CN111087564B - Organic silicon epoxy monomer modified phenolic resin and preparation method thereof - Google Patents
Organic silicon epoxy monomer modified phenolic resin and preparation method thereof Download PDFInfo
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- CN111087564B CN111087564B CN201911404311.3A CN201911404311A CN111087564B CN 111087564 B CN111087564 B CN 111087564B CN 201911404311 A CN201911404311 A CN 201911404311A CN 111087564 B CN111087564 B CN 111087564B
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Abstract
The invention discloses an organic silicon epoxy monomer modified phenolic resin and a preparation method thereof, and the preparation method comprises the following steps: 1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution; 2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the phenolic resin modified by the organic silicon epoxy monomer.
Description
Technical Field
The invention relates to a modified phenolic resin and a preparation method thereof, in particular to a phenolic resin modified by an organic silicon epoxy monomer and a preparation method thereof.
Background
As one of three thermosetting resins, phenolic resin has the characteristics of excellent heat resistance, simple synthesis process, cheap and easily available raw materials and the like, so that the phenolic resin is widely applied. However, with the development of the times and the progress of science and technology, higher requirements are put forward on the comprehensive performance of the phenolic resin. The phenolic resin has the defects of high brittleness, low peel strength, high odor during curing, high curing shrinkage rate and the like, and due to the structure of the phenolic resin, if a large number of easily-oxidized groups (such as phenolic hydroxyl, methylene and the like) exist, the heat resistance of the phenolic resin is influenced to a certain extent, so that the requirement of the phenolic resin on the performance of the material is difficult to meet.
In the modification research of phenolic resin, the organic silicon modified phenolic resin is always focused by researchers. Since the organic silicon has excellent heat resistance, flexibility and lower surface tension, the organic silicon introduced into the phenolic resin can effectively improve the comprehensive performance of the resin, but the conventional organic silicon (such as amino silicone oil, hydroxyl silicone oil and the like) has poor compatibility with the phenolic resin, the two are difficult to perform homogeneous reaction, and if the two are simply mixed, a separated structure is presented due to the higher tension between the contact surfaces of the two, so that the modification effect is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the phenolic resin modified by the organic silicon epoxy monomer and the preparation method thereof, and the resin and the preparation method thereof can effectively improve the compatibility between organic silicon and the phenolic resin.
In order to achieve the purpose, the organic silicon epoxy monomer modified phenolic resin has the chemical structure as follows:
wherein m is1And m2Are each an integer greater than 2 and less than 9.
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: (0.1-4): (0.001-0.05).
The structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Each independently hydrogen, substituted or unsubstituted C1To C30Alkyl or substituted or unsubstituted C3To C30Cycloalkyl groups of (a);
R4and R5Are each independently a single bond or a substituted or unsubstituted C1To C30An alkylene group or an alkylene ether group of (a);
X1、X2、X3、X4、X5and X6Each independently hydrogen, substituted or unsubstituted C1To C30Alkyl, substituted or unsubstituted C3To C30Cycloalkyl, substituted or unsubstituted C1To C30A substituted or unsubstituted C1To C30Alkyl ether group of (A), substituted or unsubstituted C6To C30Aryl, substituted or unsubstituted C2To C30Or substituted or unsubstituted C7To C30Aralkyl group of (1); x1、X2、X3、X4、X5And X6At least one of which is substituted or unsubstituted C6To C30Aryl or substituted or unsubstituted C2To C30The heteroaryl group of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is 1, 3-diaminodicyclopentadiene, ammonium chloride, 4-diaminodiphenylmethane, triphenylphosphine, diethylenetriamine or polyphenylsulfone.
The solvent in the step 1) is acetone, ethanol, toluene or a mixed solution of acetone and ethanol.
In the step 2), the time of the constant-temperature stirring reflux reaction is 4-12 h, and the temperature of the constant-temperature stirring reflux reaction is 55-120 ℃.
The invention has the following beneficial effects:
during specific operation, the epoxy group on the organosilicon epoxy monomer and the phenolic hydroxyl group on the thermoplastic phenolic resin are subjected to ring-opening addition reaction under the action of a catalyst in a chemical reaction mode, so that the organosilicon epoxy monomer is introduced onto the thermoplastic phenolic resin in a chemical grafting mode, and the problem of poor compatibility of organosilicon and phenolic resin is solved. Tests prove that the weight retention rate of the phenolic resin modified by the organosilicon epoxy monomer in a nitrogen atmosphere at 1000 ℃ can reach 54.015%, and meanwhile, in the air atmosphere, the pyrolysis rate of the phenolic resin modified by the organosilicon epoxy monomer at 400 ℃ is lower than that of the unmodified phenolic resin, so that the phenolic resin modified by the organosilicon epoxy monomer has good ablation resistance and thermal stability, and the preparation method is simple to operate and has low cost.
Drawings
FIG. 1 shows the preparation of silicone epoxy monomer modified phenolic resin (EPSiNR)1H-NMR spectrum;
FIG. 2 is a DSC plot of a thermoplastic phenolic resin (NR) and a silicone epoxy monomer modified phenolic resin (EPSiNR) prepared in example two;
FIG. 3 is a graph showing TG and DTG curves of EPSiNR prepared in example III under a nitrogen atmosphere;
FIG. 4 is a graph showing TG and DTG curves of EPSiNR prepared in example III in an air atmosphere;
FIG. 5 is a DMA tan delta plot of EPSiNR prepared in example three.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
the chemical structure of the organic silicon epoxy monomer modified phenolic resin is as follows:
wherein m is1And m2Are each an integer greater than 2 and less than 9.
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: (0.1-4): (0.001-0.05).
The structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Each independently hydrogen, substituted or unsubstituted C1To C30Alkyl or substituted or unsubstituted C3To C30Cycloalkyl groups of (a);
R4and R5Are each independently a single bond or a substituted or unsubstituted C1To C30An alkylene group or an alkylene ether group of (a);
X1、X2、X3、X4、X5and X6Each independently hydrogen, substituted or unsubstituted C1To C30Alkyl, substituted or unsubstituted C3To C30Cycloalkyl, substituted or unsubstituted C1To C30A substituted or unsubstituted C1To C30Alkyl ether group of (A), substituted or unsubstituted C6To C30Aryl, substituted or unsubstituted C2To C30Or substituted or unsubstituted C7To C30Aralkyl group of (1); x1、X2、X3、X4、X5And X6At least one of which is substituted or unsubstituted C6To C30Aryl or substituted or unsubstituted C2To C30The heteroaryl group of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is 1, 3-diaminodicyclopentadiene, ammonium chloride, 4-diaminodiphenylmethane, triphenylphosphine, diethylenetriamine or polyphenylsulfone.
The solvent in the step 1) is acetone, ethanol, toluene or a mixed solution of acetone and ethanol.
In the step 2), the time of the constant-temperature stirring reflux reaction is 4-12 h, and the temperature of the constant-temperature stirring reflux reaction is 55-120 ℃.
Example one
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing 10g of thermoplastic phenolic resin, 10g of organic silicon epoxy monomer and 0.01g of catalyst, mixing, putting into 120ml of solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Are each independently hydrogen;
R4and R5Are each independently a single bond;
X2、X3、X4、X5and X6Are each independently hydrogen; x1Is substituted C6Aryl of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is ammonium chloride.
The solvent in the step 1) is ethanol.
In the step 2), the time of the constant-temperature stirring reflux reaction is 4 hours, and the temperature of the constant-temperature stirring reflux reaction is 80 ℃.
Example two
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing 20g of thermoplastic phenolic resin, 23g of organic silicon epoxy monomer and 0.05g of catalyst, mixing, putting into 200ml of solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is substituted C1Alkyl groups of (a);
R4and R5Is substituted C1An alkylene group of (a);
X1、X3、X4、X5and X6Are each independently hydrogen; x2Is substituted C30Aryl of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is triphenylphosphine.
The solvent in step 1) is acetone.
In the step 2), the time of the constant-temperature stirring reflux reaction is 8 hours, and the temperature of the constant-temperature stirring reflux reaction is 60 ℃.
EXAMPLE III
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing 15g of thermoplastic phenolic resin, 30g of organic silicon epoxy monomer and 0.20g of catalyst, mixing, putting into 180ml of solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is substituted C30Alkyl groups of (a);
R4and R5Is substituted C30An alkylene group of (a);
X1、X2、X4、X5and X6Are each independently hydrogen; x3Substituted C20Aryl of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is ammonium chloride.
The solvent in the step 1) is ethanol.
In the step 2), the time of the constant-temperature stirring reflux reaction is 10 hours, and the temperature of the constant-temperature stirring reflux reaction is 85 ℃.
Example four
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing 25g of thermoplastic phenolic resin, 13g of organic silicon epoxy monomer and 0.15g of catalyst, mixing, putting into 230ml of obtained solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is substituted C10Alkyl groups of (a);
R4and R5Is substituted C20An alkylene group of (a);
X1、X2、X3、X5and X6Are each independently hydrogen; x4Is unsubstituted C6Aryl of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is 1, 3-diaminohetero cyclopentadiene.
The solvent in step 1) is toluene.
In the step 2), the time of the constant-temperature stirring reflux reaction is 6 hours, and the temperature of the constant-temperature stirring reflux reaction is 230 ℃.
EXAMPLE five
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing 14g of thermoplastic phenolic resin, 46g of organosilicon epoxy monomer and 0.21g of catalyst, mixing, putting into 180ml of solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is unsubstituted C1Alkyl groups of (a);
R4and R5Is unsubstituted C1An alkylene group of (a);
X1、X2、X3、X4and X6Are each independently hydrogen; x5Is unsubstituted C30Aryl of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is polyphenylsulfone.
The solvent in the step 1) is ethanol.
In the step 2), the time of the constant-temperature stirring reflux reaction is 4.5h, and the temperature of the constant-temperature stirring reflux reaction is 75 ℃.
EXAMPLE six
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: 0.1: 0.001.
the structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is unsubstituted C30Alkyl groups of (a);
R4and R5Is unsubstituted C30An alkylene group of (a);
X6are each independently hydrogen; x6Is unsubstituted C20Aryl of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is 4, 4-diaminodiphenylmethane.
The solvent in the step 1) is a mixed solution of acetone and ethanol.
In the step 2), the time of the constant-temperature stirring reflux reaction is 4 hours, and the temperature of the constant-temperature stirring reflux reaction is 55 ℃.
EXAMPLE seven
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: 4: 0.05.
the structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is unsubstituted C20Alkyl groups of (a);
R4and R5Is unsubstituted C20An alkylene group of (a);
X2、X3、X4、X5and X6Are each independently hydrogen; x1Is substituted C20The heteroaryl group of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is diethylenetriamine.
The solvent in step 1) is toluene.
In the step 2), the time of the constant-temperature stirring reflux reaction is 12 hours, and the temperature of the constant-temperature stirring reflux reaction is 120 ℃.
Example eight
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: 2: 0.03.
the structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is substituted C3Cycloalkyl groups of (a);
R4and R5Is substituted C1An alkylene ether group of (a);
X1、X3、X4、X5and X6Are each independently hydrogen; x2Unsubstituted C30The heteroaryl group of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is triphenylphosphine.
The solvent in step 1) is toluene.
In the step 2), the time of the constant-temperature stirring reflux reaction is 10 hours, and the temperature of the constant-temperature stirring reflux reaction is 100 ℃.
Example nine
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: 1: 0.04.
the structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is substituted C30Cycloalkyl groups of (a);
R4and R5Are each independently a single bond or a substituted or unsubstituted C1To C30An alkylene group or an alkylene ether group of (a);
X1、X2、X3、X5and X6Are each independently hydrogen; x4Is unsubstituted C2The heteroaryl group of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is diethylenetriamine.
The solvent in step 1) is toluene.
In the step 2), the time of the constant-temperature stirring reflux reaction is 5 hours, and the temperature of the constant-temperature stirring reflux reaction is 60 ℃.
Example ten
The preparation method of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin.
The mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: 4: 0.001.
the structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Is substituted C20Cycloalkyl groups of (a);
R4and R5Is substituted C20An alkylene ether group of (a);
X1、X2、X3、X4and X6Are each independently hydrogen; x5Is unsubstituted C30The heteroaryl group of (a);
n is an integer of 1 to 30.
The catalyst in the step 1) is 1, 3-diaminohetero cyclopentadiene.
The solvent in step 1) is acetone.
In the step 2), the time of the constant-temperature stirring reflux reaction is 11 hours, and the temperature of the constant-temperature stirring reflux reaction is 70 ℃.
R1、R2、R3、R6、R7And R8May also be unsubstituted C3To C30Cycloalkyl groups of (a); r4And R5May also be unsubstituted C1To C30An alkylene ether group of (a); x1、X2、X3、X4、X5And X6Each independently hydrogen, substituted or unsubstituted C1To C30Alkyl, substituted or unsubstituted C3To C30Cycloalkyl, substituted or unsubstituted C1To C30A substituted or unsubstituted C1To C30Alkyl ether group of (A), substituted or unsubstituted C6To C30Aryl, substituted or unsubstituted C2To C30Or substituted or unsubstituted C7To C30Aralkyl group of (1); x1、X2、X3、X4、X5And X6At least one of which is substituted or unsubstituted C6To C30Aryl or substituted or unsubstituted C2To C30The heteroaryl group of (a);
as can be seen from Table 1, the grafting rate of the silicone epoxy monomer on the phenolic resin can be controlled by changing the charge ratio and the reaction time.
TABLE 1
As can be seen from the figure 1, it is,1in an H-NMR spectrum, a new signal peak appears at 4.31-4.51ppm of the phenolic resin modified by the organic silicon epoxy monomer (EPSiNR) compared with the thermoplastic phenolic resin (NR), which is confirmed by the reaction of an epoxy group and a phenolic hydroxyl group, and the successful grafting of the organic silicon epoxy monomer into the NR.
As can be seen from FIG. 2, the curing curve of NR shows a sharp single exothermic peak, while the reaction curing exothermic peak of the curing curve of EPSiNR is shifted toward a low temperature direction compared with NR, and the curing window of EPSiNR is 64-181 deg.C, the curing window of NR is 130-157 deg.C, and the curing window is widened.
As can be seen from FIG. 3, the pyrolysis rate of EPSiNR is greater than NR between 394-475 ℃, mainly because of the hot rays of some organic groups on the organic silicon, while the pyrolysis rate of the modified phenolic resin is less than that of the unmodified phenolic resin at 475 ℃, and the char yield is 54.015% at 1000 ℃ and is higher than 50.654% of that of the unmodified phenolic resin.
As can be seen from FIG. 4, EPSiNR has a greater pyrolysis rate than NR before 423 ℃ due to the pyrolysis of some small molecular species in the system (impurities introduced from the silicone epoxy monomer during modification), whereas after 423 ℃ the introduced silicone gradually acts and oxidatively decomposes to SiO2The coating is coated on the surface of the resin, so that the transmission of heat and oxygen is prevented to a certain extent, and the thermal stability of the resin is improved. Furthermore, as can be seen from FIG. 5, the glass transition of EPSiNRThe temperature appears bimodal distribution, and the half-peak width is increased, which shows that EPSiNR has excellent thermo-mechanical properties.
Claims (4)
1. The organic silicon epoxy monomer modified phenolic resin is characterized by having the chemical structure as follows:
wherein m is1And m2Are integers greater than 2 and less than 9;
the preparation process of the organic silicon epoxy monomer modified phenolic resin comprises the following steps:
1) weighing thermoplastic phenolic resin, an organic silicon epoxy monomer and a catalyst, mixing, putting into a solvent, and uniformly stirring and dispersing to obtain a mixed solution;
2) putting the mixed solution obtained in the step 1) into a nitrogen atmosphere, carrying out constant-temperature reflux stirring reaction, and removing the solvent after the reaction is finished to obtain the organic silicon epoxy monomer modified phenolic resin;
the mass ratio of the thermoplastic phenolic resin, the organic silicon epoxy monomer and the catalyst in the step 1) is 1: (0.1-4): (0.001-0.05);
the structural formula of the organosilicon epoxy monomer in the step 1) is as follows:
wherein R is1、R2、R3、R6、R7And R8Each independently hydrogen, substituted or unsubstituted C1To C30Alkyl or substituted or unsubstituted C3To C30Cycloalkyl groups of (a);
R4and R5Are each independently a single bond or a substituted or unsubstituted C1To C30An alkylene group or an alkylene ether group of (a);
X1、X2、X3、X4、X5and X6Each independently hydrogen, substituted or unsubstituted C1To C30Alkyl, substituted or unsubstituted C3To C30Cycloalkyl, substituted or unsubstituted C1To C30A substituted or unsubstituted C1To C30Alkyl ether group of (A), substituted or unsubstituted C6To C30Aryl, substituted or unsubstituted C2To C30Or substituted or unsubstituted C7To C30Aralkyl group of (1); x1、X2、X3、X4、X5And X6At least one of which is substituted or unsubstituted C6To C30Aryl or substituted or unsubstituted C2To C30The heteroaryl group of (a);
n is an integer of 1 to 30.
2. The silicone epoxy monomer-modified phenolic resin of claim 1, wherein the catalyst in step 1) is 1, 3-diaminodicyclopentadiene, ammonium chloride, 4-diaminodiphenylmethane, triphenylphosphine, diethylenetriamine, or polyphenylsulfone.
3. The silicone epoxy monomer-modified phenolic resin according to claim 1, wherein the solvent in step 1) is acetone, ethanol, toluene, or a mixed solution of acetone and ethanol.
4. The silicone epoxy monomer-modified phenolic resin of claim 1, wherein in step 2), the stirring reflux reaction is carried out at a constant temperature for 4h to 12h, and the stirring reflux reaction is carried out at a constant temperature of 55 ℃ to 120 ℃.
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| JP3050456B2 (en) * | 1992-05-12 | 2000-06-12 | 宇部興産株式会社 | Heat resistant resin adhesive |
| US7365135B2 (en) * | 2004-06-14 | 2008-04-29 | Chung-Shan Institute Of Science & Technology | Method for preparing a novolac phenolic resin/silica hybrid organic-inorganic nanocomposite |
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| WO2001062829A1 (en) * | 2000-02-23 | 2001-08-30 | Georgia-Pacific Resins, Inc. | Epoxy-functional polysiloxane modified phenolic resin compositions and composites |
| CN106916267A (en) * | 2015-12-25 | 2017-07-04 | 广东生益科技股份有限公司 | A kind of organic-silicon-modified phenolic resin, Preparation method and use |
| CN108892760A (en) * | 2018-06-29 | 2018-11-27 | 西安交通大学 | A kind of epoxy cage type sesquialter siloxane phenol-formaldehyde resin modified and preparation method thereof |
| CN109880283A (en) * | 2019-01-21 | 2019-06-14 | 西安交通大学 | A kind of preparation method of the nano-silicon dioxide modified phenolic resin of surface modification |
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