoxy compound, there are 6.6-7.4ppm to represent m-phenylenediamine, diphenyl phosphite and vanillin in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent). The proton peaks on the structure benzene ring, 5.9ppm and 6.1ppm are the characteristic chemical shifts on the two imino ortho protons on the benzene ring, and the three peaks from 2.3 to 3.5ppm represent the characteristic chemical shifts of the protons on the epoxy group, 3.75ppm It is the proton peak on the methyl group of the vanillin structure.

(2) Bisphenol A type epoxy resin (CYD-014U, Yueyang Baling Huaxing Petrochemical Co., Ltd. provides) 70g, bisphenol F type epoxy resin (EPICLON 830LVP, Dainippon Ink Company provides) 30g, ammonium pyrophosphate 7g and the vanillin-based phosphorus-containing epoxy compound 4g synthesized in step (1), utilize a ball mill to mix uniformly; then add 10g of phenolic resin and 4g of 2-methylimidazole, stir and mix uniformly, first solidify at 140°C for 10 hours, and then Curing at 200°C for 1 hour to obtain a cured flame retardant epoxy resin. After testing, the UL-94V0 of the cured flame-retardant epoxy resin obtained in this example has a flexural strength of 135 MPa and a Tg of 120°C.

Embodiment 6:

(1) React 100g of vanillin, 38g of 1,6-hexamethylenediamine, and 500mL of ethanol at 40°C for 1 hour, then add 72g of dimethyl phosphite, raise the temperature to 90°C for 2 hours, precipitate with petroleum ether, and wash with ethanol Obtain the vanillin-based phosphorus-containing bisphenol shown in the following formula (12), react with 20 g of epichlorohydrin and 10 g of cetyltrimethylammonium bromide at 80° C. for 2 hours, and then add 40% NaOH aqueous solution 60 g was reacted at 50° C. for 2 hours, washed with water, and distilled to obtain a vanillin-based phosphorus-containing epoxy compound shown in the following formula (13), with an epoxy value of 0.027. According to the hydrogen nuclear magnetic resonance spectrogram of this vanillin-based phosphorus-containing epoxy compound, it can be seen that in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent), 6.7-7.1ppm represents the proton peak on the benzene ring of the vanillin structure, and 2.3-3.5 ppm represents the characteristic chemical shift of the proton on the epoxy group and the proton peak on the methylene group connected to the imine group, 1.1-1.8ppm is the structure of 1,6-hexamethylenediamine except the methylene group connected to the imine group The chemical shift of protons other than the upper proton, 3.7ppm is the proton peak on the methyl group of the vanillin structure.

(2) 100g of bisphenol F type epoxy resin (DER ^TM 354, provided by Dow Chemical), 5g of ammonium polyetherate and 8g of vanillin-based phosphorus-containing epoxy compound synthesized in step (1), were mixed uniformly by a ball mill Add 55 g of itaconic anhydride and 5 g of 2-methylimidazole, stir and mix evenly, and cure at 120° C. for 7 hours and 190° C. for 3 hours to obtain a cured flame-retardant epoxy resin. After testing, the UL-94V0 of the cured flame-retardant epoxy resin obtained in this example has a flexural strength of 125 MPa and a Tg of 145°C.

Embodiment 7:

(1) React 100g of vanillin, 24g of 1,3-propylenediamine, and 500mL of ethanol at 40°C for 1 hour, then add 2.5g of zinc chloride and 9,10-dihydro-9-oxa-10-phospha 71g of phenanthrene-10-oxide, heated up to 90°C for 2 hours, precipitated with petroleum ether, washed with ethanol to obtain the vanillin-based phosphorus-containing bisphenol shown in the following formula (14), and then mixed with 20g of epichlorohydrin and 10g of ten Hexaalkyltrimethylammonium bromide reacted at 80°C for 2 hours, then added 60g of 40% NaOH aqueous solution, reacted at 50°C for 2 hours, washed with water, and distilled to obtain the vanillin-based phosphorus-containing ring shown in the following formula (15): Oxygen compound, the epoxy value is 0.029. According to the hydrogen nuclear magnetic resonance spectrum of this vanillin-based phosphorus-containing epoxy compound, it can be seen that in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent), 6.7-8.3ppm represents 9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide and the proton peak on the benzene ring of the vanillin structure, 2.3-3.6ppm represents the characteristic chemical shift of the proton on the epoxy group and the proton peak on the methylene group connected to the imine group, 1.6ppm is the proton peak of the methylene in the middle of the 1,3-propanediamine structure, and 3.8ppm is the proton peak of the methyl group of the vanillin structure.

(2) Vanillin-based phosphorus-containing epoxy compound 10g synthesized in 100g of novolak epoxy resin (NPPN-631, provided by Nanya Plastic Industry Co., Ltd.), ammonium pyrophosphate 3g and step (1), utilizes a ball mill to mix uniformly; Then add 80g of polyamide (provided by Xuzhou Zhongyan Science and Technology Industry Co., Ltd.) and 6g of 2,4,6-tris(dimethylaminomethyl)phenol, stir and mix evenly, first cure at 80°C for 6 hours, and then at 130°C Cured at 170°C for 5 hours, and then cured at 170°C for 5 hours to obtain a cured flame retardant epoxy resin. After testing, the UL-94V0 of the cured flame-retardant epoxy resin obtained in this example has a flexural strength of 90 MPa and a Tg of 100°C.

Embodiment 8:

(1) React 100g of vanillin, 15g of ethylenediamine, and 500mL of ethanol at 40°C for 1 hour, then add 2.5g of zinc chloride and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide 71g, be heated up to 90 ℃ and react for 2 hours, petroleum ether precipitation, ethanol washing obtain the vanillin-based phosphorus-containing bisphenol shown in the following formula (16), then with 20g epichlorohydrin and 10g hexadecyl tris Methyl ammonium bromide was reacted at 80°C for 2 hours, then added 60g of 40% NaOH aqueous solution, reacted at 50°C for 2 hours, washed with water, and distilled to obtain the vanillin-based phosphorus-containing epoxy compound shown in the following formula (17). The oxygen value is 0.029. According to the hydrogen nuclear magnetic resonance spectrum of this vanillin-based phosphorus-containing epoxy compound, it can be seen that in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent), 6.7-8.3ppm represents 9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide and the proton peak on the benzene ring of the vanillin structure, 2.3-3.9ppm represents the characteristic chemical shift of the proton on the epoxy group and the proton peak on the methylene connected to nitrogen and vanillin Proton peaks on structural methyl groups.

(2) 100 g of bisphenol A type epoxy resin (E-44), 9 g of ammonium polyphosphate and 1 g of vanillin-based phosphorus-containing bisphenol synthesized in step (1), are mixed uniformly by a ball mill; then add diaminodiphenyl 20g of sulfone was stirred and mixed evenly, first cured at 100°C for 4 hours, and finally cured at 200°C for 4 hours to obtain a cured flame retardant epoxy resin. After testing, the flame retardancy of the cured flame retardant epoxy resin obtained in this example reaches UL-94V0, the bending strength is 160 MPa, and the Tg is 170°C.

Embodiment 9:

(1) React 100 g of vanillin, 50 g of 1,20-eicosanediamine, and 500 mL of ethanol at 40°C for 1 hour, then add 72 g of diphenyl phosphite, raise the temperature to 120°C and react for 0.5 hour, petroleum ether precipitates, After washing with ethanol, obtain the vanillin-based phosphorus-containing bisphenol shown in the following formula (18), then react with 20 g of epichlorohydrin and 1 g of tetrabutylammonium bromide at 100° C. for 1 hour, and then add 60 g of 40% NaOH aqueous solution , reacted at 50° C. for 2 hours, washed with water, and distilled to obtain a vanillin-based phosphorus-containing epoxy compound shown in the following formula (19), with an epoxy value of 0.021. According to the hydrogen nuclear magnetic resonance spectrogram of this vanillin-based phosphorus-containing epoxy compound, it can be seen that in ¹ H nuclear magnetic resonance (d6-DMSO is a solvent), 6.6-7.4ppm represents diphenyl phosphite and on the benzene ring of the vanillin structure. Proton peak, 2.3-3.5ppm represents the characteristic chemical shift of the proton on the epoxy group and the proton peak on the methylene connected to the imine group, 0.8-1.8ppm is the structure of 1,20-eicosane diamine The chemical shift of protons other than the protons on the methylene group connected to the imine group, 3.7ppm is the proton peak on the methyl group of the vanillin structure.

(2) 100 g of bisphenol F type epoxy resin (DER ^TM 354, provided by Dow Chemical), 5 g of ammonium polyphosphate and 5 g of vanillin-based phosphorus-containing epoxy compound synthesized in step (1), were mixed uniformly by a ball mill; Then add 50 g of phenolic resin and 1 g of 2-methylimidazole, stir and mix evenly, firstly cure at 140° C. for 10 hours, and then cure at 200° C. for 1 hour to obtain a cured flame-retardant epoxy resin. After testing, the UL-94V0 of the cured flame-retardant epoxy resin obtained in this example has a flexural strength of 100 MPa and a Tg of 110°C.

Through the comparison of Examples 1-9 and Comparative Examples 1-5, it can be seen that after curing, the flame-retardant epoxy resin composition obtained by the above-mentioned technical solution of the present invention not only has excellent flame-retardant properties, but also has high Excellent comprehensive properties such as glass transition temperature and strength.

In addition, the inventors of this case also conducted experiments with reference to Examples 1-Example 9, using other raw materials and conditions listed in this specification, and also obtained a high-efficiency flame-retardant epoxy resin composition and its excellent comprehensive performance. performance solids.

It should be pointed out that the above descriptions are only some implementations of the present invention, and those skilled in the art can make other deformations and improvements without departing from the inventive concept of the present invention, which all belong to protection scope of the present invention.

Claims (9)

1. An epoxy resin composition containing a vanillin-based phosphorus-containing flame retardant, characterized in that it comprises the following components calculated in parts by weight: 100 parts of epoxy resin, 5 to 150 parts of curing agent, curing accelerator 0 to 6 parts, 3 to 15 parts of the main flame retardant, and 0.5 to 10 parts of the flame retardant auxiliary; wherein, the flame retardant is a vanillin-based phosphorus-containing flame retardant, and has formula (1) to formula ( 4) The structure shown in either: where _R1 is R ₂ is a straight-chain alkane or aromatic hydrocarbon or alicyclic alkane structure with 2-20 carbon atoms, 0≤n≤10; The epoxy resin is selected from any one or both of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin and novolac epoxy resin More than one combination; the main flame retardant is selected from any one or a combination of two or more of ammonium polyphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium pyrophosphate; the vanillin-containing The flame retardant performance of the cured product of the epoxy resin composition based on the phosphorus-containing flame retardant is not lower than UL-94 V0, the bending strength is above 90MPa, and the glass transition temperature is above 100°C. 2. The epoxy resin composition according to claim 1, wherein the curing agent is selected from any one or a combination of two or more of amine curing agents, acid anhydride curing agents and phenolic resins. 3. The epoxy resin composition according to claim 2, characterized in that: the amine curing agent is selected from diethylenetriamine, 4,4'-diaminodiphenylmethane, amidoamine, polyamide, Any one or a combination of two or more of polyetheramine and dicyandiamide. 4. The epoxy resin composition according to claim 2, characterized in that: the acid anhydride curing agent is selected from any one or a combination of two or more in methyl hexahydrophthalic anhydride, itaconic anhydride and tung oil anhydride . 5. The epoxy resin composition according to claim 1, characterized in that: the curing accelerator is selected from any one or a combination of two or more of tertiary amines, quaternary ammonium salts, organic bases and Lewis acids. 6. The epoxy resin composition according to claim 5, characterized in that: the curing accelerator is selected from 2-methylimidazole, tetrabutylammonium bromide, 2,4,6-tri(dimethylamine Any one or a combination of two or more of phenol and boron trifluoride. 7. The cured product of the epoxy resin composition containing vanillin-based phosphorus-containing flame retardant as described in any one of claims 1-6, its flame retardancy is not lower than UL-94 V0, and its bending strength is more than 90MPa , the glass transition temperature is above 100°C. 8. The preparation method of cured product as claimed in claim 7, is characterized in that comprising: each group of the epoxy resin composition containing vanillin-based phosphorus-containing flame retardant described in any one of claims 1-6 Mix evenly, and then cure at 50-90°C for 0.5-10 hours, at 90-150°C for 0.5-10 hours, and at 150-200°C for 0-10 hours to obtain the cured product. 9. Use of the epoxy resin composition containing the vanillin-based phosphorus-containing flame retardant according to any one of claims 1-6 or the cured product according to claim 7 in the preparation of flame retardant materials.