CN115433445A - DES (data encryption standard) modified silicon dioxide reinforced unsaturated resin as well as preparation method and application thereof - Google Patents
DES (data encryption standard) modified silicon dioxide reinforced unsaturated resin as well as preparation method and application thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a DES modified silicon dioxide reinforced unsaturated resin and a preparation method and application thereof. The modified nano silicon dioxide is added into unsaturated polyester resin, so that the mechanical property of the resin can be obviously improved. Filler SiO 2 MPS-AA increased from 0% to 1.5%, at 0.5% the tensile strength of the composite increased from 42.08MPa to 62.312MPa (48.1% increase) compared to a level of 0.5% unmodified nanosilica filled resin of only 36.906MPa; using acrylic acidAnd citric acid is used as a modifier, so that the mechanical property of the composite material can be improved, and the effect of acrylic acid is good.
Description
Technical Field
The invention belongs to the field of modified resin, and particularly relates to a multiple modified silicon dioxide reinforced unsaturated resin in DES medium, and a preparation method and application thereof.
Background
The surface of the existing nano silicon dioxide has a plurality of hydroxyl groups, and hydrogen bonds are easily formed among the hydroxyl groups, so that the nano silicon dioxide is easily agglomerated and is not easily dispersed in a polymer, and the mechanical property of the composite material is poor. So the nano-silica must be surface modified when in use. The existing nano-silica surface modification technologies mainly comprise a silane coupling agent method, an alcohol ester method and a polymer method, and organic molecules are introduced into the surface of the nano-silica to improve the compatibility of the silica and a resin matrix, so that the agglomeration of the nano-silica is reduced, the technologies are effective for preventing the agglomeration of nano-silica particles, but have limited mechanical properties for improving thermosetting unsaturated polyester resin and the like, and simultaneously, the modification conditions are harsh, such as: the silane coupling agent method and the polymer modification method adopt an organic solvent, and the alcohol ester method adopts high temperature. The method is based on that double bonds, hydroxyl, carboxyl and other groups are continuously introduced into the surface of the silicon dioxide modified by the silane coupling agent, so that the reactivity of the silicon dioxide in a polymer matrix can be further improved, and the processing fluidity is improved, thereby obviously improving the mechanical property of the polymer composite material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a DES modified silicon dioxide reinforced unsaturated resin and a preparation method and application thereof. The invention takes a deep eutectic solvent as a medium, further carries out secondary modification on silicon dioxide by taking acrylic acid or citric acid and the like as modifiers on the basis of adopting silane coupling agent modification, and prepares reactive nano silicon dioxide. The modified nano silicon dioxide is added into unsaturated polyester resin, so that the mechanical property of the resin can be obviously improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Firstly, preparing a glycol-choline chloride Deep Eutectic Solvent (DES), then adding silicon dioxide and completely dispersing the silicon dioxide in the DES, adding 3-mercaptopropyltriethoxysilane (KH 590) and reacting for 24-36 h, after the reaction is finished, washing, filtering and drying to obtain a white solid (marked as SiO) 2 -MPS)；
(2) Adding the white solid in the step (1) into a glycol-choline chloride Deep Eutectic Solvent (DES), heating to 40-60 ℃ to uniformly disperse the white solid in the DES, adding an organic acid to react, centrifuging or filtering the solution after the reaction is finished to obtain a precipitate, washing the precipitate, and drying to obtain silicon dioxide powder with the organic acid grafted on the surface;
(3) And (3) taking the silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding a curing agent and unsaturated polyester resin, uniformly stirring, removing air bubbles, injecting into a mold, and curing to obtain the DES modified silicon dioxide reinforced unsaturated resin.
Preferably, the ethylene glycol-choline chloride Deep Eutectic Solvent (DES) in the steps (1) and (2) is prepared according to the following method: mixing ethylene glycol and choline chloride in a molar ratio of 2.
Preferably, the concentration of the silicon dioxide in the ethylene glycol-choline chloride Deep Eutectic Solvent (DES) in the step (1) is 5-10 g/mL.
Preferably, the adding amount ratio of the 3-mercaptopropyltriethoxysilane (KH 590) to the silica in the step (1) is 15-25mmol.
Preferably, the washing manner in step (1) is: washed several times with absolute ethanol and water.
Preferably, the drying temperature in the step (1) is 60-80 ℃, and more preferably 60 ℃; the drying time is 24h.
Preferably, the concentration of the white solid in the ethylene glycol-choline chloride Deep Eutectic Solvent (DES) in the step (2) is 0.1-0.2 g/mL, and more preferably 0.125g/mL.
Preferably, the mass ratio of the organic acid to the white solid in the step (2) is 1-2: 2 to 2.5, more preferably 4.
Preferably, the organic acid in step (2) is acrylic acid or citric acid.
Preferably, the reaction time for adding the organic acid in the step (2) is 10-15 h.
Preferably, the washing manner in step (2) is: washing with water or absolute ethyl alcohol for 3-5 times.
Preferably, the drying manner in step (2) is: drying at 60 deg.C for 24h.
Preferably, the mass ratio of the unsaturated polyester resin in the step (3) to the silica powder with the surface grafted with the organic acid is 97.5 to 98.8.
Preferably, the curing agent in the step (3) is OT curing agent.
Preferably, the addition amount of the curing agent in the step (3) is 1 to 3phr; more preferably 1phr.
Preferably, the way of removing bubbles in step (3) is: stirring evenly, putting into a vacuum oven, vacuumizing to-0.09 MPa, and removing bubbles.
Preferably, the curing treatment in step (3) is: firstly curing at 85 ℃ for 0.5h, heating to 125 ℃ and then curing for 1h, and finally heating to 150 ℃ and taking out a sample.
The DES modified silicon dioxide reinforced unsaturated resin prepared by the preparation method of the DES modified silicon dioxide reinforced unsaturated resin is provided.
The application of the DES modified silicon dioxide reinforced unsaturated resin in unsaturated resin-based artificial quartz stone can improve the mechanical property of a resin matrix on the one hand. On the other hand, after the surface of the nano-silica is modified, the nano-silica has better compatibility with a resin matrix, is more favorable for flowing and can fill the surface defects of the artificial quartz stone.
The reaction mechanism of the invention is as follows: in the case of acrylic acid as an organic acid, 3-mercaptopropyltriethoxysilane is used as a bridge, and one end of a mercapto group reacts with a carboxyl group of acrylic acid, and the other end of the mercapto group is directly connected to the surface of silica. The carbon-carbon double bond in the acrylic acid can participate in co-curing with the unsaturated polyester resin.
Compared with the prior art, the invention has the beneficial effects that:
(1) DES was developed as a green medium for chemical polymerisation on the surface of silica particles. Compared with traditional solvents including chloroform and methanol, DESs have higher surface coverage and reaction conditions are not harsh in a DES solution medium. The nano-dioxide is modified in DES medium, and the solution has easily obtained raw materials, is convenient to recover, and reduces the environmental pollution caused by solvent.
(2) The deep eutectic solvent modified nano silicon dioxide provided by the invention can enter other multifunctional micromolecules to participate in reaction with a polymer matrix while preventing the nano silicon dioxide particles from agglomeration, so that the mechanical property between the nano silicon dioxide particles and the polymer is improved.
Drawings
FIG. 1 is a schematic diagram of a silica surface modification mechanism.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The OT curatives used in the examples and comparative examples were purchased from Guangzhou Ministry and chemical Co., ltd; unsaturated polyester resin 7938 was purchased from shingyi technologies, ltd; silica is purchased from Aladdin reagents, inc.; acrylic acid was purchased from Aladdin reagents, inc.; KH590 was purchased from alatin reagent limited; ethylene glycol was purchased from Aladdin reagents, inc.; choline chloride was purchased from alatin reagent limited; citric acid was purchased from aladine reagent limited; absolute ethanol was purchased from alatin reagent limited.
Example 1
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) A DES solution (molar ratio of 2: 1) was prepared by adding 2mol of ethylene glycol and 1mol of choline chloride to a three-necked flask at 60 ℃, stirring with an electric stirring device to obtain a clear and transparent solution (DES), adding 10g of silica, and when the silica was completely dispersed in the DES solution, adding 20mmol of 3-mercaptopropyltriethoxysilane, and continuing the reaction for 24 hours. Washing with anhydrous ethanol and deionized water for several times, filtering, and collecting white Solid (SiO) 2 -MPS) was placed in an oven at 60 ℃ for 24h.
(2) Collecting 2.5g of the aboveAdding modified silicon dioxide powder into a three-neck flask containing 20ml of DES solution, heating to 60 ℃, continuously stirring to uniformly disperse the modified silicon dioxide in the DES solution, then adding 2g of acrylic acid, and reacting for 15 hours; centrifuging or filtering the solution, washing the obtained precipitate with deionized water or anhydrous ethanol (3-5 times), and drying at 60 deg.C for 24 hr to obtain silicon dioxide powder (SiO) with acrylic acid grafted on surface 2 -MPS-AA)。
(3) And (3) taking a certain amount of 0.2g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding 1phr of OT curing agent and 98.8g of unsaturated polyester resin, uniformly stirring, putting into a vacuum oven, vacuumizing to-0.09 MPa, injecting into a mold after bubbles are completely removed, putting into the oven, adding at 85 ℃, curing for 0.5h, heating to 125 ℃, curing for 1h, finally heating to 150 ℃, and taking out a sample.
Example 2
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Same as example 1
(2) Same as example 1
(3) And (3) taking a certain amount of 0.5g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding 1phr of OT curing agent and 98.5g of unsaturated polyester resin, uniformly stirring, putting into a vacuum oven, vacuumizing to-0.09 MPa, injecting into a mold after bubbles are completely removed, putting into the oven, adding at 85 ℃, curing for 0.5h, heating to 125 ℃, curing for 1h, finally heating to 150 ℃, and taking out a sample.
Example 3
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Same as example 1
(2) Same as example 1
(3) And (3) taking 1g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding 1phr of OT curing agent and 98.0g of unsaturated polyester resin, stirring uniformly, placing in a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, placing in the oven, adding and curing for 0.5h at 85 ℃, heating to 125 ℃ for curing for 1h, heating to 150 ℃, and taking out the sample.
Example 4
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Same as example 1
(2) Same as example 1
(3) And (3) taking 1.5g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2) by mass, adding 1phr of OT curing agent and 97.5g of unsaturated polyester resin, uniformly stirring, putting into a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, putting into the oven, adding and curing for 0.5h at 85 ℃, heating to 125 ℃ for curing for 1h, finally heating to 150 ℃, and taking out a sample.
Blank example
The preparation method of the unsaturated resin comprises the following steps: adding 1phr (total mass is reference) of OT curing agent and 99g of unsaturated polyester resin, stirring uniformly, putting into a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, putting into the oven, adding into the oven at 85 ℃, curing for 0.5h, heating to 125 ℃, curing for 1h, finally heating to 150 ℃, and taking out a sample.
Comparative example 1
A method for preparing unmodified silicon dioxide/unsaturated resin polyester comprises the following steps:
0.2g of silicon dioxide powder, 1phr of OT curing agent and 98.8g of unsaturated polyester resin are added, the mixture is uniformly stirred and then placed into a vacuum oven, the vacuum oven is vacuumized to-0.09 MPa at normal temperature, the mixture is injected into a mold after bubbles are completely removed, the mixture is placed into the oven to be cured for 0.5h at 85 ℃, the mixture is heated to 125 ℃ for curing for 1h, and finally the mixture is heated to 150 ℃, and a sample is taken out.
Comparative example 2
The preparation method of the unmodified silicon dioxide/unsaturated resin polyester comprises the following steps:
0.5g of silicon dioxide powder, 1phr of OT curing agent and 98.5g of unsaturated polyester resin are added, the mixture is uniformly stirred and then placed into a vacuum oven, the vacuum oven is vacuumized to-0.09 MPa at normal temperature, the mixture is injected into a mold after bubbles are completely removed, the mixture is placed into the oven to be cured for 0.5h at 85 ℃, the mixture is heated to 125 ℃ for curing for 1h, and finally the mixture is heated to 150 ℃, and a sample is taken out.
Comparative example 3
The preparation method of the unmodified silicon dioxide/unsaturated resin polyester comprises the following steps:
1g of silicon dioxide powder, then adding 1phr of OT curing agent and 98.0g of unsaturated polyester resin, stirring uniformly, putting into a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, putting into the oven, adding at 85 ℃ for curing for 0.5h, heating to 125 ℃ for curing for 1h, finally heating to 150 ℃, and taking out a sample.
Comparative example 4
The preparation method of the unmodified silicon dioxide/unsaturated resin polyester comprises the following steps:
1.5g of silicon dioxide powder, 1phr of OT curing agent and 97.5g of unsaturated polyester resin are added, the mixture is uniformly stirred and then placed into a vacuum oven, the vacuum oven is vacuumized to-0.09 MPa at normal temperature, the mixture is injected into a mold after bubbles are completely removed, the mixture is placed into the oven to be cured for 0.5h at 85 ℃, the mixture is heated to 125 ℃ for curing for 1h, and finally the mixture is heated to 150 ℃, and a sample is taken out.
The tensile strength test was performed on the products prepared in examples 1 to 4, comparative examples 1 to 4, and the blank, and the test results are shown in table 1. And (3) testing tensile strength: according to the measurement of the tensile property of GB/T1040.2 plastics, a dumbbell type tensile sample strip is prepared, and an ICS-2000 universal tester is adopted to carry out tensile strength test, wherein the tensile rate is 20mm/min, the distance between clamps is 50mm, and the gauge length is 20mm.
TABLE 1 tensile Strength test comparison List (Unit: MPa)
From table 1 it can be found that: the tensile strength of the modified silica/unsaturated resin polyester is better than that of the unmodified nano silica/unsaturated resin polyester. The tensile strength of the pure unsaturated polyester resin was 42.08MPa. The tensile strength of the composite material is increased and then decreased along with the increase of the filler, and the tensile strength is increased and then decreased in SiO 2 The maximum value of 62.312MPa is reached at a 0.5% MPS-AA content, which is increased by 48.17% compared to the pure unsaturated polyester resin. With SiO 2 A further increase in the-MPS-AA, the tensile strength of which begins to decrease. But still higher than the tensile strength of the pure unsaturated polyester resin when the addition amount reaches 1.0%.
The reason is that the reactive SiO having a double bond 2 The MPS-AA can react with the double bonds of the unsaturated polyester or of the crosslinking monomer styrene, due to the grafting of the organic chains with double bonds on their surface. During the curing process, siO on the one hand 2 -the double bond on MPS-AA reacts with the double bond on the unsaturated polyester resin, linking with the unsaturated polyester resin; on the other hand, siO 2 The double bond reaction between-MPS-AA and styrene can be linked to styrene (commercially available unsaturated resins are solutions in styrene as solvent). SiO 2 2 the-MPS-AA may be introduced into the unsaturated polyester resin system via a double bond. Thus, the inorganic particles are combined with the unsaturated polyester resin through chemical bonds, the local crosslinking density of the unsaturated polyester resin is increased, and the bonding mode between two phases of silicon dioxide and the unsaturated polyester resin is improved, so that the strength of the composite material is improved.
Example 5
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Same as example 1
(2) The "acrylic acid" in step (2) of example 1 was replaced with "citric acid", and the other steps were carried out using the same procedure as in example 1;
(3) And (3) taking 0.2g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding 1phr of OT curing agent and 98.8g of unsaturated polyester resin, uniformly stirring, putting into a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, putting into the oven, adding and curing for 0.5h at 85 ℃, heating to 125 ℃, curing for 1h, finally heating to 150 ℃, and taking out a sample.
Example 6
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Same as example 5
(2) Same as example 5
(3) And (3) taking 0.5g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding 1phr of OT curing agent and 98.5g of unsaturated polyester resin, uniformly stirring, putting into a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, putting into the oven, adding and curing for 0.5h at the temperature of 85 ℃, heating to 125 ℃ for curing for 1h, finally heating to 150 ℃, and taking out a sample.
Example 7
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Same as example 5
(2) Same as example 5
(3) And (3) taking 1g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding 1phr of OT curing agent and 98.0g of unsaturated polyester resin, uniformly stirring, putting into a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, putting into the oven, adding and curing at 85 ℃ for 0.5h, heating to 125 ℃ for curing for 1h, finally heating to 150 ℃, and taking out a sample.
Example 8
A preparation method of DES modified silicon dioxide reinforced unsaturated resin comprises the following steps:
(1) Same as example 5
(2) Same as example 5
(3) And (3) taking 1.5g of silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding 1phr of OT curing agent and 97.5g of unsaturated polyester resin, uniformly stirring, putting into a vacuum oven, vacuumizing to-0.09 MPa at normal temperature, injecting into a mold after bubbles are completely removed, putting into the oven, adding and curing for 0.5h at 85 ℃, heating to 125 ℃, curing for 1h, finally heating to 150 ℃, and taking out a sample.
The products prepared in examples 5 to 8 were subjected to tensile strength tests, and the test results are shown in table 2. And (3) testing tensile strength: according to the measurement of the tensile property of GB/T1040.2 plastics, dumbbell type tensile sample bars are prepared, an ICS-2000 universal tester is adopted to carry out tensile strength test, the tensile rate is 20mm/min, the distance between clamps is 50mm, and the gauge length is 20mm.
TABLE 2 tensile Strength test comparison List (Unit: MPa)
| Number of | 5 | 6 | 7 | 8 |
| Examples | 42.628 | 45.098 | 53.983 | 43.157 |
As shown in Table 2, the modification of the nano-silica particles by citric acid can also improve the mechanical properties of the nano-silica/unsaturated polyester resin to a certain extent
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of DES modified silicon dioxide reinforced unsaturated resin is characterized by comprising the following steps:
(1) Firstly, preparing a glycol-choline chloride deep eutectic solvent, then adding silicon dioxide and completely dispersing the silicon dioxide in the solvent, adding 3-mercaptopropyltriethoxysilane and reacting for 24-36 h, and after the reaction is finished, washing, carrying out suction filtration and drying to obtain a white solid;
(2) Adding the white solid in the step (1) into an ethylene glycol-choline chloride deep eutectic solvent, heating to 40-60 ℃ to uniformly disperse the white solid in the solvent, adding an organic acid to react, centrifuging or filtering the solution after the reaction is finished to obtain a precipitate, washing the precipitate, and drying to obtain silicon dioxide powder with the surface grafted with the organic acid;
(3) And (3) taking the silicon dioxide powder with the surface grafted with the organic acid prepared in the step (2), adding a curing agent and unsaturated polyester resin, uniformly stirring, removing air bubbles, injecting into a mold, and curing to obtain the DES modified silicon dioxide reinforced unsaturated resin.
2. The method for preparing DES modified silica reinforced unsaturated resin according to claim 1, wherein the ethylene glycol-choline chloride deep eutectic solvent in steps (1) and (2) is prepared by the following method: mixing ethylene glycol and choline chloride with the molar ratio of 2;
the concentration of the silicon dioxide in the ethylene glycol-choline chloride deep eutectic solvent in the step (1) is 5-10 g/mL;
the mass ratio of the unsaturated polyester resin in the step (3) to the silicon dioxide powder with the surface grafted with the organic acid is 96.7-98.
3. The method for preparing DES modified silica reinforced unsaturated resin according to claim 1, wherein the addition amount ratio of 3-mercaptopropyltriethoxysilane to silica in step (1) is 15-25mmol;
the concentration of the white solid in the ethylene glycol-choline chloride deep eutectic solvent in the step (2) is 0.1-0.2 g/mL;
the mass ratio of the organic acid to the white solid in the step (2) is 1-2: 2 to 2.5.
4. The method for preparing DES modified silica reinforced unsaturated resin according to claim 3, wherein the addition amount ratio of 3-mercaptopropyltriethoxysilane to silica in step (1) is 2mmol;
the concentration of the white solid in the ethylene glycol-choline chloride deep eutectic solvent in the step (2) is 0.125g/mL;
the mass ratio of the organic acid to the white solid in the step (2) is 4.
5. The method for preparing a DES modified silica-reinforced unsaturated resin according to any one of claims 1 to 4, wherein the washing in step (1) is performed by: washing with anhydrous ethanol and water for several times;
the drying temperature in the step (1) is 60-80 ℃; the drying time is 24 hours;
the organic acid in the step (2) is acrylic acid or citric acid.
6. The method for preparing the DES modified silica-reinforced unsaturated resin as claimed in claim 5, wherein the reaction time of the step (2) by adding the organic acid is 10-15 h;
the washing mode of the step (2) is as follows: washing with water or absolute ethyl alcohol for 3-5 times;
the drying mode in the step (2) is as follows: drying at 60 deg.C for 24h.
7. The method for preparing DES modified silica reinforced unsaturated resin according to any one of claims 1 to 4, wherein the curing agent in step (3) is OT curing agent;
the addition amount of the curing agent in the step (3) is 1 to 3phr.
8. The method of claim 7, wherein the step (3) of removing bubbles comprises the following steps: stirring uniformly, placing in a vacuum oven, vacuumizing to-0.09 MPa, and removing bubbles;
the curing treatment mode in the step (3) is as follows: firstly curing at 85 ℃ for 0.5h, heating to 125 ℃ and then curing for 1h, and finally heating to 150 ℃, and taking out a sample.
9. The DES modified silica reinforced unsaturated resin prepared by the method of any one of claims 1 to 8.
10. Use of the DES modified silica reinforced unsaturated resin of claim 9 in unsaturated resin based synthetic quartz stone.
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