CN114573816B - A kind of epoxy-based MQ silicone resin and its preparation method and application - Google Patents

Abstract

The invention discloses an ^epoxy -based ^MQ _{silicone resin} , _a preparation method and application thereof ^. and/or (I-2), the structural formula of the ^M chain unit is shown in the following formula (II), and the structural formula of the Q chain unit is shown in the following formula (III), in the formula, a is selected from a positive integer of 10-1000, b is selected from a positive integer from 10 to 1000, c is selected from a positive integer from 10 to 1000, and (a+b)/c=0.6 to 2; the epoxy-based MQ silicone resin can effectively improve the phase with phenolic epoxy resin It can be blended with phenolic epoxy resin in any proportion to prepare transparent modified phenolic epoxy resin; more importantly, the prepared transparent modified phenolic epoxy resin has toughness Simultaneously with the mechanical properties (tensile strength, tensile modulus) have been improved.

Description

A kind of epoxy-based MQ silicone resin and its preparation method and application

technical field

The invention relates to the technical field of epoxy resin modification, in particular to an epoxy-based MQ silicone resin, a preparation method thereof, and an application in preparing a transparent modified phenolic epoxy resin.

Background technique

As one of the three traditional thermosetting resins (epoxy, phenolic and unsaturated polyester), epoxy resin has good mechanical and adhesive properties and is widely used in various industries, such as coatings, adhesives, electronic packaging, engineering plastics and composites etc. Due to the high crosslinking density of epoxy resin, its toughness is reduced, which limits its application, so toughening modification is required.

Adding flexible silicone segments is a common means of toughening epoxy, as in the article "The effect of epoxy–silicone copolymer content on the thermal and mechanical properties of curedepoxy resin modified with siloxane", chemically combining epoxy resin with hydroxyl-terminated silane Graft modification, using silane-modified epoxy resin as a toughening agent and compound curing with unmodified epoxy resin, it is found that the toughness of the cured product is greatly improved, but its tensile strength is significantly reduced. Another example is the article "The mechanical properties and toughening mechanisms of an epoxypolymer modified with polysiloxane-based core-shell particles", adding modified polysiloxane-based core-shell particles to the epoxy resin to improve the fracture toughness of the cured product, but the tensile strength and The modulus is significantly lower.

MQ silicone resin is a silicone resin with a double-layer structure composed of tetrafunctional siloxane polycondensation chains (Q) and monofunctional siloxane chains (M). It is methyl MQ silicone resin, vinyl MQ silicone resin, hydrogen-containing MQ silicone resin, etc., and is often used as a reinforcing material and tackifier for silicone rubber. Due to the low polarity of MQ silicone resin, it is rarely used as a toughening material in epoxy resin with high polarity.

Contents of the invention

Aiming at the above-mentioned problems existing in the prior art, the present invention discloses an epoxy-based MQ silicone resin and its preparation method and its application in the preparation of transparent modified phenolic epoxy resins. The epoxy-based MQ silicone resin can effectively Improve the compatibility and interfacial interaction with phenolic epoxy resin, and blend with phenolic epoxy resin in any proportion to prepare transparent modified phenolic epoxy resin; more importantly, the prepared transparent modified Reactive phenolic epoxy resin, its toughness and mechanical properties (tensile strength, tensile modulus) have been simultaneously improved.

The specific technical scheme is as follows:

An epoxy-based MQ silicone resin, the general molecular expression of which is (M ^R ) _a (M ^M ) _b Q _c , and the structural formula of the M ^R chain link is as follows: (I-1) and/or (I-2) Show:

The structural formula of the ^M chain link is shown in the following formula (II):

The structural formula of the Q chain link is shown in the following formula (Ⅲ):

In the formula, a is selected from a positive integer of 5-1000, b is selected from a positive integer of 10-1000, c is selected from a positive integer of 10-1000, and (a+b)/c=0.6-2.

The epoxy-based MQ silicone resin disclosed by the invention has a novel structure, and its end group is eugenol glycidyl ether or o-eugenol glycidyl ether, which is liquid at normal temperature, has excellent thermal stability, and has an initial decomposition temperature (T- _5% ) Higher than 300°C; excellent compatibility with phenolic epoxy resin, can be mixed in any proportion, the prepared modified phenolic epoxy resin has excellent transparency, and its tensile strength, bending strength, impact strength can be Obtain a large synchronous improvement; and by adjusting the ratio of (a+b)/c (that is, the ratio of M/Q), the molecular weight of the epoxy-based MQ silicone resin can be adjusted, thereby regulating the performance of the modified phenolic epoxy resin.

Preferably, a is selected from 5-150, b is selected from 10-150, and c is selected from 10-200; more preferably, a is selected from 5-25, b is selected from 14-25, and c is selected from 10-84.

The present invention also discloses a preparation method of the epoxy-based MQ silicone resin, comprising the steps of:

Step 1. Hydrolyzing and condensing tetramethyldisiloxane, hexamethyldisiloxane and silicon dioxide precursors under the action of catalyst A to obtain hydrogen-containing MQ silicone resin;

The silicon dioxide precursor is selected from tetraethyl orthosilicate and/or sodium silicate;

The catalyst A is selected from one or more of hydrochloric acid, sulfuric acid, toluenesulfonic acid;

Step 2, the hydrogen-containing MQ silicone resin prepared in step 1 and the phenolic epoxy monomer are subjected to a hydrosilylation reaction under the action of catalyst B to obtain epoxy-based MQ silicone resin;

The phenolic epoxy monomer is selected from eugenol epoxy and/or o-eugenol epoxy.

The catalyst B is selected from one or more of platinum catalysts, palladium catalysts and rhodium catalysts.

In step 1:

The molar ratio of the silicon dioxide precursor, tetramethyldisiloxane and hexamethyldisiloxane is 1:0.1～1:0.1～1;

Controlling the feeding molar ratio of the three raw materials within the above-mentioned range can ensure that (a+b)/c=0.6～2 in the prepared epoxy-based MQ silicone resin, thereby ensuring that the prepared epoxy-based MQ silicone resin Has body structure.

The hydrolytic condensation uses water and ethanol as solvents, and the mass of water and ethanol accounts for 10-30wt of the total mass of tetramethyldisiloxane, hexamethyldisiloxane and silicon dioxide precursor respectively %;

The mass of the catalyst A is 2 to 65 wt% of the total mass of the tetramethyldisiloxane, hexamethyldisiloxane and silicon dioxide precursor;

For the hydrolysis and condensation, the temperature is 30-80° C., and the holding time is 1-5 hours.

Preferably, in step 1, all raw materials except the silica precursor are first 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 hydrolysis condensation temperature Controlled in 30 ~ 60min.

All raw materials except the silicon dioxide precursor include tetramethyldisiloxane, hexamethyldisiloxane, catalyst A, ethanol and water.

It has been found through experiments that the molecular weight distribution of the prepared epoxy-based MQ silicone resin can be controlled within a narrower range by adopting the above-mentioned preferred order of addition.

In step 2:

The mass ratio of the hydrogen-containing MQ silicone resin to the phenolic epoxy monomer is 1:0.2-1;

The mass of the catalyst B is 20-100ppm of the silicon-hydrogen bond content in the hydrogen-containing MQ silicone resin;

The temperature of the hydrosilylation reaction is 50-90° C., and the holding time is 4-10 hours.

The invention also discloses a preparation method of a transparent modified phenolic epoxy resin, which uses the above-mentioned epoxy-based MQ silicone resin as a raw material, and mixes the epoxy-based MQ silicone resin with the phenolic epoxy resin in any proportion mixing and curing to prepare a transparent modified phenolic epoxy resin.

The curing agent used in the curing has no special requirements, and is selected from common types in the field, such as polyamine type, acid anhydride type, phenolic type, etc.

It is found through mechanical performance tests that when the epoxy-based MQ silicone resin is added in an appropriate amount, the transparent modified phenolic epoxy resin prepared by the present invention has a lower impact than the cured product of the phenolic epoxy resin alone. Strength, flexural strength and tensile strength have all been significantly improved.

Through comparative tests, if the eugenol glycidyl ether end group or the o-eugenol glycidyl ether end group of the epoxy MQ silicone resin disclosed in the present invention is replaced by the allyl glycidyl ether end group or 1,2-epoxy-4-vinylcyclohexane terminal group, the modified phenolic epoxy resin obtained by the same preparation process as above, firstly, it is opaque, and secondly, the impact strength has also been significantly improved, but However, the bending strength and tensile strength showed obvious deterioration.

Preferably, the phenolic epoxy resin is selected from bisphenol epoxy resins and/or polyphenol epoxy resins. The above phenolic epoxy resins are all selected from common types in this area, such as bisphenol type epoxy resins are selected from bisphenol A type epoxy resins, bisphenol F epoxy resins and the like; polyphenol type epoxy resins are selected from novolak Epoxy and more.

Epoxy-based MQ silicone resin disclosed by the present invention can be mixed with phenolic epoxy resin in any proportion, even under very high addition (as the mass ratio of epoxy-based MQ silicone resin to phenolic epoxy resin is 80 : 20) is still a transparent material. For example, the mass ratio of the epoxy-based MQ silicone resin to the phenolic epoxy resin is 5:95˜80:20. However, with the increase of the amount of epoxy-based MQ silicone resin, the tensile strength and bending strength of the prepared transparent modified phenolic epoxy resin will be sacrificed; and the addition amount is too small to improve the mechanical properties. significantly. Preferably, the mass ratio of the epoxy-based MQ silicone resin to the phenolic epoxy resin is 10:90˜50:50. That is, the mass ratio of the epoxy-based MQ silicone resin to the phenolic epoxy resin is 10:90, and the feed ratio of the epoxy-based MQ silicone resin is increased to a mass ratio of 50:50. Within this range, the tensile strength and flexural strength of the prepared transparent modified phenolic epoxy resin can meet the requirements for use, and have excellent toughness. More preferably, the mass ratio of the epoxy-based MQ silicone resin to the phenolic epoxy resin is 20:80.

Compared with prior art, the present invention has following advantage:

1. The present invention discloses a novel epoxy-based MQ silicone resin, which is liquid at room temperature and has excellent thermal stability; and by adjusting the ratio of (a+b)/c (i.e. the ratio of M/Q Ratio) can adjust the molecular weight of the epoxy-based MQ silicone resin, thereby regulating the performance of the modified phenolic epoxy resin.

2. The epoxy-based MQ silicone resin disclosed in the present invention has changed the shortcomings of traditional organic silicon resins that phase separation occurs in the toughening of epoxy resins, resulting in opacity. The epoxy-based MQ silicone resin can be miscible with phenolic epoxy resins in any proportion and The cured products are all transparent.

3. The epoxy-based MQ silicone resin disclosed in the present invention changes the shortcomings of the traditional silicone resin that the tensile properties of the resin are greatly reduced when the epoxy resin is toughened. The epoxy-based MQ silicone resin can make the toughened phenol The tensile strength, bending strength and impact strength of the epoxy-like resin have been greatly improved simultaneously.

Description of drawings

Fig. 1 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of the eugenol epoxy MQ silicone resin prepared by embodiment 1;

Fig. 2 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of the o-eugenol epoxy MQ silicone resin prepared by embodiment 2;

Fig. 3 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of the AGEMQ prepared in comparative example 2;

Fig. 4 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of the EVCMQ that comparative example 3 prepares;

Fig. 5 is an optical photograph of cured products prepared in Application Examples 1-5 and Comparative Application Examples 1-4 respectively.

Detailed ways

In order to further clarify the purpose, technical solutions and advantages of the present invention, the present invention will be further described in detail below in conjunction with specific examples, but the protection scope of the present invention is not limited thereby.

In the following examples, the proton nuclear magnetic resonance spectrum ¹ H-NMR adopts a Bruker Avance400 nuclear magnetic resonance spectrometer, and uses CDCl ₃ as a deuterated solvent.

Tensile strength and flexural strength were tested using a universal testing machine (Zwick/Roell Z020).

Impact strength was tested using a pendulum impact tester (CEAST 9050).

Example 1

Mix 5.4g (0.04mol) of tetramethyldisiloxane, 19.5g (0.12mol) of hexamethyldisiloxane, 20g of water, 15g of ethanol, and 3.3g of hydrochloric acid. Tetraethyl orthosilicate 60g (0.3mol), reacted for 3 hours, added toluene to extract, wash and separate the liquid, and distilled under reduced pressure to obtain a colorless and transparent hydrogen-containing MQ silicone resin.

Mix 25g of hydrogen-containing MQ silicone resin, 17.6g (0.08mol) of eugenol epoxy, and Castel catalyst (50ppm) and heat up to 70°C for 8 hours to obtain eugenol epoxy MQ silicone resin, which is denoted as EUEPMQ.

Fig. 1 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of EUEPMQ prepared in this embodiment, observe this figure and can confirm, the EUEPMQ prepared in this embodiment, molecular weight is 4230, and molecular weight distribution is 1.3, with reference to above-mentioned molecular expression general formula, then a =5, b=15, c=20.

Example 2

Mix 5.4g (0.04mol) of tetramethyldisiloxane, 19.5g (0.12mol) of hexamethyldisiloxane, 20g of water, 15g of ethanol, and 3.3g of hydrochloric acid. Tetraethyl orthosilicate 60g (0.3mol), reacted for 3 hours, added toluene to extract, wash and separate the liquid, and distilled under reduced pressure to obtain a colorless and transparent hydrogen-containing MQ silicone resin.

Mix 25g of hydrogen-containing MQ silicone resin, 17.6g (0.08mol) of o-eugenol epoxy, and Custer catalyst (50ppm) and heat up to 70°C for 8 hours to obtain o-eugenol epoxy MQ silicone resin, which is denoted as o-EUEPMQ .

Fig. 2 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of the o-EUEPMQ prepared in this embodiment, observing this figure can confirm, the o-EUEPMQ prepared in this embodiment has a molecular weight of 4320 and a molecular weight distribution of 1.3, referring to the above-mentioned molecular expression general Formula, then a=5, b=15, c=20.

Example 3

Mix 5.4g (0.04mol) of tetramethyldisiloxane, 19.5g (0.12mol) of hexamethyldisiloxane, 20g of water, 15g of ethanol, 3.3g of hydrochloric acid, and 60g (0.3mol) of ethyl orthosilicate , heated up to 70°C for 3 hours, added toluene to extract, wash and separate the liquid, and distilled under reduced pressure to obtain a colorless and transparent hydrogen-containing MQ silicone resin.

Mix 25g of hydrogen-containing MQ silicone resin, 17.6g (0.08mol) of eugenol epoxy, and Castel catalyst (50ppm) uniformly and raise the temperature to 70°C for 8 hours to obtain eugenol epoxy MQ silicone resin.

After characterization, the product prepared in this example has a molecular weight of 6780 and a molecular weight distribution of 2.0. Referring to the above molecular expression formula, a=8, b=24, c=32.

Example 4

Mix 6.7g (0.05mol) of tetramethyldisiloxane, 8.1g (0.05mol) of hexamethyldisiloxane, 25g of water, 15g of ethanol, and 3.3g of hydrochloric acid, and after 30min from room temperature to 60°C, add Tetraethyl orthosilicate 70g (0.34mol), reacted for 3h, added hexamethyldisiloxane for extraction, washed with water and separated, then distilled under reduced pressure to obtain a colorless and transparent hydrogen-containing MQ silicone resin.

Mix 25g of hydrogen-containing MQ silicone resin, 22g (0.1mol) of eugenol epoxy, and Castel catalyst (30ppm) and raise the temperature to 80°C for 6 hours to obtain eugenol epoxy MQ silicone resin.

After characterization, the product prepared in this example has a molecular weight of 15,000 and a molecular weight distribution of 1.4. Referring to the above molecular expression formula, a=24, b=24, c=80.

Example 5

Mix 13.4g (0.1mol) of tetramethyldisiloxane, 32.4g (0.2mol) of hexamethyldisiloxane, 20g of water, 20g of ethanol, and 3.3g of hydrochloric acid. 60 g (0.3 mol) of ethyl orthosilicate, reacted for 3 hours, added hexamethyldisiloxane to extract, wash and separate the liquid, and then distilled under reduced pressure to obtain a colorless and transparent hydrogen-containing MQ silicone resin.

Mix 50 g of hydrogen-containing MQ silicone resin, 44 g (0.2 mol) of eugenol epoxy, and Castel catalyst (30 ppm) and heat up to 80° C. for 6 hours to obtain eugenol epoxy MQ silicone resin.

After characterization, the product prepared in this example has a molecular weight of 3800 and a molecular weight distribution of 1.2. Referring to the above molecular expression formula, a=6, b=14, c=10.

Example 6

Mix 6.7g (0.05mol) of tetramethyldisiloxane, 8.1g (0.05mol) of hexamethyldisiloxane, 25g of water, 15g of ethanol, and 53g of hydrochloric acid. 72 g (0.34 mol) of sodium bicarbonate, reacted for 4 hours, added toluene to extract, wash and separate the liquid, and distilled under reduced pressure to obtain a colorless and transparent hydrogen-containing MQ silicone resin.

Mix 25g of hydrogen-containing MQ silicone resin, 22g (0.1mol) of eugenol epoxy, and Castel catalyst (30ppm) and raise the temperature to 80°C for 6 hours to obtain eugenol epoxy MQ silicone resin.

After characterization, the product prepared in this example has a molecular weight of 15800 and a molecular weight distribution of 1.5. Referring to the above molecular expression formula, a=25, b=25, c=84.

Comparative example 1

24.3g (0.15mol) of hexamethyldisiloxane, 15g of water, 15g of ethanol, and 2g of hydrochloric acid were mixed uniformly. After 30 minutes, the temperature was raised from room temperature to 50°C, and after adding 62.4g (0.25mol) of ethyl orthosilicate, the temperature was raised to 70 After reacting at ℃ for 3 hours, ethyl acetate was added to extract and washed with water several times, and the ethyl acetate was distilled off under reduced pressure to obtain a colorless transparent liquid methyl MQ silicone resin.

Comparative example 2

The preparation process is basically the same as in Example 1, except that 9.12 g (0.08 mol) of allyl glycidyl ether is used instead of eugenol epoxy. The product prepared in this comparative example is denoted as AGEMQ.

Fig. 3 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of the AGEMQ that this comparative example prepares, observes this figure and can confirm, the AGEMQ that this comparative example prepares, molecular weight is 3620, and molecular weight distribution is 1.3, and molecular expression general formula is (M ^R ) _a (M ^M ) _b Q _c , then a=5, b=15, c=20.

Wherein the structural formula of the M ^R chain link changes, as shown in the following formula, and the remaining structures remain unchanged:

Comparative example 3

The preparation process is basically the same as that in Example 1, except that 9.94 g (0.08 mol) of 1,2-epoxy-4-vinylcyclohexane is used instead of eugenol epoxy. The product prepared in this comparative example is denoted as EVCMQ.

Fig. 4 is the proton nuclear magnetic resonance spectrum ¹ H-NMR of the EVCMQ that this comparative example prepares, observes this figure and can confirm, the EVCMQ that this comparative example prepares, molecular weight is 3540, and molecular weight distribution is 1.3, and molecular expression general formula is (M ^R ) _a (M ^M ) _b Q _c , then a=5, b=15, c=20.

Wherein the structural formula of the M ^R chain link changes, as shown in the following formula, and the remaining structures remain unchanged:

Performance Testing

1. Mix the products prepared respectively in each embodiment and each comparative example with bisphenol A epoxy resin (E51) in parts by weight of 20:80, add 20 parts of curing agent isophorone diamine and mix evenly, inject Steel mold curing detection performance. The curing conditions are 80°C/2h, 150°C/2h, and the test results, including tensile strength, notched impact strength, and bending strength, are listed in Table 1 below. Table 1 also lists the data of the epoxy resin cured product (comparative application example 4) that is only obtained by mixing 100 parts by weight of bisphenol A epoxy resin (E51) with 20 parts of curing agent isophorone diamine and then curing comparing.

Table 1

Note: The numbers of the application examples and application comparison examples in the table correspond to the numbers of the corresponding examples. Taking application example 1 as an example, it means that the MQ silicone resin used is prepared in example 1; taking application example 1 as an example , which means that the MQ silicone resin used is prepared in Comparative Example 1.

Comparing the data in Table 1, it can be found that after adding the eugenol epoxy MQ silicone resin or o-eugenol epoxy MQ silicone resin prepared by the present invention in E51, the tensile strength, flexural strength, and impact resistance of the cured epoxy resin The strength has been significantly improved at the same time, indicating that the epoxy-based MQ silicone resin can effectively improve the mechanical properties of the bisphenol epoxy cured product without affecting the transparency of the resin. And if the epoxy-based MQ silicone resin prepared by the present invention is replaced by the methyl MQ silicone resin prepared in Comparative Example 1 or the epoxy-based MQ silicone resin with different end groups prepared in Comparative Examples 2 and 3, although it will also significantly improve The toughness of bisphenol-based epoxy cured products will not only greatly affect the transparency of the resin, but also cause a significant deterioration in tensile strength and bending strength.

Two, the eugenol epoxy MQ silicone resin prepared in Example 4 and the bisphenol A epoxy resin (E51) are respectively pressed at 10:90 (recorded as application example 5), 50:50 (recorded as application example 6), 80 : 20 parts by weight (recorded as application example 7) are mixed, and then correspondingly add 22 parts, 16 parts, and 10 parts of curing agent isophorone diamine respectively after mixing evenly, inject steel mold and solidify and test 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 and the bisphenol F epoxy resin (NPEF-170) are 20:80 (referred to as application example 8), 10:90 (referred to as application example 9) , 5:95 (recorded as application example 10) and 0:100 (recorded as application comparative example 5) are mixed in parts by weight, and then 21, 23, 24, 25 parts of curing agent isophorone diamine are added in sequence and mixed evenly Afterwards, pour into the steel mold to solidify and test the performance. The curing conditions were the same as above, and the test results are listed in Table 3 below.

table 3

Four, the eugenol epoxy MQ silicone resin prepared in Example 4 and the polyphenol epoxy resin (novolak epoxy resin) are respectively pressed 20:80 (recorded as application example 11), 0:100 (recorded as application comparative example 6) were mixed in parts by weight, and then 25 and 30 parts of curing agent 3,3'-diaminodiphenyl sulfone were added in turn and mixed evenly, and then injected into a steel mold for curing and testing performance. The curing conditions were the same 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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