CN112876364B - Acrylate monomer and preparation method thereof, and acrylate monomer repair material and application thereof - Google Patents
Acrylate monomer and preparation method thereof, and acrylate monomer repair material and application thereof Download PDFInfo
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- CN112876364B CN112876364B CN202110053851.2A CN202110053851A CN112876364B CN 112876364 B CN112876364 B CN 112876364B CN 202110053851 A CN202110053851 A CN 202110053851A CN 112876364 B CN112876364 B CN 112876364B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
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Abstract
The invention provides an acrylate monomer and a preparation method thereof, and an acrylate monomer repair material and application thereof, and belongs to the technical field of photocuring materials. The invention provides an acrylate monomer, which has a chemical structure shown in a formula I, wherein in the formula I, R is H, Me or Et; r1Me, Et or Pr; r' is H or Me. The acrylate monomer provided by the invention is used for preparing the repair material, can be rapidly cured in a short time, has good mechanical strength after being cured, can be used for healing the insulation microcracks encapsulated by the dry-type hollow shunt reactor, and realizes effective repair of the microcracks. Experimental results show that the conversion rate of double bonds of the repair material prepared from the acrylate monomer reaches 57.98% when the repair material is irradiated for 60s, the bending strength of the cured material is 114.99MPa, the bending modulus is 3.15GPa, and the compressive strength is 207.69 MPa.
Description
Technical Field
The invention relates to the technical field of photocuring materials, in particular to an acrylate monomer and a preparation method thereof, and an acrylate monomer repair material and application thereof.
Background
The dry-type hollow parallel reactor has the advantages of small maintenance amount, low cost, easy installation and the like, is generally used in a power system and is used as important reactive compensation equipment in a transformer substation, the dry-type hollow parallel reactor is mainly used for providing inductive reactance to consume excessive capacitive reactive power of the power system so as to achieve the aim of maintaining the voltage level of the power system, and the safe operation of the dry-type hollow parallel reactor is directly related to the power quality and the safety of a power grid. Since eighties's dry-type air core shunt reactor was put into use in our country, the dry-type air core shunt reactor burning out incidents happened occasionally, the reason for this was that all fault dry-type air core shunt reactor packaging insulation all appeared the crackle of different degree, lead to packaging surface electric field distortion, and then cause partial discharge, or receive the erosion of external conditions such as rainwater in the environment, cause the turn-to-turn short circuit, and then cause the reactor burning out.
However, the problem of insulation microcrack encapsulation of the dry-type hollow parallel reactor belongs to the industrial problem, the dry-type hollow parallel reactor has not been concerned by colleges and research institutions at home and abroad for a long time, the repair research on the insulation microcrack encapsulation is less, the prior art discloses an insulation microcrack encapsulation repair penetrating agent as disclosed in an invention patent with the publication number of CN110862747A, but the curing time is long, the room temperature curing needs 3 days, and meanwhile, the mechanical property of the cured material is poor, and the tensile shear strength is only 8 MPa; patent publication No. CN110606913A discloses an acrylic repair material which has a relatively short curing time but a bending strength after curing of only 88.37 MPa.
Therefore, a repair material having a short curing time and high mechanical strength after curing is desired.
Disclosure of Invention
The invention aims to provide an acrylate monomer and a preparation method thereof, and an acrylate monomer repair material and application thereof. The acrylate monomer repair material provided by the invention has short visible light curing time and excellent mechanical strength after curing.
The invention provides an acrylate monomer, which has a chemical structure shown in a formula I:
in the formula I, R is H, Me or Et; r1Me, Et or Pr; r' is H or Me.
The invention provides a preparation method of the acrylate monomer in the technical scheme, which comprises the following steps:
(1) carrying out coupling reaction on a biomass raw material, acid and an aldehyde group monomer to obtain bio-based bisphenol;
(2) carrying out ring-opening etherification reaction on the bio-based bisphenol obtained in the step (1), a catalyst and epoxy chloropropane, and then adding a solvent and sodium hydroxide to carry out ring-closing reaction to obtain bio-based epoxy resin;
(3) and (3) carrying out ring-opening reaction on the bio-based epoxy resin obtained in the step (2), triphenylphosphine, hydroquinone and an acrylic monomer to obtain an acrylate monomer.
Preferably, the biomass raw material in the step (1) comprises one of 4-methyl guaiacol, 4-ethyl guaiacol and 4-propyl guaiacol.
Preferably, the aldehyde-based monomer in the step (1) includes one of formaldehyde, acetaldehyde and propionaldehyde.
Preferably, the ratio of the biomass raw material to the amount of aldehyde monomer in the step (1) is 2.2: (0.8 to 1.5).
Preferably, the ratio of the amounts of bio-based bisphenol to epichlorohydrin in step (2) is 1: (18-25).
Preferably, the acrylic monomer in the step (3) includes acrylic acid or methacrylic acid.
The invention also provides an acrylate monomer repair material which comprises the acrylate monomer in the technical scheme or the acrylate monomer prepared by the preparation method in the technical scheme, a reactive diluent, a photoinitiator and an auxiliary initiator.
Preferably, the mass ratio of the acrylate monomer, the reactive diluent, the photoinitiator and the co-initiator is x (10-x): (0.05-0.15): 0.05-0.15), wherein x is 1-9.
The invention also provides application of the acrylate monomer repairing material in the technical scheme in repairing the insulation microcracks of the dry-type hollow shunt reactor.
The invention provides an acrylate monomer, which has a chemical structure shown in a formula I:
in the formula I, R is H, Me or Et; r1Me, Et or Pr; r' is H or Me. The acrylate monomer provided by the invention is used for preparing the repair material, can be rapidly cured and bonded with cracks in a short time, and the cured material has good mechanical strength, can be used for healing the insulation microcracks encapsulated by the dry-type hollow parallel reactor, and realizes effective repair of the microcracks. Experimental results show that the conversion rate of double bonds of the repair material prepared from the acrylate monomer reaches 57.98% when the repair material is illuminated for 60s, the conversion rate of the double bonds is high, and the curing time is short; the bending strength of the material after complete curing is 114.99MPa, the bending modulus is 3.15GPa, the compression strength is 207.69MPa, and the material has excellent mechanical strength.
Drawings
FIG. 1 is an IR spectrum of BCF-BP, BCF-EP and BCF-EA prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of BCF-BP prepared in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of BCF-EP prepared in example 1;
FIG. 4 is a nuclear magnetic hydrogen spectrum of BCF-EA prepared in example 1;
FIG. 5 is a nuclear magnetic hydrogen spectrum of BCF-EMA prepared in example 2.
Detailed Description
The invention provides an acrylate monomer, which has a chemical structure shown in a formula I:
in the formula I, R is H, Me or Et; r1Me, Et or Pr; r' is H or Me.
In the present invention, R is H, R1When Me and R' are H, the chemical structural formula of the acrylate monomer is
In the present invention, R is H, R1When Me and R' are Me, the chemical structural formula of the acrylate monomer is
The acrylate monomer provided by the invention is used for preparing the repair material, a double-bond structure contained in the acrylate monomer can be reacted and cured under visible light, and meanwhile, the monomer has a substituent group with a proper size, so that the acrylate monomer can be rapidly cured and bonded with cracks in a short time; the rigid benzene ring structure contained in the monomer can ensure that the material has better mechanical strength after being cured, and can be used for healing the insulation microcracks encapsulated by the dry-type hollow parallel reactor and realizing the effective repair of the microcracks.
The invention provides a preparation method of the acrylate monomer in the technical scheme, which comprises the following steps:
(1) carrying out coupling reaction on a biomass raw material, acid and an aldehyde group monomer to obtain bio-based bisphenol;
(2) carrying out ring-opening etherification reaction on the bio-based bisphenol obtained in the step (1), a catalyst and epoxy chloropropane, and then adding a solvent and sodium hydroxide to carry out ring-closing reaction to obtain bio-based epoxy resin;
(3) and (3) carrying out ring-opening reaction on the bio-based epoxy resin obtained in the step (2), triphenylphosphine, hydroquinone and an acrylic monomer to obtain an acrylate monomer.
The present invention is not particularly limited as far as the sources of the above components are concerned, unless otherwise specified, and any commercially available product or product prepared by a conventional preparation method known to those skilled in the art may be used.
According to the invention, a biomass raw material is subjected to coupling reaction with an acid and an aldehyde monomer to obtain the bio-based bisphenol.
In the present invention, the reaction equation of the coupling reaction is shown in formula II:
in the present invention, the biomass feedstock preferably includes one of 4-methyl guaiacol, 4-ethyl guaiacol, and 4-propyl guaiacol, and more preferably 4-methyl guaiacol.
In the present invention, the aldehyde-based monomer preferably includes one of formaldehyde, acetaldehyde and propionaldehyde, and more preferably formaldehyde.
In the present invention, the ratio of the amounts of the biomass raw material and the aldehyde group monomer is preferably 2.2: (0.8 to 1.5), and more preferably 2.2: 1.
In the present invention, the aldehyde monomer is preferably added in the form of an aldehyde monomer solution. The mass concentration of the aldehyde monomer is not specially limited, and the ratio of the biomass raw material to the aldehyde monomer is ensured to be within the range. In the present invention, the mass concentration of the aldehyde monomer solution is preferably 37%.
In the present invention, the acid preferably includes one of phosphoric acid, hydrochloric acid and hydrobromic acid, and more preferably phosphoric acid. In a preferred embodiment of the present invention, the phosphoric acid has a mass concentration of preferably 83 to 90%, and more preferably 85%. In the present invention, the ratio of the amount of the biomass raw material to the volume of the acid is preferably 0.22mol (5 to 9) mL, and more preferably 0.22 mol/7 mL. In the invention, the phosphoric acid provides an acidic environment, so that the biomass raw material and the aldehyde monomer are subjected to coupling reaction under an acidic condition.
According to the invention, preferably, the biomass raw material and the acid are mixed firstly, and then the aldehyde group monomer solution is added for coupling reaction. According to the invention, firstly, the biomass raw material and the acid are mixed, and then the aldehyde group monomer solution is added, so that the biomass raw material can be fully dissolved and uniformly dispersed in the system, and meanwhile, the system is in an acidic environment, and the coupling reaction of the aldehyde group monomer and the biomass raw material is facilitated to obtain a target product.
In the invention, the mixing temperature of the biomass raw material and the acid is preferably 45-55 ℃, and more preferably 50 ℃; the mixing time is preferably 25-35 min, and more preferably 30 min.
In the present invention, the aldehyde monomer solution is preferably added dropwise; the dropping rate is preferably 7-10 s/0.05mL, and more preferably 8-9 s/0.05 mL. In the invention, the dropwise addition can avoid the formation of a multi-crosslinking structure product due to overhigh local concentration.
In the invention, the temperature of the coupling reaction is preferably 85-95 ℃, and more preferably 90 ℃; the time of the coupling reaction is preferably 5.5-6.5 h, and more preferably 6 h.
In the present invention, the coupling reaction is preferably carried out under stirring conditions; the stirring is preferably mechanical stirring; the stirring speed is preferably 150-250 r/min, and more preferably 200 r/min.
In the present invention, the coupling reaction is preferably carried out under nitrogen protection. In the present invention, the nitrogen protection can prevent the biomass raw material from being oxidized by oxygen in the air.
After the coupling reaction is completed, the present invention preferably performs a post-treatment on the product of the coupling reaction to obtain the bio-based bisphenol. In the present invention, the post-treatment preferably comprises cooling, water washing, recrystallization and column chromatography, which are sequentially performed. The operations of cooling, washing with water, recrystallization and column chromatography which are sequentially carried out in the invention are not particularly limited, and the operations of cooling, washing with water, recrystallization and column chromatography which are well known to those skilled in the art can be adopted. In the present invention, the solvent for recrystallization is preferably toluene.
After the bio-based bisphenol is obtained, the bio-based bisphenol, a catalyst and epoxy chloropropane are subjected to ring-opening etherification reaction, and a solvent and sodium hydroxide are added for ring-closing reaction to obtain the bio-based epoxy resin.
In the present invention, the reaction equation of the ring-opening etherification and ring-closing reaction is shown in formula III:
in the invention, the ratio of the amounts of the bio-based bisphenol to the epichlorohydrin is preferably 1 (18-25), and more preferably 1: 20.
In the present invention, the catalyst preferably includes one of tetrabutylammonium bromide, tetrabutylammonium chloride and benzyltrimethylammonium chloride, and more preferably tetrabutylammonium bromide. In the present invention, the ratio of the amount of the bio-based bisphenol to the amount of the catalyst is preferably 1 (0.05 to 0.08), and more preferably 1: 0.06. In the invention, the catalyst makes epichlorohydrin open ring and carry out etherification reaction with phenolic hydroxyl of bio-based bisphenol.
In the invention, the temperature of the ring-opening etherification reaction is preferably 85-95 ℃, and more preferably 90 ℃; the time of the ring-opening etherification reaction is preferably 5.5-6.5 h, and more preferably 6 h.
After the ring-opening etherification reaction is completed, the invention preferably carries out reduced pressure distillation on the product of the ring-opening etherification reaction to remove the excessive epichlorohydrin in the system.
After the reduced pressure distillation is finished, the solvent and sodium hydroxide are added into the reaction system to carry out a ring-closing reaction, so as to obtain the bio-based epoxy resin.
In the present invention, the solvent is preferably toluene. In the invention, the mass ratio of the bio-based bisphenol to the solvent is preferably 1 (15-25), more preferably 1: 20; the mass ratio of the bio-based bisphenol to the sodium hydroxide is preferably 1 (2.0-3.0), and more preferably 1: 2.4. In the present invention, the sodium hydroxide is preferably added in the form of an aqueous sodium hydroxide solution, and the mass concentration of the aqueous sodium hydroxide solution is preferably 20 to 40 wt%, and more preferably 30 wt%.
In the invention, the temperature of the ring-closure reaction is preferably 85-95 ℃, and more preferably 90 ℃; the time of the ring-closure reaction is preferably 2.5-3.5 h, and more preferably 3 h.
After the ring-closure reaction is completed, the invention preferably carries out post-treatment on the product of the ring-closure reaction to obtain the bio-based epoxy resin. In the present invention, the post-treatment preferably includes cooling, water washing, reduced pressure distillation, drying and column chromatography, which are sequentially performed. The operations of cooling, washing with water, reduced pressure distillation, drying and column chromatography which are sequentially carried out are not particularly limited, and the operations of cooling, washing with water, reduced pressure distillation, drying and column chromatography which are well known to those skilled in the art can be adopted. In the present invention, the temperature reduction is preferably to room temperature. In the invention, the drying temperature is preferably 50-70 ℃, more preferably 60 ℃, and the drying time is preferably 10-14 h, more preferably 12 h.
In the invention, the bio-based bisphenol, a catalyst and epichlorohydrin are subjected to ring-opening etherification reaction, a solvent and sodium hydroxide are added to perform ring-closing reaction, preferably under the condition of stirring, preferably mechanically stirring, and the stirring speed is preferably 150-250 r/min, more preferably 200 r/min.
In the invention, the bio-based bisphenol, a catalyst and epichlorohydrin are subjected to ring-opening etherification reaction, and then a solvent and sodium hydroxide are added to perform ring-closing reaction, preferably under the protection of nitrogen. In the present invention, the nitrogen protection can prevent the bio-based bisphenol from being oxidized by oxygen in the air.
After the bio-based epoxy resin is obtained, the bio-based epoxy resin, triphenylphosphine, hydroquinone and acrylic monomers are subjected to ring-opening reaction to obtain the acrylate monomer.
In the present invention, the reaction equation of the ring-opening reaction is shown in formula IV:
in the invention, the mass ratio of the triphenylphosphine to the bio-based epoxy resin is preferably (0.005-0.015) to 1, and more preferably 0.01: 1. In the present invention, the triphenylphosphine is a catalyst.
In the present invention, the mass ratio of hydroquinone to bio-based epoxy resin is preferably (0.0005 to 0.0015) to 1, and more preferably 0.001 to 1. In the invention, hydroquinone is used as a polymerization inhibitor.
In the invention, the acrylic monomer is preferably added after the bio-based epoxy resin is mixed with triphenylphosphine and hydroquinone. In the invention, the mixing temperature of the bio-based epoxy resin, triphenylphosphine and hydroquinone is preferably 95-105 ℃, more preferably 100 ℃, and the mixing time is preferably 2-7 min, more preferably 5 min.
In the present invention, the ratio of the amounts of the bio-based epoxy resin and the acrylic monomer is preferably 1 (1.5 to 2.5), and more preferably 1: 2.04. In the invention, the temperature of the ring-opening reaction is preferably 100-110 ℃, and more preferably 105 ℃; the ring-opening reaction time is preferably 3-6 h, and more preferably 4 h.
In the invention, the ring-opening reaction of the bio-based epoxy resin, triphenylphosphine, hydroquinone and acrylic monomers is preferably carried out under stirring conditions, the stirring is preferably mechanical stirring, and the stirring speed is preferably 150-250 r/min, and more preferably 200 r/min.
After the ring-opening reaction is completed, the invention preferably performs column chromatography on the product of the ring-opening reaction to obtain the acrylate monomer. The operation of the column chromatography is not particularly limited in the present invention, and the operation of the column chromatography known to those skilled in the art may be employed.
The invention can fully carry out the reaction and avoid side reaction by controlling the technical parameters of the dosage of each raw material, the reaction temperature and time of each step, the charging sequence and the like, thereby obtaining the target product.
The invention also provides an acrylate monomer repair material which comprises the acrylate monomer, the reactive diluent, the photoinitiator and the co-initiator.
The present invention is not particularly limited in the kinds of the reactive diluent, the photoinitiator and the co-initiator, and those known to those skilled in the art can be used. In the present invention, the reactive diluent is preferably triethylene glycol dimethacrylate; the photoinitiator is preferably camphorquinone; the coinitiator is preferably dimethylaminoethyl methacrylate.
In the invention, the mass ratio of the acrylate monomer, the reactive diluent, the photoinitiator and the co-initiator is preferably x (10-x): (0.05-0.15): 0.05-0.15), wherein x is 1-9, and more preferably 5:5:0.1: 0.1.
The invention limits the mass content of each component in the range, can ensure that the repair material has lower viscosity and strong fluidity, and has shorter curing time and higher mechanical strength after curing.
In the present invention, the preparation method of the acrylate monomer repair material preferably includes: and mixing the acrylate monomer, the reactive diluent, the photoinitiator and the co-initiator to obtain the acrylate monomer repairing material. In the invention, the acrylate monomer and the reactive diluent are preferably mixed firstly, and then the photoinitiator and the coinitiator are added. In the present invention, the addition of the photoinitiator and co-initiator is preferably carried out under exclusion of light. In the present invention, the light-shielding reaction can avoid chemical reaction during the preparation process. In the invention, the mixing of the acrylate monomer, the reactive diluent, the photoinitiator and the co-initiator is preferably carried out under a stirring condition, the stirring is preferably mechanical stirring, and the stirring speed is preferably 150-250 r/min, and more preferably 200 r/min; the stirring time is preferably 3-5 h, and more preferably 4 h; the stirring temperature is preferably 20-30 ℃, and more preferably 25 ℃.
In the invention, chemical reaction does not occur among the components in the preparation process of the acrylate monomer repair material, and the chemical reaction occurs under the illumination condition when the acrylate monomer repair material is used.
After the stirring is finished, the invention preferably carries out defoaming treatment on the stirred product to obtain the acrylate monomer repairing material. In the invention, the defoaming treatment is preferably vacuum defoaming, and the vacuum degree of the vacuum defoaming is preferably 0.02-0.1 MPa, and more preferably 0.09 MPa; the time for vacuum defoaming is preferably 1.5-2.5 h, and more preferably 2 h.
After the acrylate monomer repair material is obtained, the acrylate monomer repair material is preferably stored under the condition of keeping out of the sun so as to avoid curing of the repair material.
The invention also provides application of the acrylate monomer repairing material in the technical scheme in repairing the insulation microcracks of the dry-type hollow shunt reactor. The application of the acrylate monomer repair material in the repair of the insulation microcracks of the dry-type hollow shunt reactor is not particularly limited, and the acrylate monomer repair material can be applied to the repair of the insulation microcracks of the dry-type hollow shunt reactor by adopting the application scheme of the acrylate monomer repair material which is well known by the technical personnel in the field. In the invention, the application of the acrylate monomer repair material in the repair of the insulation microcracks encapsulated by the dry-type hollow parallel reactor is preferably to permeate the acrylate monomer repair material into the insulation microcracks encapsulated by the dry-type hollow parallel reactor and then to cure the acrylate monomer repair material under the condition of visible light.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Under the protection of nitrogen, adding 0.22mol of 4-methyl guaiacol and 7mL of 85% phosphoric acid (the mass ratio of 4-methyl guaiacol to phosphoric acid is 0.22mol:7mL) into a three-necked bottle provided with a mechanical stirring device, a thermometer and a reflux condensing device, stirring at 200r/min for 5min, heating to 50 ℃, keeping the system at a constant temperature for 30min, dropwise adding 0.1mol of formaldehyde aqueous solution (the mass concentration of formaldehyde is 37%, the mass ratio of 4-methyl guaiacol to formaldehyde is 2.2:1, the dropwise adding rate is 8s/0.05mL), heating to 90 ℃ for reaction for 6h to obtain a golden yellow red product, cooling the product to room temperature, washing with water to neutrality, recrystallizing by using toluene as a solvent, and performing column chromatography to obtain a white crystal product, namely bio-based bisphenol BCF-BP;
(2) under the protection of nitrogen, 0.1mol of BCF-BP, 2mol of epichlorohydrin and 0.006mol of tetrabutylammonium bromide (the mass ratio of the BCF-BP to the epichlorohydrin is 1:20, and the mass ratio of the BCF-BP to the tetrabutylammonium bromide is 1:0.06) are added into a three-mouth bottle provided with a mechanical stirring device, a thermometer and a reflux condensing device, the temperature is raised to 90 ℃ for reaction for 6 hours, the excess epichlorohydrin in the system is removed by reduced pressure distillation, 2mol of toluene and 0.24mol of sodium hydroxide (an aqueous solution of sodium hydroxide, wherein the mass concentration of the sodium hydroxide is 30 wt%, the mass ratio of the BCF-BP to the toluene is 1:20, and the mass ratio of the BCF-BP to the sodium hydroxide is 1:2.4) are added, the system is heated to 90 ℃ for reaction for 3 hours, the system is cooled to room temperature, washed by water, the toluene in the system is removed by reduced pressure distillation, the system is dried at 60 ℃ for 12 hours, obtaining white needle-shaped resin crystals and bio-based epoxy resin BCF-EP after column chromatography;
(3) adding 0.1mol of BCF-EP into a three-neck flask provided with a stirrer, a gas-guide tube and a condenser tube, taking 1 wt% of triphenylphosphine as a catalyst, taking 0.1 wt% of hydroquinone as a polymerization inhibitor (the mass ratio of the BCF-EP to the triphenylphosphine is 100:1, and the mass ratio of the BCF-EP to the hydroquinone is 100:0.1), heating to 100 ℃ to fully melt the BCF-EP, adding 0.204mol of acrylic acid (the mass ratio of the BCF-EP to the acrylic acid is 1:2.04), heating to 105 ℃ to react for 4 hours, cooling and carrying out column chromatography to obtain a colorless and transparent product, namely the acrylic ester monomer BCF-EA.
The structural formula of the acrylate monomer is:
example 2
(1) Under the protection of nitrogen, adding 0.22mol of 4-methyl guaiacol and 7mL of 85% phosphoric acid (the mass ratio of 4-methyl guaiacol to phosphoric acid is 0.22mol:7mL) into a three-necked bottle provided with a mechanical stirring device, a thermometer and a reflux condensing device, stirring at 200r/min for 5min, heating to 50 ℃, keeping the system at a constant temperature for 30min, dropwise adding 0.1mol of formaldehyde aqueous solution (the mass concentration of formaldehyde is 37%, the mass ratio of 4-methyl guaiacol to formaldehyde is 2.2:1, the dropwise adding rate is 8s/0.05mL), heating to 90 ℃ for reaction for 6h to obtain a golden yellow red product, cooling the product to room temperature, washing with water to neutrality, recrystallizing by using toluene as a solvent, and performing column chromatography to obtain a white crystal product, namely bio-based bisphenol BCF-BP;
(2) under the protection of nitrogen, 0.1mol of BCF-BP, 2mol of epichlorohydrin and 0.006mol of tetrabutylammonium bromide (the mass ratio of the BCF-BP to the epichlorohydrin is 1:20, and the mass ratio of the BCF-BP to the tetrabutylammonium bromide is 1:0.06) are added into a three-mouth bottle provided with a mechanical stirring device, a thermometer and a reflux condensing device, the temperature is raised to 90 ℃ for reaction for 6 hours, the excess epichlorohydrin in the system is removed by reduced pressure distillation, 2mol of toluene and 0.24mol of sodium hydroxide (an aqueous solution of sodium hydroxide, wherein the mass concentration of the sodium hydroxide is 30 wt%, the mass ratio of the BCF-BP to the toluene is 1:20, and the mass ratio of the BCF-BP to the sodium hydroxide is 1:2.4) are added, the system is heated to 90 ℃ for reaction for 3 hours, the system is cooled to room temperature, washed by water, the toluene in the system is removed by reduced pressure distillation, the system is dried at 60 ℃ for 12 hours, obtaining white needle-shaped resin crystals and bio-based epoxy resin BCF-EP after column chromatography;
(3) adding 0.1mol of BCF-EP into a three-neck flask provided with a stirrer, a gas-guide tube and a condenser tube, taking 1 wt% of triphenylphosphine as a catalyst, taking 0.1 wt% of hydroquinone as a polymerization inhibitor (the mass ratio of the BCF-EP to the triphenylphosphine is 100:1, and the mass ratio of the BCF-EP to the hydroquinone is 100:0.1), heating to 100 ℃ to fully melt the BCF-EP, adding 0.204mol of methacrylic acid (the mass ratio of the BCF-EP to the methacrylic acid is 1:2.04), heating to 105 ℃ to react for 4 hours, cooling, and carrying out column chromatography to obtain a colorless and transparent product, namely, the methacrylate monomer BCF-EMA.
The structural formula of the methacrylate monomer is as follows:
example 3
An acrylate monomer repair material is composed of 5 parts of the acrylate monomer prepared in example 1, 5 parts of triethylene glycol dimethacrylate, 0.1 part of camphorquinone and 0.1 part of dimethylaminoethyl methacrylate; the preparation method comprises the following steps:
(1) adding 5 parts of acrylate monomer and 5 parts of triethylene glycol dimethacrylate into a reaction vessel, and stirring for 2 hours at 25 ℃ and 200 r/mim;
(2) adding camphorquinone 0.1 part and dimethylaminoethyl methacrylate 0.1 part, stirring at 25 deg.C under dark condition and 200r/mim for 2 hr, vacuum defoaming at 25 deg.C and vacuum degree of 0.09MPa in a vacuum oven for 2 hr, and placing in a dark container for use.
Example 4
A methacrylate monomer repair material consists of 5 parts of methacrylate monomer prepared in example 2, 5 parts of triethylene glycol dimethacrylate, 0.1 part of camphorquinone and 0.1 part of dimethylaminoethyl methacrylate; the preparation method comprises the following steps:
(1) adding 5 parts of methacrylate monomer and 5 parts of triethylene glycol dimethacrylate into a reaction vessel, and stirring for 2 hours at 25 ℃ and 200 r/mim;
(2) adding camphorquinone 0.1 part and dimethylaminoethyl methacrylate 0.1 part, stirring at 25 deg.C under dark condition and 200r/mim for 2 hr, vacuum defoaming at 25 deg.C and vacuum degree of 0.09MPa in a vacuum oven for 2 hr, and placing in a dark container for use.
Comparative example 1
A repair material comprises 5 parts of a commercially available adhesive Bis-GMA, 5 parts of triethylene glycol dimethacrylate, 0.1 part of camphorquinone and 0.1 part of dimethylaminoethyl methacrylate; the preparation method comprises the following steps:
(1) adding 5 parts of commercially available adhesive Bis-GMA and 5 parts of triethylene glycol dimethacrylate into a reaction vessel, and stirring at 25 ℃ and 200r/mim for 2 hours;
(2) adding camphorquinone 0.1 part and dimethylaminoethyl methacrylate 0.1 part, stirring at 25 deg.C under dark condition and 200r/mim for 2 hr, vacuum defoaming at 25 deg.C and vacuum degree of 0.09MPa in a vacuum oven for 2 hr, and placing in a dark container for use.
The IR spectra of BCF-BP, BCF-EP and BCF-EA of example 1 were tested and the results are shown in FIG. 1. As can be seen from FIG. 1, when BCF-BP reacts with epichlorohydrin to generate BCF-EP, 3457cm-1Disappearance of the characteristic peak attributed to the phenolic hydroxyl group in BCF-BP, 910cm-1A characteristic peak ascribed to an epoxy group in BCF-EP appeared, confirming that almost all phenolic hydroxyl groups were converted to epoxy groups; in the infrared spectrum of BCF-EA, the characteristic peak of the epoxy group disappears, 1700cm-1And 1621cm-1The absorption peaks corresponding to carbonyl and carbon-carbon double bond appear, which proves that almost all epoxy groups react with acrylic acid to generate the target product.
The nuclear magnetic hydrogen spectra of BCF-BP, BCF-EP, BCF-EA in example 1 and BCF-EMA in example 2 were measured, and the results are shown in FIGS. 2 to 5. The prepared intermediates and the assignment of hydrogen to acrylate and methacrylate monomers are given in fig. 2 to 5, demonstrating that the target product is obtained.
Performance testing
Test subjects: repair materials of example 3, example 4 and comparative example 1.
(1) The experimental method comprises the following steps: testing by using a Fourier infrared transform spectrometer, firstly preparing a potassium bromide sheet by using a tabletting method, coating a small amount of prepared repair material on the potassium bromide sheet, and quickly testing to obtain an infrared absorption spectrum of the potassium bromide sheet; taking out the tested sample, curing for 60s by using a visible light curing lamp, and performing infrared spectrum test, wherein the length of C-C double bond in the acrylate or methacrylate is 1635cm when comparing the infrared spectrum of two times-1The absorption peak area becomes smaller after curing, while the content of C ═ O double bonds in the product during polymerization is unchanged at 1720cm-1The absorption peak area of (A) also does not change. Thus, the carbonyl group is at 1720cm-1The absorption peak intensity was used as an internal standard, and the intensity of the absorption peak of C ═ C double bond after curing was analyzed, and the conversion of double bond was calculated using the following formula, and the results were averaged 5 times and shown in table 1.
Wherein A isC＝CIndicates that the C ═ C double bond is 1635cm-1Absorption peak area of (A)C＝ODenotes a C ═ O double bond at 1720cm-1The absorption peak area of (B) is 0 represents uncured, and t represents cured.
(2) The experimental method comprises the following steps: preparing a stainless steel detachable die with the thickness of 25 (+ -0.1) mm multiplied by 2 (+ -0.1) mm, preparing a glass plate, covering a layer of polytetrafluoroethylene film on the glass plate, placing the die on the polytetrafluoroethylene film, injecting a repairing liquid into the die, covering a layer of polytetrafluoroethylene film, covering a layer of glass plate, curing by using a light curing lamp, overlapping the curing position and the previous light curing position along the radius, wherein the curing time is 30s, both the front side and the back side are cured, taking out a sample after the light curing time is over, polishing, and storing in a water bath at the temperature of 37 (+ -1) ℃ for 24 hours; taking out the sample strip after the water bath is finished, accurately measuring the thickness and the width of the sample strip, carrying out three-point bending test on a universal testing machine, and recording the breaking load, wherein the loading speed is 1 mm/min; flexural strength and elastic modulus were calculated using the formulas, and the results of 10 sets of tests were averaged and are shown in Table 1.
(3) The experimental method comprises the following steps: injecting a repairing material into a cylindrical grinding tool with the height of 6 (+ -0.1) mm and the diameter of 4 (+ -0.1) mm, tightly pressing the upper bottom surface and the lower bottom surface of the cylinder by polytetrafluoroethylene films, covering the upper surface by glass slides, then illuminating, taking out samples after the curing is finished, grinding by abrasive paper, performing compression test by using a universal testing machine, wherein the load rate is 1mm/min, averaging 10 groups of test results, and the results are listed in Table 1.
Table 1 performance test data for each repair material
As can be seen from table 1, when the light is cured for 60s, the double bond conversion rate of the repair material is above 40%, wherein the double bond conversion rate of the repair material prepared in example 3 is the highest and is 57.98 ± 0.55%; the double bond conversion rate of the repair material prepared in example 4 is low, 44.38 ± 0.50%; but still meets the use requirements. After curing, the repair materials prepared in examples 3 and 4 have higher flexural strength, flexural modulus and compressive strength than the commercial adhesives and better mechanical strength. In conclusion, the repair material provided by the invention is short in curing time and high in mechanical property after curing, can be used for healing the encapsulated insulation microcracks of the dry-type hollow parallel reactor, and realizes effective repair of the encapsulated insulation microcracks.
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. An acrylate monomer having the chemical structure of formula i:
in the formula I, R is H, Me or Et; r1Me, Et or Pr; r' is H or Me.
2. A method for preparing the acrylate monomer according to claim 1, comprising the steps of:
(1) carrying out coupling reaction on a biomass raw material, acid and an aldehyde group monomer to obtain bio-based bisphenol;
(2) carrying out ring-opening etherification reaction on the bio-based bisphenol obtained in the step (1), a catalyst and epoxy chloropropane, and then adding a solvent and sodium hydroxide to carry out ring-closing reaction to obtain bio-based epoxy resin;
(3) carrying out ring-opening reaction on the bio-based epoxy resin obtained in the step (2), triphenylphosphine, hydroquinone and acrylic monomers to obtain an acrylate monomer;
the biomass raw material in the step (1) is selected from one of 4-methyl guaiacol, 4-ethyl guaiacol and 4-propyl guaiacol;
the aldehyde monomer in the step (1) is selected from one of formaldehyde, acetaldehyde and propionaldehyde;
the acid in the step (1) is phosphoric acid;
the structural formula of the bio-based bisphenol in the step (1) is shown in the specification
；
The catalyst in the step (2) is selected from one of tetrabutylammonium bromide, tetrabutylammonium chloride and benzyltrimethylammonium chloride;
the structural formula of the bio-based epoxy resin in the step (2) is shown in the specification
；
The acrylic monomer in the step (3) is selected from acrylic acid or methacrylic acid.
3. The method for preparing the acrylate monomer according to claim 2, wherein the ratio of the amount of biomass raw material to the amount of aldehyde monomer in the step (1) is 2.2: (0.8 to 1.5).
4. The process for the preparation of acrylic ester monomers according to claim 2, characterized in that the ratio of the amounts of substance of bio-based bisphenol to epichlorohydrin in step (2) is 1: (18-25).
5. An acrylate monomer repair material comprises the following components: acrylate monomer, reactive diluent, photoinitiator and co-initiator; the acrylate monomer according to claim 1.
6. The acrylate monomer repair material of claim 5, wherein the mass ratio of the acrylate monomer, the reactive diluent, the photoinitiator and the co-initiator is x (10-x): (0.05-0.15): 0.05-0.15), wherein x is 1-9.
7. Use of the acrylate monomer repair material according to claim 5 or 6 for repairing insulation microcracks of a dry-type air-core shunt reactor enclosure.
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