CN108503798B

CN108503798B - High-heat-residue-weight modified epoxy resin and preparation method and application thereof

Info

Publication number: CN108503798B
Application number: CN201810349662.8A
Authority: CN
Inventors: 邹华维; 李�瑞; 陈洋; 罗杰民; 梁梅
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2018-04-18
Filing date: 2018-04-18
Publication date: 2021-03-02
Anticipated expiration: 2038-04-18
Also published as: CN108503798A

Abstract

The invention discloses a modified epoxy resin, and provides a pre-reaction epoxy resin which is prepared from the following components in parts by weight: 100 parts of epoxy resin, 3.16-6.31 parts of polyfunctional silane and 0.25-1.0 part of catalyst. The invention also provides an organic silicon modified epoxy resin which is prepared from the following components in parts by weight: 103.41-107.41 parts of pre-reaction epoxy resin, 0-40 parts of organic silicon intermediate, 0.25-1.0 part of catalyst and 25.5-45 parts of curing agent. The invention creatively utilizes the multi-functionality silane micromolecules to carry out pre-reaction on the epoxy molecules, thereby increasing the active functional group amount of the epoxy resin, and then introduces the organosilicon intermediate with the end capped by hydroxyl through grafting, thereby obviously improving the impact toughness of the epoxy curing system, effectively improving the compatibility of organosilicon and epoxy resin, obviously improving the thermal degradation stability and the thermal residual weight rate of the epoxy curing system, and slowing down the degradation process of the curing system.

Description

High-heat-residue-weight modified epoxy resin and preparation method and application thereof

Technical Field

The invention relates to a high-heat-residue modified epoxy resin and a preparation method and application thereof.

Background

Epoxy resins generally refer to high molecular oligomers containing two or more epoxy groups, having an organic compound such as alicyclic, aliphatic or aromatic as a skeleton, and capable of forming a thermosetting material of use by a reaction between the epoxy groups. Epoxy resins are generally liquid or solid prepolymers which have a linear structure and do not cure themselves, so that curing agents are required for curing the prepolymers before they can be used as materials. In practice, the epoxy resin refers to a resin formulation containing a curing agent and other additives or a cured product thereof. The most common are glycidyl ether type epoxy resins, wherein bisphenol a type epoxy resins account for about 80% of the epoxy resin market.

Epoxy resins have a high cohesive strength and therefore have a particularly high adhesive strength and a particularly broad adhesive surface, and can bond almost all materials except polyolefins. No micromolecule is separated out in the curing reaction process of the epoxy resin, so that the shrinkage rate of the epoxy resin is very low in the curing process, the shrinkage rate is less than 2 percent, and the epoxy resin is the one with the minimum shrinkage rate in the thermosetting resin. The epoxy resin has good chemical stability, and the epoxy resin without impurities such as salt, alkali and the like is not easy to deteriorate. Because the epoxy resin has the advantages, the epoxy resin can be widely used in various fields such as adhesives, coatings, light industry, machinery, construction, aerospace, electronic and electrical insulating materials, advanced composite materials and the like.

However, epoxy resin has the disadvantage of poor heat resistance, so that the application of epoxy resin in some high and new technology industries is limited, and particularly the wide application of epoxy resin in composite materials such as structural materials is limited. The structure of the material determines the performance of the material to a great extent, and in order to meet different performance requirements, the epoxy resin can be modified to meet the performance requirements.

For example, the toughness and the heat residual weight of methylphenyl organosilicon oligomer modified epoxy resin, such as common gold, 2013(08) discloses methylphenyl organosilicon oligomer modified epoxy resin, the heat residual weight of which at 600 ℃ is 27.19 percent, is improved by 21.83 percent compared with unmodified epoxy resin, but the requirement of practical application cannot be met.

Disclosure of Invention

In order to solve the problems, the invention provides a high-heat-residue modified epoxy resin and a preparation method and application thereof.

The invention provides a pre-reaction epoxy resin which is prepared from the following components in parts by weight:

100 parts of epoxy resin, 3.16-6.31 parts of polyfunctional silane and 0.25-1.0 part of catalyst.

Preferably, the composition is prepared from the following components in parts by weight:

100 parts of epoxy resin, 4.21-6.31 parts of polyfunctional silane and 0.5-1.0 part of catalyst.

More preferably, the composition is prepared from the following components in parts by weight:

100 parts of epoxy resin, 6.31 parts of polyfunctional silane and 0.5-0.75 part of catalyst.

Further, the epoxy resin is epoxy resin E51 or E44; and/or the multifunctional silane is isocyanatopropyl triethoxysilane or tetraethoxysilane; and/or the catalyst is butyl tin dilaurate or tetraisopropyl titanate.

The invention provides a method for preparing the pre-reaction epoxy resin, which comprises the following steps:

taking the raw materials according to the proportion, and reacting the epoxy resin and the polyfunctional silane in the presence of a catalyst to obtain the pre-reaction epoxy resin.

Further, the pre-reacted epoxy resin is prepared by the following method: adding epoxy resin and polyfunctional silane into a reactor under an inert environment, adding a catalyst at 50 +/-5 ℃, and reacting for 3-5 hours to obtain the epoxy resin-modified epoxy resin.

The use of the pre-reacted epoxy resin in the preparation of an organosilicon intermediate modified epoxy resin.

The invention provides an organic silicon modified epoxy resin which is prepared from the following components in parts by weight:

103.41-107.41 parts of pre-reaction epoxy resin, 0-40 parts of organic silicon intermediate, 0.25-1.0 part of catalyst and 25.5-45 parts of curing agent.

104.71-107.31 parts of pre-reaction epoxy resin, 10-40 parts of organic silicon intermediate, 0.5-1.0 part of catalyst and 34-40 parts of curing agent.

106.81-107.06 parts of pre-reaction epoxy resin, 20-40 parts of organic silicon intermediate, 0.5-0.75 part of catalyst and 40 parts of curing agent.

Further, the organosilicon intermediate is a hydroxyl-terminated methylphenyl organosilicon intermediate or a hydroxyl-terminated phenyl organosilicon intermediate; and/or, the catalyst is butyl tin dilaurate or tetraisopropyl titanate; and/or the curing agent is 4,4' -diamino-3, 3 ' -dichlorodiphenylmethane or 4,4' -diaminodiphenylmethane.

The invention provides a method for preparing the organic silicon modified epoxy resin, which comprises the following steps:

(1) adding an organic silicon intermediate into the pre-reaction epoxy resin, and reacting to obtain a prepolymer IE-Z;

(2) and (3) uniformly mixing the prepolymer IE-Z with a curing agent, defoaming and curing to obtain the epoxy resin.

Wherein, in the step (1), the prepolymer IE-Z is prepared by the following method: and adding an organic silicon intermediate into the pre-reaction epoxy resin, stirring, heating to 150 +/-10 ℃, adding a catalyst, and reacting for 4-6 hours to obtain the epoxy resin.

In the step (2), the dosage of the curing agent is calculated according to the equivalent of active hydrogen and the epoxy value of the prepolymer IE-Z; and/or the curing process is 140-160 ℃/1-3 h + 170-190 ℃/1-3 h.

The modified epoxy resin is used for preparing high-temperature, thermal protection and fire-resistant materials or appliances.

Preferably, the high temperature, thermal protection and refractory material or appliance is an aerospace high temperature, thermal protection and refractory material or appliance.

The invention provides a high-heat-residue-weight modified epoxy resin and a preparation method and application thereof, and the invention creatively utilizes multi-functionality silane micromolecules to carry out pre-reaction on epoxy molecules, thereby improving the active functional group amount of the epoxy resin, and then introduces a hydroxyl-terminated organosilicon intermediate through grafting; according to the invention, more flexible organosilicon intermediates can be introduced by utilizing the method, so that the impact toughness of an epoxy curing system is obviously improved, the compatibility of organosilicon and epoxy resin is effectively improved, the thermal degradation stability and the thermal residual weight rate of the organosilicon and epoxy resin are obviously improved, and the degradation process of the curing system is slowed down.

Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.

The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Drawings

FIG. 1 shows the preparation of IE-Z prepolymer;

FIG. 2 is an infrared spectrum of IPTS pretreatment E51;

FIG. 3 is an IR spectrum of IE, PMPS-Z and IE-Z10 prepolymer;

FIG. 4 is a graph of the effect of PMPS-Z content on tensile properties of IE-Z/MOCA cure systems;

FIG. 5 is a graph of the impact of PMPS-Z content on the impact performance of IE-Z/MOCA cure system;

FIG. 6 is a Scanning Electron Microscope (SEM) image of IE-Z/MOCA cure system × 500: (a) IE, (b) IE-Z10, (c) IE-Z30, (d) E-Z10, (E) E-Z30;

FIG. 7 is a statistical plot of the dispersed phase size for the IE-Z/MOCA cure system: (a) IE-Z10, (b) IE-Z30, (c) E-Z10, (d) E-Z30;

FIG. 8 is a IE-Z/MOCA cure system at N₂TG (a) and DTG (b) curves for atmosphere measurements;

FIG. 9 is tan delta (a) and E' (b) curves for the IE-Z/MOCA cure system.

Detailed Description

The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.

Epoxy resin: e51, technical grade, south american star synthetic materials ltd;

organosilicon intermediate: hydroxy-terminated methylphenyl silicone intermediate, technical grade;

curing agent: 4,4 '-diamino-3, 3' -dichlorodiphenylmethane, technical grade, febrile beil chemical ltd;

multifunctional silanes: isopropyltriethoxysilane isocyanate, analytically pure, Shanghai Crystal pure science and technology Co., Ltd;

catalyst: butyltin dilaurate, analytically pure, was produced by the chemical reagent factory of Syngnathus, City.

Example 1

(1) Expanding the number of reactive functional groups of the epoxy resin

To a three-necked flask equipped with a thermometer, mechanical stirrer and inert gas device were added 100g of epoxy resin (E51) and 6.31g of Isocyanatopropyltriethoxysilane (IPTS) in that order. Increasing the temperature of the system and starting the stirring device until the temperature is constant at 50 ℃, adding 0.5 wt% of butyltin dilaurate (DBTDL), and taking a little product every hour for infrared test until the characteristic absorption peak of isocyanate (-NCO) in an infrared spectrum is 2270cm^-1And finishing the reaction after the epoxy resin disappears to obtain the pre-reaction epoxy resin (IE).

(2) Preparation of prepolymer (IE-Z) of hydroxyl terminated organosilicon intermediate modified Pre-reacted epoxy resin

To a three-necked flask equipped with a thermometer, mechanical stirrer and inert gas apparatus was added the corresponding pretreated epoxy resin IE and hydroxy-terminated methylphenyl silicone intermediate in the proportions shown in Table 1. The system temperature was raised and the stirring apparatus was turned on until the temperature was constant at 150 ℃, 0.5 wt.% of butyltin dilaurate was added, and the reaction was terminated after 4 hours to obtain a prepolymer (IE-Z). The reaction process is shown in figure 1.

(3) Curing and forming

According to the proportion in Table 1, prepolymer (IE-Z) and curing agent (MOCA) with corresponding mass are weighed in a 250mL beaker, the mixture is stirred to be uniform at 80 ℃, and then the mixture is placed in a vacuum oven for defoaming treatment.

After the defoaming process is finished, the mixture is cast in a preheated polytetrafluoroethylene mold, and then the mixture is placed in a blast oven to be cured according to the curing process of 140-160 ℃/1-3 h + 170-190 ℃/1-3 h. After curing is complete, the bars are removed from the mold and ready for use.

Table 1 formula table of hydroxyl-terminated organosilicon intermediate modified epoxy resin

Sample name	Silane/g	Epoxy resin/g	Organosilicon intermediates/g	Curing agent/g
					IE	6.31	100	0	40
IE-Z10	6.31	100	10	40
					IE-Z20	6.31	100	20	40
IE-Z30	6.31	100	30	40
					IE-Z40	6.31	100	40	40

Example 2

The hydroxyl terminated silicone intermediate modified epoxy resin was prepared by reacting the preparation method of example 1 with the formulation tables of tables 1-2.

TABLE 1-2 formulation table of hydroxyl-terminated organosilicon intermediate modified epoxy resin

Sample name	Silane/g	Epoxy resin/g	Catalyst and process for preparing same	Organosilicon intermediates/g	Curing agent/g
						IE-Z20-1	4.21	100	0.75	20	25.5
IE-Z20-2	3.16	100	0.25	20	40
						IE-Z20-3	6.13	100	0.5	20	45
IE-Z20-4	6.31	100	1	20	34

Comparative example 1

(1) Preparation of prepolymer (E-Z) of hydroxyl-terminated organosilicon intermediate-modified epoxy resin

To a three-necked flask equipped with a thermometer, mechanical stirrer and inert gas apparatus was added the corresponding epoxy resin (E51) and hydroxy-terminated methylphenyl silicone intermediate in the proportions shown in Table 2. The system temperature was raised and the stirring apparatus was turned on until the temperature was constant at 150 ℃, 0.5 wt.% of butyltin dilaurate was added, and the reaction was terminated after 4 hours to obtain prepolymer (E-Z). (2) Curing and forming

Weighing the prepolymer (E-Z) and the curing agent with corresponding mass in a 250mL beaker according to the mixture ratio of Table 2, stirring the mixture to be uniform at 80 ℃, and then placing the mixture into a vacuum oven for defoaming treatment. After the defoaming process is finished, the mixture is cast in a preheated polytetrafluoroethylene mold, and then the mixture is placed in a blast oven to be cured according to the curing process of 140-160 ℃/1-3 h + 170-190 ℃/1-3 h. After curing is complete, the bars are removed from the mold and ready for use.

TABLE 2 formulation table of hydroxyl-terminated organosilicon intermediate modified epoxy resin

Sample name	Epoxy resin/g	Organosilicon intermediates/g	Curing agent/g
				E
	100	0	40
				E-Z10	100	10	40
E-Z30	100	30	40

The beneficial effects of the invention are illustrated by way of experimental examples as follows:

experimental example 1 Infrared (FTIR) Spectroscopy analysis

The invention characterizes whether the grafting reaction of the hydroxyl of PMPS-Z and the active ethoxy of the pre-reacted epoxy resin IE is successfully carried out or not by infrared (FTIR) spectrum analysis. FIG. 2 shows the IR spectra of the raw materials Isopropyltriethoxysilane (IPTS), IPTS reacted with epoxy resin for 4h (IE-4) and IPTS reacted with epoxy resin for 5h (IE-5). In FIG. 3, (a) is an IR spectrum of a pre-reacted epoxy resin IE prepared in the step (1) of example 1, (b) is an IR spectrum of a raw material silicone intermediate (PMPS-Z), and (c) is an IR spectrum of a prepolymer IE-Z10 prepared in the step (2) of example 1.

The spectrum of IPTS in FIG. 2 shows that the concentration is 2270cm^-1A stretching vibration characteristic absorption peak of isocyanic acid radical (-NCO) in IPTS appears; from the IE-4 and IE-5 spectra in FIG. 2, it can be seen that 2270cm is obtained after pretreatment of the epoxy resin with IPTS for 4h and 5h, respectively^-1The characteristic absorption peaks at the position (a) and (b) obviously disappear, and the characteristic absorption peak of N-H stretching vibration is newly appeared at the position (3410 cm-1), which shows that IPTS can completely react with E51 within 4H under the condition of 50 ℃. Thus, the pretreatment reaction conditions were set to 50 ℃ for 4 hours.

As can be seen from FIG. 3(c), 1130cm^-1And 1030cm^-1New peak is assigned to the characteristic absorption peak of Si-O-C and Si-O-Si, and the epoxy matrix is 914cm^-1And 833cm^-1The characteristic absorption peak of (A) is retained.

In conclusion, the infrared spectrum results show that the hydroxyl group of PMPS-Z successfully undergoes a grafting reaction with the active ethoxy group of the pre-reacted epoxy resin IE, and the grafting reaction is consistent with the pre-reaction (figure 1).

Experimental example 2 mechanical Properties

The mechanical properties of the invention are characterized by tensile strength, elongation at break and impact strength, and FIG. 4 shows the influence of the PMPS-Z content of the organosilicon intermediate on the tensile strength (a) and elongation at break (b) of an IE-Z/MOCA curing system. FIG. 5 is a graph of the effect of the level of silicone intermediate PMPS-Z on the impact strength of IE-Z/MOCA cured systems.

As can be seen from FIG. 4(a), after the flexible silicone intermediate PMPS-Z is introduced into the epoxy matrix, the tensile strength of the cured system tends to decrease,the elongation at break tends to increase and then decrease. As can be seen from FIG. 5, the impact strength of the cured system tended to increase with increasing silicone intermediate addition, and when PMPS-Z was added at 40phr, the impact strength of the cured system was 1.79kJ/m²Compared with a pure sample, the impact toughness of the epoxy curing system is improved by 14.74%, which shows that the introduction of the flexible organosilicon intermediate has a certain improvement effect on the impact toughness of the epoxy curing system.

EXAMPLE 3 microscopic morphology analysis (SEM)

The compatibility of the silicone (PMPS-Z) and the epoxy resin (E51) is characterized by a scanning electron microscope. FIG. 6 is an SEM image of impact cross-section of the cured systems of example IE-Z/MOCA and comparative example E-Z/MOCA, and FIG. 7 is a statistical plot of the dispersed phase size of the cured systems of example IE-Z/MOCA and comparative example E-Z/MOCA.

FIG. 6(a) is an SEM image of a pure IE sample having a very smooth and flat cross-section without the presence of dispersed phase; FIGS. 6(b) and (c) are SEM images of IE-Z10 and IE-Z30, respectively, whose cross-sections become uneven and the appearance of a small amount of dispersed phase can be observed, but the phase interface is relatively blurred; FIGS. 6(d) and (E) are SEM images of E-Z10 and E-Z30, respectively, and it is apparent that the appearance of the dispersed phase is observed and the dispersed phase size is not uniform.

As can be seen from FIG. 7, the IE-Z10 and IE-Z30 systems have a small number of dispersed phases and are distributed very uniformly, and the size of the dispersed phases is mainly concentrated to about 2.5 μm; the E-Z10 and E-Z30 systems have large span of dispersed phase distribution, nonuniform distribution and obviously larger dispersed phase size than the IE-Z/MOCA curing system.

In conclusion, by comparing SEM images of IE-Z/MOCA and E-Z/MOCA curing systems, the compatibility of the organic silicon (PMPS-Z) and the epoxy resin (E51) is effectively improved by the method of extending the reactive group amount of the E51 matrix through multifunctional IPTS and then grafting and introducing the organic silicon intermediate.

EXAMPLE 4 thermogravimetric analysis (TGA)

The thermal degradation stability and the thermal residual weight rate of the material prepared by the invention are characterized by thermogravimetric analysis (TGA). FIG. 8 is an IE-Z/MOCA cure system at N₂Thermal stability profile measured under atmosphere: (a) heat generationA heavy (TG) curve, (b) a slightly-quotient thermogravimetric (DTG) curve, and Table 3 lists the thermal stability parameters associated with IE-Z/MOCA cure systems, including the initial decomposition temperature (T)_5％) Temperature (T) corresponding to maximum thermal decomposition rate_max) And heat residual weight at 800 ℃.

As can be seen from FIG. 8 and Table 3, the introduction of PMPS-Z has no effect on the thermal degradation mechanism of the epoxy curing system, but on the initial decomposition temperature (T) of the system_5％) The IE-Z/MOCA curing system has weak promotion effect, the degradation rate of the IE-Z/MOCA curing system is obviously lower than that of a pure sample system in a high-temperature region above 400 ℃, and finally the thermal residual weight of the IE-Z40/MOCA curing system is obviously higher than that of the pure sample curing system at 800 ℃, and particularly, when the addition amount of PMPS-Z is 40phr, the residual weight of the IE-Z40/MOCA curing system at 800 ℃ is 36.02%, which is improved by 62.70% compared with that of the pure sample IE/MOCA curing system.

TABLE 3 thermal stability related parameters of IE-Z/MOCA curing systems

In conclusion, compared with IE-Z/MOCA and E-Z/MOCA curing systems, the thermal degradation stability and residual weight of the IE-Z curing system are obviously superior to those of the E-Z curing system; the result shows that the method for introducing PMPS-Z after pretreating the E51 matrix by IPTS is more effective in improving the thermal degradation stability and the thermal residual weight ratio of the epoxy curing system than the method for directly introducing PMPS-Z. Therefore, the method for pretreating the E51 matrix by IPTS can slow down the degradation process of the curing system and improve the thermal degradation stability and the thermal residual weight rate of the system.

Experimental example 5 dynamic thermomechanical analysis test (DMA)

The Tg of the product prepared according to the invention was characterized by dynamic thermo-mechanical analysis test (DMA), fig. 9 is a graph of dynamic thermo-mechanical analysis of IE-Z/MOCA cure system: (a) tan delta curve, (b) E' curve,table 4 lists DMA values, including glass transition temperature (T), for IE-Z/MOCA cure systems_g) Storage modulus (E'), and crosslink density (Ve).

As can be seen from FIG. 9(a), the glass transition temperature of the PMPS-Z modified epoxy curing system shifts to a high temperature region, and the glass transition temperature of the curing system increases with the increase in the addition amount of PMPS-Z of silicone, and when the addition amount of PMPS-Z is 40phr, the T of the curing system_gT of pure IE system at 162.61 DEG C_gThe temperature is increased by 10.37 ℃.

TABLE 4 DMA eigenvalues for IE-Z/MOCA cure system

Sample name	T_g(℃)	E’at 40℃(MPa)	V_e(mol/dm³)
				IE	152.24	2394	1.7851
IE-Z10	157.34	2646	2.2358
				IE-Z20	159.78	2642	2.6289
IE-Z30	154.68	1915	2.0844
				IE-Z40	162.61	2111	2.4265

In conclusion, the invention provides a high-heat-residue-weight modified epoxy resin, a preparation method and application thereof, and the invention creatively utilizes multi-functionality silane micromolecules to carry out pre-reaction on epoxy molecules, thereby improving the active functional group amount of the epoxy resin, and then introduces a hydroxyl-terminated organosilicon intermediate through grafting; according to the invention, more flexible organosilicon intermediates can be introduced by utilizing the method, so that the impact toughness of an epoxy curing system is obviously improved, the compatibility of organosilicon and epoxy resin is effectively improved, the thermal degradation stability and the thermal residual weight rate of the organosilicon and epoxy resin are obviously improved, and the degradation process of the curing system is slowed down.

Claims

1. An organic silicon modified epoxy resin is characterized in that: the composition is prepared from the following components in parts by weight:

103.41-107.41 parts of pre-reaction epoxy resin, 10 parts of organic silicon intermediate, 0.25-1.0 part of catalyst and 25.5-45 parts of curing agent;

the pre-reaction epoxy resin is prepared from the following components in parts by weight: 100 parts of epoxy resin, 3.16-6.31 parts of polyfunctional silane and 0.25-1.0 part of catalyst;

the organosilicon intermediate is a hydroxyl-terminated methylphenyl organosilicon intermediate or a hydroxyl-terminated phenyl organosilicon intermediate; the multifunctional silane is isocyanatopropyl triethoxysilane or tetraethoxysilane.

2. The silicone-modified epoxy resin according to claim 1, characterized in that: the composition is prepared from the following components in parts by weight:

103.41 parts of pre-reaction epoxy resin, 10 parts of organosilicon intermediate, 0.5-1.0 part of catalyst and 34-40 parts of curing agent.

3. The silicone-modified epoxy resin according to claim 2, characterized in that: the composition is prepared from the following components in parts by weight:

103.41 parts of pre-reaction epoxy resin, 10 parts of organosilicon intermediate, 0.5-0.75 part of catalyst and 40 parts of curing agent.

4. The silicone-modified epoxy resin according to any one of claims 1 to 3, characterized in that: the catalyst is butyl tin dilaurate or tetraisopropyl titanate; and/or the curing agent is 4,4' -diamino-3, 3 ' -dichlorodiphenylmethane or 4,4' -diaminodiphenylmethane.

5. The silicone-modified epoxy resin according to claim 1, characterized in that: the pre-reaction epoxy resin is prepared from the following components in parts by weight:

6. The silicone-modified epoxy resin according to claim 5, characterized in that: the pre-reaction epoxy resin is prepared from the following components in parts by weight:

7. The silicone-modified epoxy resin according to claim 5 or 6, characterized in that: the epoxy resin is epoxy resin E51 or E44; and/or the catalyst is butyl tin dilaurate or tetraisopropyl titanate.

8. The silicone-modified epoxy resin according to claim 1, characterized in that: the pre-reacted epoxy resin is prepared by the following method: taking raw materials according to the proportion of claim 1, reacting epoxy resin and polyfunctional silane in the presence of a catalyst to obtain pre-reaction epoxy resin.

9. The silicone-modified epoxy resin according to claim 8, characterized in that: the pre-reacted epoxy resin is prepared by the following method: adding epoxy resin and polyfunctional silane into a reactor under an inert environment, adding a catalyst at 50 +/-5 ℃, and reacting for 3-5 hours to obtain the epoxy resin-modified epoxy resin.

10. A method for preparing the silicone-modified epoxy resin according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:

(1) adding an organic silicon intermediate into the pre-reaction epoxy resin, and reacting to obtain a prepolymer IE-Z; the prepolymer IE-Z is prepared by the following method: adding an organic silicon intermediate into the pre-reaction epoxy resin, stirring, heating to 150 +/-10 ℃, adding a catalyst, and reacting for 4-6 hours to obtain the epoxy resin;

11. The method of claim 10, wherein:

12. Use of the silicone-modified epoxy resin of any one of claims 1 to 9 in the preparation of high temperature, thermal protective and fire resistant materials or appliances.

13. Use according to claim 12, characterized in that: the high-temperature, thermal protection and refractory material or appliance is an aerospace high-temperature, thermal protection and refractory material or appliance.

14. Use of the pre-reacted epoxy resin of any one of claims 1 to 9 in the preparation of the silicone-modified epoxy resin of any one of claims 1 to 9.