CN114573816B - Epoxy MQ silicon resin and preparation method and application thereof - Google Patents
Epoxy MQ silicon resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an epoxy MQ silicon resin, a preparation method and application thereof, and the molecular expression general formula is (M) R ) a (M M ) b Q c ，M R The chain links are of the formulae (I-1) and/or (I-2), M M The structural formula of the chain link is shown as the following formula (II), the structural formula of the chain link Q is shown as the following formula (III), wherein, a is selected from positive integers of 10 to 1000, b is selected from positive integers of 10 to 1000, c is selected from positive integers of 10 to 1000, and (a + b)/c =0.6 to 2; the epoxy MQ silicon resin can effectively improve the compatibility and the interface action with the phenol epoxy resin, and is blended with the phenol epoxy resin in any proportion for preparing the transparent modified phenol epoxy resin; more importantly, the toughness and the mechanical properties (tensile strength and tensile modulus) of the prepared transparent modified phenolic epoxy resin are synchronously improved.
Description
Technical Field
The invention relates to the technical field of epoxy resin modification, in particular to epoxy MQ silicon resin, a preparation method thereof and application thereof in preparation of transparent modified phenol epoxy resin.
Background
The epoxy resin is one of three traditional thermosetting resins (epoxy, phenolic aldehyde and unsaturated polyester), has good mechanical and bonding properties, and is widely applied to various industries, such as coating, adhesive, electronic packaging, engineering plastics, composite materials and the like. Due to the high crosslinking density of the epoxy resin, the toughness of the epoxy resin is reduced, and the application of the epoxy resin is limited, so toughening modification is needed.
The addition of a flexible silicone segment is a common toughening epoxy means, such as The article "The effect of epoxy-silicone copolymer content on The thermal and mechanical properties of cured epoxy resin with modified silicone, the epoxy resin and hydroxyl-terminated silane are subjected to chemical grafting modification, and The silane-modified epoxy resin is used as a toughening agent to be compounded and cured with unmodified epoxy resin. As also shown in The article "The mechanical properties and fastening mechanisms of an epoxy resin with a polysiloxane-based core-shell particles" The addition of modified polysiloxane shell core particles to an epoxy resin increases The fracture toughness of The cured product, but The tensile strength and modulus are significantly reduced.
The MQ silicone resin is a silicone resin with a double-layer structure, which is composed of four-functionality siloxane condensation chain links (Q) and single-functionality siloxane chain links (M), and is divided into methyl MQ silicone resin, vinyl MQ silicone resin, hydrogen-containing MQ silicone resin and the like according to the difference of surface organic groups, and is commonly used as a reinforcing material, a tackifier and the like of silicone rubber. Because of the low polarity of MQ silicone resin, MQ silicone resin is rarely used as a toughening material in epoxy resin with high polarity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses epoxy MQ silicon resin, a preparation method thereof and application thereof in preparing transparent modified phenol epoxy resin, wherein the epoxy MQ silicon resin can effectively improve the compatibility and the interface action with the phenol epoxy resin, and can be blended with the phenol epoxy resin in any proportion for preparing the transparent modified phenol epoxy resin; more importantly, the toughness and the mechanical properties (tensile strength and tensile modulus) of the prepared transparent modified phenolic epoxy resin are synchronously improved.
The specific technical scheme is as follows:
an epoxy MQ silicon resin with a molecular expression general formula of (M) R ) a (M M ) b Q c ，M R The structural formula of the segment is shown by the following formulas (I-1) and/or (I-2):
M M the structural formula of the chain link is shown as the following formula (II):
the structural formula of the Q chain link is shown as the following formula (III):
wherein a is a positive integer of 5 to 1000, b is a positive integer of 10 to 1000, c is a positive integer of 10 to 1000, and (a + b)/c =0.6 to 2.
The epoxy MQ silicon resin disclosed by the invention is novel in structure, the terminal group of the epoxy MQ silicon resin is eugenol glycidyl ether or o-eugenol glycidyl ether, the epoxy MQ silicon resin is liquid at normal temperature, the thermal stability is excellent, and the initial decomposition temperature (T) -5％ ) Higher than 300 ℃; the modified phenol epoxy resin has excellent compatibility with phenol epoxy resin, can be mixed in any proportion, has excellent transparency, and can synchronously and greatly improve the tensile strength, the bending strength and the impact strength; and the molecular weight of the epoxy MQ silicon resin can be adjusted by adjusting the ratio of (a + b)/c (namely the ratio of M/Q), so that the performance of the modified phenolic epoxy resin can be regulated and controlled.
Preferably, a is selected from 5 to 150, b is selected from 10 to 150, c is selected from 10 to 200; more preferably, a is selected from 5 to 25, b is selected from 14 to 25, and c is selected from 10 to 84.
The invention also discloses a preparation method of the epoxy MQ silicon resin, which comprises the following steps:
step 1, performing hydrolytic condensation on tetramethyl disiloxane, hexamethyl disiloxane and silicon dioxide precursors under the action of a catalyst A to obtain hydrogen-containing MQ silicon resin;
the silicon dioxide precursor is selected from ethyl orthosilicate and/or sodium silicate;
the catalyst A is selected from one or more of hydrochloric acid, sulfuric acid and methyl benzene sulfonic acid;
the phenolic epoxy monomer is selected from eugenol epoxy and/or o-eugenol epoxy.
The catalyst B is one or more selected from a platinum catalyst, a palladium catalyst and a rhodium catalyst.
In the step 1:
the feeding molar ratio of the silicon dioxide precursor to the tetramethyldisiloxane to the hexamethyldisiloxane is 1:0.1 to 1:0.1 to 1;
by controlling the feeding molar ratio of the three raw materials within the range, the (a + b)/c = 0.6-2 in the prepared epoxy MQ silicon resin can be ensured, so that the prepared epoxy MQ silicon resin is ensured to have a body type structure.
The hydrolysis condensation takes water and ethanol as solvents, and the mass of the water and the ethanol respectively accounts for 10-30 wt% of the total mass of the tetramethyl disiloxane, the hexamethyl disiloxane and the silicon dioxide precursor;
the mass of the catalyst A is 2-65 wt% of the total mass of the tetramethyldisiloxane, the hexamethyldisiloxane and the silicon dioxide precursor;
the hydrolysis condensation is carried out at the temperature of 30-80 ℃ and the heat preservation time is 1-5 h.
Preferably, in step 1, all raw materials except the silica precursor are mixed and heated to the hydrolysis condensation temperature, and then the silica precursor is added for further reaction; preferably, the time from room temperature to heating to the hydrolytic condensation temperature is controlled to be 30 to 60min.
All raw materials except the silicon dioxide precursor comprise tetramethyl disiloxane, hexamethyl disiloxane, a catalyst A, ethanol and water.
Experiments show that the molecular weight distribution of the prepared epoxy MQ silicon resin can be controlled in a narrower range by adopting the preferable feeding sequence.
In the step 2:
the mass ratio of the hydrogen-containing MQ silicon resin to the phenol epoxy monomer is 1:0.2 to 1;
the mass of the catalyst B is 20-100 ppm of the content of the silicon hydrogen bond in the hydrogen-containing MQ silicon resin;
the hydrosilylation reaction is carried out at the temperature of 50-90 ℃ and the heat preservation time is 4-10 h.
The invention also discloses a preparation method of the transparent modified phenol epoxy resin, which takes the epoxy MQ silicon resin as the raw material, mixes the epoxy MQ silicon resin and the phenol epoxy resin in any proportion, and prepares the transparent modified phenol epoxy resin after curing.
The curing agent used for the curing is not particularly required and is selected from the common categories in the field, such as polyamine type, anhydride type, phenolic type and the like.
Mechanical property tests show that when the epoxy MQ silicon resin is added in a proper amount, the impact strength, the bending strength and the tensile strength of the transparent modified phenolic epoxy resin prepared by the invention are remarkably improved compared with those of a single phenolic epoxy resin cured product.
Through comparison tests, if the eugenol glycidyl ether end group or the o-eugenol glycidyl ether end group of the epoxy MQ silicon resin disclosed by the invention is replaced by the allyl glycidyl ether end group or the 1,2-epoxy-4-vinyl cyclohexane end group which also contains epoxy groups, the modified phenol epoxy resin obtained by adopting the same preparation process is opaque firstly, and secondly, the impact strength is obviously improved, but the bending strength and the tensile strength are obviously deteriorated.
Preferably, the phenolic epoxy resin is selected from a bisphenol type epoxy resin and/or a polyphenol type epoxy resin. The above phenolic epoxy resins are all selected from the common categories in the art, such as bisphenol type epoxy resins selected from bisphenol a type epoxy resins, bisphenol F epoxy resins, and the like; the polyphenol type epoxy resin is selected from novolac epoxy resins and the like.
The epoxy MQ silicon resin disclosed by the invention can be mixed with the phenolic epoxy resin in any proportion, and is still a transparent material even under the condition of extremely high addition (such as the mass ratio of the epoxy MQ silicon resin to the phenolic epoxy resin is 80). For example, the mass ratio of the epoxy MQ silicon resin to the phenolic epoxy resin is 5: 95-80: 20. but with the increase of the addition amount of the epoxy MQ silicon resin, the tensile strength and the bending strength of the prepared transparent modified phenol epoxy resin are sacrificed; however, the addition amount is too small, and the improvement of mechanical properties is not significant. Preferably, the mass ratio of the epoxy MQ silicon resin to the phenolic epoxy resin is 10: 90-50: 50. namely, the mass ratio of the epoxy group MQ silicon resin to the phenol epoxy resin is 10:90, and increasing the feed ratio of the epoxy MQ silicon resin to the mass ratio of the epoxy MQ silicon resin to the epoxy MQ silicon resin of 50:50. within this range, the transparent modified phenol epoxy resin obtained can satisfy the use requirements in terms of tensile strength and flexural strength, and has excellent toughness. Preferably, the mass ratio of the epoxy group MQ silicon resin to the phenolic epoxy resin is 20:80.
compared with the prior art, the invention has the following advantages:
1. the invention discloses epoxy MQ silicon resin with a novel structure, which is liquid at room temperature and has excellent thermal stability; and the molecular weight of the epoxy MQ silicon resin can be adjusted by adjusting the ratio of (a + b)/c (namely the ratio of M/Q), so that the performance of the modified phenolic epoxy resin can be regulated and controlled.
2. The epoxy MQ silicon resin disclosed by the invention overcomes the defect that the traditional organic silicon resin is opaque due to phase separation during toughening of the epoxy resin, can be mutually soluble with the phenol epoxy resin in any proportion, and has transparent cured products.
3. The epoxy MQ silicon resin disclosed by the invention overcomes the defect that the tensile property of the resin is greatly reduced when the traditional organic silicon resin toughens the epoxy resin, and can synchronously and greatly improve the tensile strength, the bending strength and the impact strength of the toughened phenol epoxy resin.
Drawings
FIG. 1 shows a schematic representation ofNuclear magnetic resonance hydrogen spectrum of eugenol epoxy MQ silicon resin prepared in example 1 1 H-NMR；
FIG. 2 is the hydrogen nuclear magnetic resonance spectrum of o-eugenol epoxy MQ silicon resin prepared in example 2 1 H-NMR；
FIG. 3 is a NMR hydrogen spectrum of AGEMQ prepared in comparative example 2 1 H-NMR；
FIG. 4 is the NMR hydrogen spectra of EVCMQ prepared in comparative example 3 1 H-NMR；
FIG. 5 is an optical photograph of the cured products prepared in application examples 1 to 5 and comparative application examples 1 to 4, respectively.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific examples, which should not be construed as limiting the scope of the present invention.
In the following examples, NMR spectra 1 H-NMR Using Bruker Avance400 Nuclear magnetic resonance spectrometer, CDCl 3 Is a deuterated solvent.
Tensile strength and flexural strength were measured using a universal material tester (Zwick/Roell Z020).
Impact strength was measured using a pendulum impact tester (CEAST 9050).
Example 1
5.4g (0.04 mol) of tetramethyldisiloxane, 19.5g (0.12 mol) of hexamethyldisiloxane, 20g of water, 15g of ethanol and 3.3g of hydrochloric acid are mixed, after the temperature is raised from room temperature to 70 ℃ for 30min, 60g (0.3 mol) of ethyl orthosilicate is added, after the reaction is carried out for 3h, toluene is added for extraction, water washing and liquid separation are carried out, and then, colorless and transparent hydrogen-containing MQ silicon resin is obtained by reduced pressure distillation.
Uniformly mixing 25g of hydrogen-containing MQ silicon resin, 17.6g (0.08 mol) of eugenol epoxy and 50ppm of a Kanster catalyst, heating to 70 ℃, and reacting for 8 hours to obtain the eugenol epoxy MQ silicon resin, which is recorded as EUEPMQ.
FIG. 1 is the NMR hydrogen spectra of EUEPMQ prepared in this example 1 H-NMR was observed in the figure to confirm that EUEPMQ prepared in this example had a molecular weight of 4230 and a molecular weight distribution of 1.3, and that a = referring to the above molecular expression formula5，b＝15，c＝20。
Example 2
5.4g (0.04 mol) of tetramethyldisiloxane, 19.5g (0.12 mol) of hexamethyldisiloxane, 20g of water, 15g of ethanol and 3.3g of hydrochloric acid are mixed, after the temperature is raised from room temperature to 70 ℃ for 30min, 60g (0.3 mol) of ethyl orthosilicate is added, after the reaction is carried out for 3h, toluene is added for extraction, water washing and liquid separation are carried out, and then, colorless and transparent hydrogen-containing MQ silicon resin is obtained by reduced pressure distillation.
25g of hydrogen-containing MQ silicon resin, 17.6g (0.08 mol) of o-eugenol epoxy and 50ppm of a Kanst catalyst are uniformly mixed and heated to 70 ℃ for reaction for 8 hours to obtain o-eugenol epoxy MQ silicon resin which is marked as o-EUEPMQ.
FIG. 2 shows the NMR spectra of o-EUEPMQ prepared in this example 1 H-NMR observation of this figure confirmed that o-EUEPMQ prepared in this example had a molecular weight of 4320 and a molecular weight distribution of 1.3, and referring to the above molecular expression formula, a =5, b =15, c =20.
Example 3
5.4g (0.04 mol) of tetramethyldisiloxane, 19.5g (0.12 mol) of hexamethyldisiloxane, 20g of water, 15g of ethanol, 3.3g of hydrochloric acid and 60g (0.3 mol) of tetraethoxysilane are mixed, the mixture is heated to 70 ℃ to react for 3 hours, toluene is added to extract water, and liquid separation is carried out by water washing, and then, colorless and transparent hydrogen-containing MQ silicon resin is obtained by reduced pressure distillation.
Uniformly mixing 25g of hydrogen-containing MQ silicon resin, 17.6g (0.08 mol) of eugenol epoxy and 50ppm of a Kanst catalyst, heating to 70 ℃, and reacting for 8 hours to obtain the eugenol epoxy MQ silicon resin.
The molecular weight of the product prepared in this example was 6780, the molecular weight distribution was 2.0, and referring to the above molecular expression formula, a =8, b =24, c =32.
Example 4
6.7g (0.05 mol) of tetramethyldisiloxane, 8.1g (0.05 mol) of hexamethyldisiloxane, 25g of water, 15g of ethanol and 3.3g of hydrochloric acid are mixed, after the temperature is raised from room temperature to 60 ℃ for 30min, 70g (0.34 mol) of ethyl orthosilicate is added, after reaction is carried out for 3h, hexamethyldisiloxane is added to extract water, liquid separation is carried out, and then, colorless and transparent hydrogen-containing MQ silicon resin is obtained by reduced pressure distillation.
Uniformly mixing 25g of hydrogen-containing MQ silicon resin, 22g (0.1 mol) of eugenol epoxy and 30ppm of Kanst catalyst, heating to 80 ℃, and reacting for 6 hours to obtain the eugenol epoxy MQ silicon resin.
The molecular weight of the product prepared in this example was 15000, the molecular weight distribution was 1.4, and with reference to the above molecular expression formula, a =24, b =24, c =80.
Example 5
13.4g (0.1 mol) of tetramethyldisiloxane, 32.4g (0.2 mol) of hexamethyldisiloxane, 20g of water, 20g of ethanol and 3.3g of hydrochloric acid are mixed, after the temperature is raised from room temperature to 60 ℃ for 30min, 60g (0.3 mol) of tetraethoxysilane is added, after 3h of reaction, hexamethyldisiloxane is added to extract water and wash liquid, and then, colorless and transparent hydrogen-containing MQ silicon resin is obtained by reduced pressure distillation.
50g of hydrogen-containing MQ silicon resin, 44g (0.2 mol) of eugenol epoxy and 30ppm of Kanst catalyst are uniformly mixed and heated to 80 ℃ for reaction for 6 hours to obtain the eugenol epoxy MQ silicon resin.
The product prepared in this example was characterized by a molecular weight of 3800 and a molecular weight distribution of 1.2, and with reference to the above general expression of molecules, a =6,b =14,c =10.
Example 6
6.7g (0.05 mol) of tetramethyldisiloxane, 8.1g (0.05 mol) of hexamethyldisiloxane, 25g of water, 15g of ethanol and 53g of hydrochloric acid are mixed, after the temperature is raised from room temperature to 70 ℃ for 30min, 72g (0.34 mol) of sodium silicate is added, after reaction for 4h, toluene is added for extraction, water washing and liquid separation are carried out, and then, colorless and transparent hydrogen-containing MQ silicon resin is obtained by reduced pressure distillation.
Uniformly mixing 25g of hydrogen-containing MQ silicon resin, 22g (0.1 mol) of eugenol epoxy and 30ppm of a Kanst catalyst, heating to 80 ℃, and reacting for 6 hours to obtain the eugenol epoxy MQ silicon resin.
The product prepared in this example was characterized by a molecular weight of 15800 and a molecular weight distribution of 1.5, and referring to the above molecular expression formula, a =25, b =25, c =84.
Comparative example 1
24.3g (0.15 mol) of hexamethyldisiloxane, 15g of water, 15g of ethanol and 2g of hydrochloric acid are uniformly mixed, after the temperature is raised from room temperature to 50 ℃ for 30min, 62.4g (0.25 mol) of tetraethoxysilane is added, the temperature is raised to 70 ℃ for reaction for 3h, ethyl acetate is added for extraction and water washing for multiple times, and the ethyl acetate is removed by reduced pressure distillation to obtain colorless transparent liquid methyl MQ silicon resin.
Comparative example 2
The preparation process is essentially the same as in example 1, except that 9.12g (0.08 mol) of allyl glycidyl ether are used instead of eugenol epoxy. The product prepared in this comparative example was designated as AGEMQ.
FIG. 3 is a NMR hydrogen spectrum of AGEMQ prepared in this comparative example 1 H-NMR was observed to confirm that the molecular weight of AGEMQ prepared in this comparative example was 3620, the molecular weight distribution was 1.3, and the general molecular expression formula was (M) R ) a (M M ) b Q c Then a =5,b =15,c =20.
Wherein M is R The structural formula of the chain link is changed, and the rest structures are unchanged as shown in the following formula:
comparative example 3
The preparation process is essentially the same as in example 1, except that 9.94g (0.08 mol) 1,2-epoxy-4-vinylcyclohexane is used instead of eugenol epoxy. The product prepared in this comparative example was designated EVCMQ.
FIG. 4 is the NMR hydrogen spectra of EVCMQ prepared in this comparative example 1 H-NMR was observed to confirm that EVCMQ prepared in this comparative example had a molecular weight of 3540, a molecular weight distribution of 1.3, and a molecular expression formula of (M) R ) a (M M ) b Q c Then a =5,b =15,c =20.
Wherein M is R The structural formula of the chain link is changed, and the rest structures are unchanged as shown in the following formula:
performance test
1. The products prepared in each example and in each comparative example were mixed with bisphenol a epoxy resin (E51) at a ratio of 20:80 parts by weight of the raw materials are mixed, 20 parts of curing agent isophorone diamine is added and evenly mixed, and then the mixture is injected into a steel die to cure and detect the performance. The curing conditions were 80 ℃/2h,150 ℃/2h, and the test results, including tensile strength, notched impact strength, and flexural strength, are listed in table 1 below. Table 1 also shows data for comparison of cured epoxy resin (comparative application example 4) obtained by uniformly mixing and curing only 100 parts by weight of bisphenol A epoxy resin (E51) and 20 parts of isophorone diamine as a curing agent.
TABLE 1
Note: the application examples and the application comparative examples in the table all correspond to the numbers of the corresponding examples, and by taking the application example 1 as an example, the MQ silicone resin adopted is the one prepared in the example 1; taking the application comparative example 1 as an example, the MQ silicone resin adopted is the one prepared in the comparative example 1.
Compared with the data in table 1, the data show that after the eugenol epoxy MQ silicon resin or the o-eugenol epoxy MQ silicon resin prepared by the invention is added into E51, the tensile strength, the bending strength and the impact strength of the epoxy resin cured material are synchronously and obviously improved, which indicates that the epoxy group MQ silicon resin can effectively improve the mechanical property of the bisphenol epoxy cured material without influencing the transparency of the resin. If the epoxy MQ silicone resin prepared by the invention is replaced by the methyl MQ silicone resin prepared by the comparative example 1 or the epoxy MQ silicone resins with different terminal groups prepared by the comparative examples 2 and 3, although the toughness of the bisphenol epoxy cured material is obviously improved, the transparency of the resin is greatly influenced, and the tensile strength and the bending strength are greatly deteriorated.
2. Eugenol epoxy MQ silicone resin prepared in example 4 and bisphenol a epoxy resin (E51) were each prepared as 10:90 (as application example 5), 50:50 (note application example 6), 80:20 (application example 7), adding 22 parts, 16 parts and 10 parts of curing agent isophorone diamine respectively, mixing uniformly, and injecting into a steel die for curing and detecting performance. The curing conditions were the same as above and the test results are listed in table 2 below.
TABLE 2
3. The o-eugenol epoxy MQ silicone resin prepared in example 2 was mixed with bisphenol F epoxy resin (NPEF-170) at a ratio of 20:80 (as application example 8), 10:90 (as application example 9), 5:95 (denoted as application example 10) and 0:100 (application comparative example 5), then 21, 23, 24 and 25 parts of curing agent isophorone diamine are respectively added in sequence and mixed evenly, and then injected into a steel die for curing and detecting performance. The curing conditions were the same as above and the test results are listed in table 3 below.
TABLE 3
4. The eugenol epoxy MQ silicon resin prepared in example 4 and the polyphenol epoxy resin (novolac epoxy resin) are respectively mixed according to the proportion of 20:80 (as application example 11), 0:100 (marked as application comparative example 6), then adding 25 and 30 parts of curing agent 3,3' -diaminodiphenyl sulfone respectively in sequence, mixing uniformly, injecting into a steel die, and curing and detecting performance. The curing conditions were as above and the test results are listed in table 4 below.
TABLE 4
Claims (10)
1. An epoxy MQ silicon resin is characterized in that the molecular expression formula is (M) R ) a (M M ) b Q c ，M R The structural formula of the chain link is as followsRepresented by the following formulae (I-1) and/or (I-2):
M M the structural formula of the chain link is shown as the following formula (II):
the structural formula of the Q chain link is shown as the following formula (III):
wherein a is a positive integer of 5 to 1000, b is a positive integer of 10 to 1000, c is a positive integer of 10 to 1000, and (a + b)/c =0.6 to 2.
2. The epoxy MQ silicone resin of claim 1, wherein a is selected from the group consisting of 5 to 150, b is selected from the group consisting of 10 to 150, and c is selected from the group consisting of 10 to 200.
3. A method for preparing an epoxy MQ silicone resin according to claim 1 or 2, characterized by comprising the steps of:
step 1, performing hydrolytic condensation on tetramethyl disiloxane, hexamethyl disiloxane and silicon dioxide precursors under the action of a catalyst A to obtain hydrogen-containing MQ silicon resin;
the silicon dioxide precursor is selected from ethyl orthosilicate and/or sodium silicate;
the catalyst A is selected from one or more of hydrochloric acid, sulfuric acid and methyl benzene sulfonic acid;
step 2, carrying out hydrosilylation reaction on the hydrogen-containing MQ silicon resin prepared in the step 1 and a phenol epoxy monomer under the action of a catalyst B to obtain epoxy MQ silicon resin;
the phenolic epoxy monomer is selected from eugenol epoxy and/or o-eugenol epoxy;
the catalyst B is one or more selected from a platinum catalyst, a palladium catalyst and a rhodium catalyst.
4. The process for preparing epoxy MQ silicone resins according to claim 3, characterized in that, in step 1:
the feeding molar ratio of the silicon dioxide precursor to the tetramethyldisiloxane to the hexamethyldisiloxane is 1:0.1 to 1:0.1 to 1;
the hydrolysis condensation takes water and ethanol as solvents, the mass of the water accounts for 10-30 wt% of the total mass of the tetramethyl disiloxane, the hexamethyldisiloxane and the silicon dioxide precursor, and the mass of the ethanol also accounts for 10-30 wt% of the total mass of the tetramethyl disiloxane, the hexamethyldisiloxane and the silicon dioxide precursor;
the mass of the catalyst A is 2-65 wt% of the total mass of the tetramethyldisiloxane, the hexamethyldisiloxane and the silicon dioxide precursor.
5. The method for preparing an epoxy MQ silicone resin according to claim 3, wherein in step 1:
the hydrolysis condensation is carried out at the temperature of 30-80 ℃ and the heat preservation time is 1-5 h.
6. The method for preparing an epoxy MQ silicone resin according to claim 3, wherein in step 2:
the mass ratio of the hydrogen-containing MQ silicon resin to the phenol epoxy monomer is 1:0.2 to 1;
the mass of the catalyst B is 20-100 ppm of the content of the silicon hydrogen bond in the hydrogen-containing MQ silicon resin.
7. The method for preparing an epoxy MQ silicone resin according to claim 3, wherein in step 2:
the hydrosilylation reaction is carried out at the temperature of 50-90 ℃ and the heat preservation time is 4-10 h.
8. A preparation method of transparent modified phenol epoxy resin is characterized in that epoxy MQ silicon resin as claimed in claim 1 or 2 is used as raw material, the epoxy MQ silicon resin and phenol epoxy resin are mixed in any proportion, and the transparent modified phenol epoxy resin is prepared after curing.
9. The method for producing a transparent modified phenolic epoxy resin according to claim 8, wherein the phenolic epoxy resin is selected from a bisphenol type epoxy resin and/or a polyphenol type epoxy resin.
10. The method for preparing a transparent modified phenolic epoxy resin according to claim 8, wherein the mass ratio of the epoxy group MQ silicon resin to the phenolic epoxy resin is 10: 90-50: 50.
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