CN113121349B - Flame-retardant vinyl ester resin monomer and preparation thereof, flame-retardant vinyl ester resin condensate and preparation thereof - Google Patents
Flame-retardant vinyl ester resin monomer and preparation thereof, flame-retardant vinyl ester resin condensate and preparation thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a flame-retardant vinyl ester resin monomer and preparation thereof, a flame-retardant vinyl ester resin condensate and preparation thereof. The flame-retardant vinyl ester resin monomer disclosed by the invention has a structure shown in a formula I, a formula II or a formula III, and the flame-retardant vinyl ester resin monomer introduces a biphenyl structure of magnolol into a vinyl structure, so that the flame-retardant vinyl ester resin monomer has an excellent flame-retardant effect under the condition that no flame retardant is added. Meanwhile, the flame-retardant vinyl ester resin provided by the invention contains active allyl functional groups in a monomer structure, and can further perform a grafting reaction to introduce other types of functional groups to prepare different types of flame-retardant vinyl ester resins. In addition, the flame-retardant vinyl ester resin cured product obtained by using the flame-retardant vinyl ester resin also has excellent flame-retardant performance.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a flame-retardant vinyl ester resin monomer and preparation thereof, a flame-retardant vinyl ester resin condensate and preparation thereof.
Background
The industrial vinyl ester resin has excellent performances of good fluidity, moldability, chemical resistance, low curing temperature and the like, but has a low oxygen index, and releases a large amount of smoke and heat during combustion, thereby limiting the wide application of the resin to a certain extent.
At present, the method for improving the flame retardant property of vinyl ester resin mainly comprises adding a phosphorus-nitrogen flame retardant and a silicon-containing flame retardant, however, the flame retardant property of the vinyl ester resin is not completely improved by adding the flame retardant, and secondary pollution to the environment can be caused. For example: the phosphorus-nitrogen flame retardant has an obvious effect on improving the oxygen index of the vinyl ester resin, but improves the flame retardant property of the resin and increases the smoke release of the resin, so that secondary pollution is easily caused; while the silicon-containing flame retardant can obviously reduce the heat release and smoke release of the vinyl ester resin, the improvement of the oxygen index is limited, and the problem existing in the combustion of the vinyl ester resin cannot be comprehensively solved.
In addition, in the prior art, the structure of a vinyl ester resin monomer is also rarely changed directly, so that the purpose of intrinsic flame retardance of vinyl resin is realized. Accordingly, there is an urgent need to develop a vinyl ester resin monomer having excellent intrinsic flame retardant properties while being capable of reducing smoke release and heat release.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a flame-retardant vinyl ester resin monomer and preparation thereof, a flame-retardant vinyl ester resin cured product and preparation thereof. The flame-retardant vinyl ester resin monomer provided by the invention has excellent intrinsic flame retardance and simultaneously has lower heat release and smoke release.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a flame-retardant vinyl ester resin monomer, which has a structure shown in a formula I, a formula II or a formula III:
in the formula I, the formula II and the formula III:
The invention also provides a preparation method of the flame-retardant vinyl ester resin monomer, which comprises the following steps:
mixing magnolol, vinyl acyl chloride reactants, an acid-binding agent and an organic solvent, carrying out a first substitution reaction, and then heating to carry out a second substitution reaction to obtain the flame-retardant vinyl ester resin monomer;
the vinyl chloride reactant comprises acryloyl chloride or methacryloyl chloride.
Preferably, the molar ratio of the magnolol and vinyl acyl chloride reactants is 1 (2-3).
Preferably, the temperature of the first substitution reaction is 0-10 ℃ and the time is 15-30 min; the temperature of the second substitution reaction is 30-50 ℃, and the time is 6-12 h.
The invention also provides a preparation method of the flame-retardant vinyl ester resin monomer, which comprises the following steps:
mixing magnolol, vinyl isocyanate reactants, an organic tin catalyst and an organic solvent, and carrying out addition reaction to obtain the flame-retardant vinyl ester resin monomer;
the vinyl isocyanate-based reactant includes isocyanoethyl methacrylate or methacryloyl isocyanate.
Preferably, the organotin catalyst comprises dibutyltin dilaurate and/or dibutyltin diacetate; the mass ratio of the organic tin catalyst to the vinyl isocyanate reactant is (0.001-0.01): 1.
preferably, the temperature of the addition reaction is 30-50 ℃ and the time is 6-12 h.
The invention also provides a flame-retardant vinyl ester resin which comprises the following components in parts by weight:
65-80 parts of a flame-retardant vinyl ester resin monomer;
19-35 parts of a diluent;
the flame-retardant vinyl ester resin monomer is the flame-retardant vinyl ester resin monomer in the technical scheme or the flame-retardant vinyl ester resin monomer obtained by the preparation method in the technical scheme;
the diluent comprises one or more of styrene, alpha-methyl styrene and divinyl benzene.
The invention also provides a flame-retardant vinyl ester resin cured product, which comprises the following preparation raw materials in parts by weight:
84-115 parts of flame-retardant vinyl ester resin
0.5-2 parts of an accelerator;
1.5-10 parts of a curing agent;
the flame-retardant vinyl ester resin is the flame-retardant vinyl ester resin in the technical scheme;
the promoter comprises organic acid cobalt;
the curing agent comprises one or more of methyl ethyl ketone peroxide, benzoyl peroxide and tert-butyl perbenzoate.
The invention also provides a preparation method of the flame-retardant vinyl ester resin cured product, which comprises the following steps:
mixing vinyl ester resin, an accelerator and a curing agent, and carrying out curing reaction to obtain a cured flame-retardant vinyl ester resin;
the temperature of the curing reaction is 30-160 ℃.
The invention provides a flame-retardant vinyl ester resin monomer which has a structure shown in a formula I, a formula II or a formula III. According to the flame-retardant vinyl ester resin monomer, the biphenyl structure of magnolol is introduced into the vinyl structure, and the biphenyl structure in magnolol has good char-forming performance, so that the flame-retardant vinyl ester resin monomer has an excellent essential flame-retardant effect under the condition that no flame retardant is added. Moreover, the vinyl ester resin monomer has good char-forming performance, and can effectively block heat exchange and smoke release. Meanwhile, the vinyl ester resin monomer structure contains active allyl functional groups, and can further generate grafting reaction to introduce other types of functional groups to prepare different types of flame-retardant vinyl ester resins.
The invention also provides a preparation method of the flame-retardant vinyl ester resin monomer, the flame-retardant vinyl ester resin monomer can be prepared by one-step reaction, the steps are simple, and the large-scale production is easy to realize. Moreover, the method provided by the invention has the advantages of mild reaction conditions, short period and high yield.
The invention also provides a flame-retardant vinyl ester resin which comprises the following components in parts by weight: 65-80 parts of a flame-retardant vinyl ester resin monomer and 19-35 parts of a diluent; the flame-retardant vinyl ester resin monomer is the flame-retardant vinyl ester resin monomer in the technical scheme or the flame-retardant vinyl ester resin monomer obtained by the preparation method in the technical scheme. The flame-retardant vinyl ester resin monomer has good char-forming performance, so the flame-retardant vinyl ester resin obtained by the flame-retardant vinyl ester resin monomer also has excellent flame-retardant performance. Moreover, the vinyl ester resin monomer has good char-forming performance, and can effectively block heat exchange and smoke release. Therefore, the flame retardant vinyl ester resin provided by the invention has lower heat release and smoke release.
The invention also provides a flame-retardant vinyl ester resin cured product obtained by using the flame-retardant vinyl ester resin, which comprises the following preparation raw materials in parts by weight: 84-115 parts of flame-retardant vinyl ester resin; 0.5-2 parts of an accelerator; 1.5-10 parts of a curing agent. The results of the examples show that the cured vinyl ester resin provided by the invention has an oxygen index of 30-33% and a total heat release amount of 65-70.2 MJ/m2The total smoke release amount is 25.4-30.6 m2The flame-retardant vinyl ester resin condensate provided by the invention is proved to have higher oxygen index, lower heat release and smoke release.
Drawings
FIG. 1 is a FT-IR diagram of the flame retardant vinyl ester resin monomer obtained in example 1;
FIG. 2 is a 1H-NMR spectrum of a flame retardant vinyl ester resin monomer obtained in example 1;
FIG. 3 is a FT-IR plot of the flame retardant vinyl ester resin monomer obtained in example 3;
FIG. 4 shows the flame retardant vinyl ester resin monomer obtained in example 31H-NMR spectrum.
Detailed Description
The invention provides a flame-retardant vinyl ester resin monomer, which has a structure shown in a formula I, a formula II or a formula III:
in the formula I, the formula II and the formula III:
The invention also provides a preparation method of the flame-retardant vinyl ester resin monomer in the technical scheme, which comprises the following steps:
mixing magnolol, vinyl acyl chloride reactants, an acid-binding agent and an organic solvent, carrying out a first substitution reaction, and then heating to carry out a second substitution reaction to obtain the flame-retardant vinyl ester resin monomer;
the vinyl chloride reactant comprises acryloyl chloride or methacryloyl chloride.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
In the invention, when the magnolol reacts with vinyl chloride reactants, the obtained flame-retardant vinyl ester resin monomer has a structure shown in a formula I.
In the invention, the acid-binding agent preferably comprises one or more of triethylamine, pyridine or potassium carbonate; further preferred is triethylamine. In the present invention, the organic solvent preferably includes one or more of chloroform, tetrahydrofuran, dichloromethane and acetone.
In the invention, the mole ratio of the magnolol and the acid-binding agent is preferably 1 (2-3), and more preferably 1 (2-2.2). In the invention, the molar ratio of the magnolol to the vinyl acyl chloride reactant is preferably 1 (2-3), and more preferably 1 (2-2.2). In the present invention, the amount ratio of the vinyl chloride-based reactant to the organic solvent is preferably 1g (3 to 50) mL, and more preferably 1g (3 to 10) mL.
In the present invention, the order of mixing the magnolol, the vinyl acyl chloride reactant, the acid-binding agent, and the organic solvent is preferably: mixing the magnolol, an acid-binding agent and a part of organic solvent to obtain a magnolol solution; mixing the vinyl acyl chloride reactant with the balance of organic solvent, and carrying out substitution reaction to obtain a vinyl acyl chloride reactant solution; and dropwise adding the vinyl chloride reactant solution into the magnolol solution.
In the invention, the volume ratio of the partial organic solvent to the rest organic solvent is preferably (4-9): 1. in the invention, in the first substitution reaction, the dripping time is preferably controlled within 10-30 min, and more preferably within 15-30 min; the preferable temperature of the dropwise addition is 0-10 ℃, and the further preferable temperature is 2-5 ℃. In the invention, the dropping temperature refers to the temperature of the magnolol solution during dropping.
In the invention, the dripping condition is controlled under the above condition, so that the over-fast first substitution reaction and incomplete reaction can be avoided, and the yield of the final product is improved.
In the present invention, the temperature of the first substitution reaction is preferably 0 to 10 ℃, and more preferably 2 to 5 ℃. In the present invention, the time of the first substitution reaction is preferably 25 to 35min, and more preferably 25 to 30 min. The first substitution reaction is carried out in a low-temperature environment, a relatively mild reaction environment is provided for magnolol and vinyl acyl chloride reactants, on one hand, heat generation in the reaction process can be avoided, the temperature is too high, side reactions are generated, and further the yield is improved; on the other hand, the low-temperature reaction environment can reduce the volatilization of acryloyl chloride or methacryloyl chloride, so that the reaction is more complete, and the yield can be further improved.
In the present invention, the first substitution reaction is preferably carried out in a protective atmosphere, which is preferably nitrogen. The method carries out the first substitution reaction in the protective atmosphere, can avoid the contact of vinyl chloride reactants and moisture in the air to generate byproducts, and is favorable for improving the yield of final products.
In the present invention, the temperature of the second substitution reaction is preferably 30 to 50 ℃, and more preferably 30 to 45 ℃. In the present invention, the time of the second substitution reaction is preferably 6 to 12 hours, and more preferably 10 to 12 hours. In the present invention, the second substitution reaction is preferably carried out in a protective atmosphere, which is preferably nitrogen.
After the second substitution reaction, the method preferably further comprises the steps of carrying out suction filtration on the obtained reaction liquid of the second substitution reaction, and sequentially washing, drying and vacuum rotary evaporation on the obtained filtrate.
The operation of the suction filtration is not particularly limited in the present invention, and may be performed by a conventional technique known to those skilled in the art. In the invention, the filtration can remove hydrochloride generated in the reaction.
In the present invention, the washing preferably comprises: and sequentially carrying out alkali washing and water washing. In the invention, the alkaline washing agent is preferably NaOH solution; the concentration of the NaOH solution is preferably 1-5 wt%, and more preferably 3-5 wt%. In the present invention, the number of the alkali washing is preferably 1 to 2, and more preferably 1. In the present invention, the volume ratio of the reaction solution to the alkali cleaning agent is preferably 1: (0.1 to 0.6); more preferably 1: (0.4-0.6). In the present invention, the washing agent is preferably deionized water; the number of washing with water is preferably 2 to 4, and more preferably 3. In the present invention, the volume ratio of the reaction solution to the washing reagent is preferably 1: (0.1 to 1); more preferably 1: (0.4-0.6).
The invention removes some impurities generated in the reaction process, such as hydrochloric acid, a small amount of hydrochloride which cannot be completely removed by filtration and vinyl chloride reactants which do not completely react, by NaOH solution and deionized water.
In the present invention, the dried desiccant preferably includes anhydrous magnesium sulfate and/or anhydrous calcium chloride, and more preferably anhydrous magnesium sulfate. In the invention, the dosage ratio of the drying agent to the reaction liquid is preferably (0.2-1): 1; more preferably (0.3 to 0.8): 1.
in the present invention, the vacuum degree of the vacuum rotary evaporation is preferably-0.08 to-0.02 MPa, and more preferably-0.06 to-0.04 MPa. In the invention, the temperature of the vacuum rotary evaporation is preferably 20-45 ℃, and more preferably 30-40 ℃. In the invention, the rotating speed of the vacuum rotary evaporation is preferably 40-120 r/min; further preferably 60 to 100 r/min.
In the invention, the vacuum rotary evaporation can remove the organic solvent.
The invention also provides a preparation method of the flame-retardant vinyl ester resin monomer in the technical scheme, which comprises the following steps:
mixing magnolol, vinyl isocyanate reactants, an organic tin catalyst and an organic solvent, and carrying out addition reaction to obtain the flame-retardant vinyl ester resin monomer;
the vinyl isocyanate reactant comprises isocyano ethyl methacrylate or methacryloyl isocyanate.
In the invention, when the magnolol reacts with the vinyl isocyanate reactant, the obtained flame-retardant vinyl ester resin monomer has a structure shown in a formula II or a formula III.
In the present invention, the organotin catalyst preferably includes dibutyltin dilaurate and/or dibutyltin diacetate, and more preferably dibutyltin dilaurate. In the present invention, the kind of the organic solvent is preferably the same as the above technical solution, and is not described herein again.
In the present invention, the mass ratio of the organotin catalyst to the vinyl isocyanate-based reactant is (0.001 to 0.01):1, and more preferably (0.005 to 0.01): 1. In the present invention, the molar ratio of the magnolol to the vinyl isocyanate reactant and the usage ratio of the vinyl isocyanate reactant to the organic solvent are the same as those mentioned above, and are not described herein again.
In the present invention, the order of mixing the magnolol, the vinyl isocyanate-based reactant, the organotin catalyst, and the organic solvent is preferably: mixing the magnolol, the organic tin catalyst and part of organic solvent to obtain a magnolol solution; mixing the vinyl isocyanate reactant and the balance of organic solvent to obtain a vinyl isocyanate reactant solution; and dropwise adding the vinyl isocyanate reactant solution into the magnolol solution.
In the present invention, the volume ratio of the part of the organic solvent to the rest of the organic solvent is the same as the above-mentioned volume ratio, and the detailed description thereof is omitted. In the invention, in the addition reaction, the dripping time is preferably 10-30 min, and more preferably 15-30 min; the preferable temperature of the dropwise addition is 20-30 ℃, and the further preferable temperature is 25-30 ℃. In the invention, the dropping temperature refers to the temperature of the magnolol solution during dropping.
In the invention, the temperature of the addition reaction is preferably 30-50 ℃, and more preferably 25-30 ℃. In the invention, the time of the addition reaction is preferably 6-12 h, and more preferably 10-12 h. In the present invention, the addition reaction is preferably carried out in a protective atmosphere, which is preferably nitrogen. The method carries out addition reaction in a protective atmosphere, can avoid the contact of vinyl isocyanate reactants and moisture in the air to generate byproducts, and is favorable for improving the yield of final products.
After the addition reaction, the present invention preferably further comprises: and cooling the reaction liquid after the addition reaction to 20-30 ℃, and then carrying out vacuum rotary evaporation. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used. In the present invention, the vacuum rotary evaporation conditions are the same as the above-mentioned vacuum rotary evaporation conditions, and are not described herein again.
The invention also provides a flame-retardant vinyl ester resin which comprises the following components in parts by weight: 65-80 parts of flame-retardant vinyl ester resin monomer and 19-35 parts of diluent.
The flame-retardant vinyl ester resin provided by the invention comprises 65-80 parts by weight of a flame-retardant vinyl ester resin monomer, preferably 77-80 parts; the flame-retardant vinyl ester resin monomer is the flame-retardant vinyl ester resin monomer in the technical scheme or the flame-retardant vinyl ester resin monomer prepared by the preparation method in the technical scheme.
The flame-retardant vinyl ester resin provided by the invention comprises 19-35 parts by weight of diluent, preferably 19-30 parts by weight of flame-retardant vinyl ester resin monomer. In the present invention, the diluent preferably includes one or more of styrene, α -methylstyrene and divinylbenzene, and is more preferably styrene.
In the present invention, the flame retardant vinyl ester resin is preferably prepared by the following steps: and mixing the vinyl ester resin monomer with a diluent to prepare the vinyl ester resin.
In the present invention, the mixing is preferably performed by stirring. The stirring operation is not particularly limited in the present invention, and may be carried out by a conventional technique by a person skilled in the art.
In the invention, the mixing temperature is preferably 20-40 ℃; more preferably 30 to 35 ℃.
The invention also provides a flame-retardant vinyl ester resin cured product, which comprises the following preparation raw materials in parts by weight: 84-115 parts of flame-retardant vinyl ester resin, 0.5-2 parts of accelerator and 2-10 parts of curing agent.
The raw materials for preparing the flame-retardant vinyl ester resin cured product comprise 84-115 parts of flame-retardant vinyl ester resin, and preferably 96-110 parts. In the present invention, the vinyl ester resin is the vinyl ester resin described in the above technical aspect.
The raw materials for preparing the flame-retardant vinyl ester resin cured product comprise 0.5-2 parts by weight of an accelerator, preferably 0.5-1 part by weight of a flame-retardant vinyl ester resin. In the present invention, the accelerator preferably includes organic acid cobalt species, which preferably include cobalt isooctanoate and/or cobalt naphthenate.
The raw materials for preparing the flame-retardant vinyl ester resin cured product comprise 1.5-10 parts by weight of curing agent, preferably 1.5-5 parts by weight of flame-retardant vinyl ester resin. In the present invention, the curing agent preferably includes one or more of methyl ethyl ketone peroxide, benzoyl peroxide and t-butyl perbenzoate.
The invention also provides a preparation method of the flame-retardant vinyl ester resin cured product, which comprises the following steps:
and mixing vinyl ester resin, an accelerator and a curing agent, and carrying out curing reaction to obtain the flame-retardant vinyl ester resin cured product.
In the present invention, the order in which the vinyl ester resin, the accelerator and the curing agent are mixed is preferably: carrying out first mixing on the vinyl ester resin and a curing agent to obtain a first mixture; and carrying out second mixing on the accelerant and the first mixture to obtain a second mixture.
In the present invention, the first mixing and the second mixing are preferably performed by stirring. The stirring operation is not particularly limited in the present invention, and may be carried out by a conventional technique by a person skilled in the art.
In the invention, the temperature of the first mixing is preferably 20-40 ℃; more preferably 30 to 35 ℃. In the present invention, the time for the first mixing is preferably 1 to 3min, and more preferably 1 to 2 min.
In the invention, the temperature of the second mixing is preferably 20-40 ℃; more preferably 30 to 35 ℃. In the present invention, the time for the second mixing is preferably 1 to 3min, and more preferably 1 to 2 min.
After the second mixing, the present invention preferably further comprises subjecting the obtained mixture to vacuum defoaming treatment, and subjecting the defoamed liquid to a curing reaction.
The operation of the vacuum defoaming treatment is not particularly limited, and can be performed by adopting the conventional technical means of the technical personnel in the field. In the invention, the vacuum defoaming treatment can remove bubbles generated in the mixing process.
In the invention, the temperature of the curing reaction is preferably 30-160 ℃; more preferably 40 to 130 ℃. In the invention, the curing reaction time is preferably 3-6 h, and more preferably 4-5 h.
The following examples are provided to describe the flame retardant vinyl ester resin monomer and preparation thereof, the flame retardant vinyl ester resin cured product and preparation thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 12g of magnolol and 10g of triethylamine were dissolved in 100mL of dichloromethane to obtain a magnolol solution.
(2) 10g of methacryloyl chloride was dispersed in 20mL of methylene chloride to obtain a methacryloyl chloride solution.
(3) Under the protection of nitrogen, dropwise adding the methacryloyl chloride solution into the magnolol solution at 2 ℃, controlling the dropwise adding time to be about 30min, reacting at 2 ℃ for 30min after completing the dropwise adding, then heating to 30 ℃, and reacting for 10 h.
(4) Carrying out suction filtration on the obtained reaction solution, removing triethylamine hydrochloride generated in the reaction, and washing for 1 time by using 50mL of 5 wt% NaOH solution; after washing 3 times with 50mL of deionized water, 15g of anhydrous magnesium sulfate was added to dry the washed reaction solution.
(5) And (3) carrying out vacuum rotary evaporation on the dried reaction solution under the conditions of vacuum degree of-0.06 MPa, temperature of 35 ℃ and 80r/min to obtain 14.0g of flame-retardant vinyl ester resin monomer, wherein the yield is 75%.
FIG. 1 is a FT-IR chart of the flame retardant vinyl ester resin monomer obtained in example 1, 1732cm-1Infrared characteristic absorption peak of 1638cm-1Infrared characteristic absorption peak at position of C ═ C double bond, 1199cm-1And the infrared characteristic absorption peak of C-O is shown. The results of the infrared spectrogram prove that: the phenolic hydroxyl group in the magnolol reacts with the methacryloyl chloride, and the C ═ C double bond in the vinyl ester is successfully introduced into the magnolol, so that an ideal product is synthesized.
FIG. 2 shows the flame retardant vinyl ester resin monomer obtained in example 11The H-NMR spectrum, in which 5.55ppm and 6.05ppm correspond to the chemical shifts of hydrogen in vinyl ester, indicates that magnolol and methacryloyl chloride have reacted successfully.
Example 2
(1) Dissolving 12g of magnolol and 10g of triethylamine in 90mL of trichloromethane to obtain a magnolol solution.
(2) Acryloyl chloride, 8.5g, was dissolved in 10mL of chloroform to give an acryloyl chloride solution.
(3) Under the protection of nitrogen, dripping the acryloyl chloride solution into the magnolol solution at 5 ℃, controlling the dripping time to be about 15min, reacting at 5 ℃ for 30min after finishing dripping, and then heating to 30 ℃ for reacting for 10 h.
(4) And (3) carrying out suction filtration on the obtained reaction liquid, removing triethylamine hydrochloride generated in the reaction, washing the reaction liquid for 1 time by using 50mL of 3 wt% NaOH solution, washing the reaction liquid for 3 times by using 50mL of deionized water, and then adding 20g of anhydrous magnesium sulfate to dry the washed reaction liquid.
(4) And (3) carrying out vacuum rotary evaporation on the dried reaction solution under the conditions of vacuum degree of-0.06 MPa, temperature of 35 ℃ and 80r/min to obtain 13.4g of the flame-retardant vinyl ester resin monomer, wherein the yield is 78%.
Example 3
(1) 12g of magnolol and 0.01g of dibutyltin dilaurate were dissolved in 90mL of acetone to obtain a magnolol solution.
(2) 14g of isocyanoethyl methacrylate was dissolved in 10mL of acetone to obtain an isocyanoethyl methacrylate solution.
(3) Under the protection of nitrogen, dropwise adding the isocyano ethyl methacrylate solution into the magnolol solution at 25 ℃, controlling the dropwise adding time to be about 10min, then heating to 40 ℃, and reacting for 12 h.
(4) The reaction solution obtained above was cooled to 25 ℃ and then acetone was removed by rotary evaporation at 50 ℃.
(5) And (3) carrying out vacuum rotary evaporation on the dried reaction solution under the conditions of vacuum degree of-0.06 MPa, temperature of 50 ℃ and 100r/min to obtain 20.4g of the flame-retardant vinyl ester resin monomer, wherein the yield is 90%.
FIG. 3 is a FT-IR plot of the flame retardant vinyl ester resin monomer obtained in example 3 at 1733cm-1Infrared characteristic absorption peak of 1629cm-1And the infrared characteristic absorption peak of C ═ C double bond is shown. Infrared results prove that phenolic hydroxyl in magnolol reacts with isocyano ethyl methacrylate, and C ═ C double bond in isocyano ethyl methacrylate is successfully introduced into magnolol, so that an ideal product is synthesized.
FIG. 4 is a photograph of the product obtained in example 31The H-NMR spectrum, in which 5.61ppm and 6.14ppm correspond to the chemical shifts of the hydrogen in the vinyl ester, indicates the successful reaction of magnolol and isocyanatoethyl methacrylate.
Example 4
(1) 12g of magnolol and 0.01g of dibutyltin dilaurate were dissolved in 80mL of tetrahydrofuran to obtain a magnolol solution.
(2) 10.2g of methacryloyl isocyanate was dissolved in 20mL of tetrahydrofuran to obtain a methacryloyl isocyanate solution.
(3) Under the protection of nitrogen, dropwise adding the methacryloyl isocyanate solution into the magnolol solution at 25 ℃, controlling the dropwise adding time to be about 20min, and then heating to 45 ℃ for reaction for 12 h.
(4) The reaction solution obtained above is cooled to 25 ℃, and then acetone is removed by rotary evaporation at 40 ℃.
(5) And (3) carrying out vacuum rotary evaporation on the dried reaction solution under the conditions of vacuum degree of-0.06 MPa, temperature of 40 ℃ and 80r/min to obtain 16.4g of vinyl ester resin monomer, wherein the yield is 87%.
Application example 1
(1) 79 parts of the flame-retardant vinyl ester resin monomer obtained in example 1 and 19 parts of styrene were uniformly mixed and stirred at a temperature of 30 ℃ to obtain a vinyl ester resin.
(2) Adding 1.5 parts of methyl ethyl ketone peroxide into the vinyl ester resin obtained in the step (1), stirring for 1min at the temperature of 30 ℃, then adding 0.5 part of cobalt isooctanoate, and stirring for 2 min. After being stirred uniformly, the mixture is vacuumized and bubbles in the system are discharged. And after the bubbles are completely discharged, carrying out curing reaction at the temperature of 100 ℃ for 4 hours to obtain the flame-retardant vinyl ester resin cured product.
Application example 2
(1) To 78 parts of the flame retardant vinyl ester resin monomer obtained in example 3, 20 parts of styrene was added and stirred at a temperature of 30 ℃ to obtain a vinyl ester resin.
(2) Adding 1.5 parts of methyl ethyl ketone peroxide into the vinyl ester resin obtained in the step (1), stirring for 1min at the temperature of 30 ℃, then adding 0.5 part of cobalt isooctanoate, and stirring for 2 min. After being stirred uniformly, the mixture is vacuumized and bubbles in the system are discharged. And after the bubbles are completely discharged, carrying out curing reaction at the temperature of 100 ℃ for 4 hours to obtain the flame-retardant vinyl ester resin cured product.
The oxygen index, heat release and smoke release of the cured flame retardant vinyl ester resin obtained in application example 1 and application example 2 were measured by the test methods in GB/T2406-93 and ISO 5660, respectively, and the results are shown in Table 1.
TABLE 1 comparison of Properties of vinyl ester resin cured products of application example 1 and application example 2 with bisphenol a type vinyl ester resin
| Sample (I) | Oxygen index (%) | Heat release (MJ/m)2) | Smoke release (m)2) |
| Bisphenol a type vinyl ester resin | 21 | 97.1 | 40.8 |
| Application example 1 | 33 | 65 | 25.4 |
| Application example 2 | 30 | 70.2 | 30.6 |
As can be seen from table 1, the cured flame retardant vinyl ester resin prepared in application example 1 and application example 2 has a higher oxygen index, lower heat release and smoke release, and better intrinsic flame retardant effect, compared with bisphenol a type vinyl ester resin.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A flame retardant vinyl ester resin monomer having a structure represented by formula II or formula III:
in the formulas II and III:
2. a preparation method of a flame-retardant vinyl ester resin monomer with a structure shown in a formula II or a formula III is characterized by comprising the following steps:
mixing magnolol, vinyl isocyanate reactants, an organic tin catalyst and an organic solvent, and carrying out addition reaction to obtain the flame-retardant vinyl ester resin monomer;
the vinyl isocyanate reactant comprises isocyano ethyl methacrylate or methacryloyl isocyanate;
in the formulas II and III:
3. the production method according to claim 2, characterized in that the organotin catalyst comprises dibutyltin dilaurate and/or dibutyltin diacetate; the mass ratio of the organic tin catalyst to the vinyl isocyanate reactant is (0.001-0.01): 1.
4. the preparation method according to claim 2, wherein the temperature of the addition reaction is 30-50 ℃ and the time is 6-12 h.
5. The flame-retardant vinyl ester resin is characterized by comprising the following components in parts by weight: 65-80 parts of a flame-retardant vinyl ester resin monomer; 19-35 parts of a diluent;
the flame-retardant vinyl ester resin monomer is the flame-retardant vinyl ester resin monomer of claim 1 or the flame-retardant vinyl ester resin monomer obtained by the preparation method of any one of claims 2 to 4;
the diluent comprises one or more of styrene, alpha-methyl styrene and divinyl benzene.
6. The flame-retardant vinyl ester resin cured product is characterized by comprising the following preparation raw materials in parts by weight: 84-115 parts of flame-retardant vinyl ester resin; 0.5-2 parts of an accelerator; 1.5-10 parts of a curing agent;
the flame retardant vinyl ester resin is the flame retardant vinyl ester resin of claim 5; the promoter comprises organic acid cobalt; the curing agent comprises one or more of methyl ethyl ketone peroxide, benzoyl peroxide and tert-butyl perbenzoate.
7. The method for producing a cured flame-retardant vinyl ester resin according to claim 6, comprising the steps of:
mixing the flame-retardant vinyl ester resin, an accelerator and a curing agent, and carrying out curing reaction to obtain a cured flame-retardant vinyl ester resin; the temperature of the curing reaction is 30-160 ℃.
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| CN112457472A (en) * | 2020-11-25 | 2021-03-09 | 广东工业大学 | Low-viscosity bio-based magnolol epoxy resin and preparation method thereof |
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