Phenol-biphenylene epoxy resin as well as synthesis and application thereof

Abstract

The invention belongs to the field of polymer synthesis, and particularly discloses a synthesis method of phenol-biphenylene type epoxy resin, which comprises the following steps: carrying out etherification reaction on phenol-biphenylene type resin and epichlorohydrin under the assistance of an auxiliary agent # imgabs0 # in a formula 1, and carrying out ring-closure reaction under alkaline substances, negative pressure and a gradient temperature control mechanism to obtain the phenol-biphenylene type epoxy resin. The phenol-biphenylene type epoxy resin is prepared; the gradient temperature control mechanism comprises n heat preservation reaction platforms, the temperature of the first heat preservation platform is 35-45 DEG C, and the temperature of the nth heat preservation platform is 50-60 DEG C; n is an integer greater than or equal to 2. The invention further discloses the prepared phenol-biphenylene epoxy resin and application of the phenol-biphenylene epoxy resin in end capping of electronic devices. According to the method, the epoxidation conversion rate and efficiency of the phenol-biphenylene type epoxy resin can be effectively improved, and the chlorine content can be effectively reduced.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of special epoxy resins, and in particular to a method for preparing an epoxy resin containing a biphenyl structure. Background Art

[0002] At present, the most commonly used epoxy resin in electronic device packaging is o-cresol epoxy resin (ECN). Due to the high water absorption and melt viscosity of this resin, its application in large-scale integrated circuits is limited. People have developed a variety of new epoxy resins. The performance of epoxy resin is closely related to its molecular main chain structure. By introducing some special structural units into the main chain of the resin molecule, epoxy resins with different properties can be obtained. In order to meet the requirements of the continuous development of electronic packaging for epoxy resins, researchers have developed a series of high-performance epoxy resins with high temperature resistance and low hygroscopicity, mainly including low-stress, high-temperature resistant, low-hygroscopic epoxy resins with biphenyl, fluorene, naphthalene ring, dicyclopentadiene, etc. as the skeleton structure. The introduction of biphenyl groups in the skeleton of biphenyl-type epoxy resin has the characteristics of low melt viscosity, low hygroscopicity, high heat resistance and high flame retardancy. It has excellent application prospects in the field of electronic packaging materials and has become a hot topic of research. The industrial production and application of this product have been completed abroad. The total chlorine content of the synthesized product is less than 750ppm, the organic chlorine content of the high-purity product is 200-300ppm, and the organic chlorine content of the ultra-high purity product is 100-200ppm.

[0003] Since the chlorine atoms in epoxy resin are slowly released during use, they cause corrosion of metal circuits, thus shortening the service life of electronic components. As people's requirements for electronic appliances become higher and higher, the purity requirements for the basic resin in the electronic appliance industry are also getting higher and higher, and the lower the residual chlorine content, the better. The presence of chloride ions in epoxy resin is related to the reaction process. In the synthesis process of epoxy resin, in addition to normal reactions, there are also side reactions, and chloride ions mainly come from side reactions. Therefore, controlling side reactions is the main factor in reducing chloride ions and is the key to process control.

[0004] So far, the domestic biphenyl epoxy resin is mainly concentrated in the theoretical research stage of colleges and universities, and a few companies are in the experimental exploration stage. However, due to the high chlorine content of the synthesized product, it is difficult to meet the performance requirements of downstream customers and no industrial products have been formed.

[0005] Therefore, it is urgent to develop low-chlorinated biphenyl epoxy resins for use as packaging materials for high-end electronic components and solve domestic technical problems. Summary of the invention

[0006] Aiming at the current mainstream process, i.e., the reduced pressure azeotropic process, there are problems such as high etherification temperature, long reaction time, hydrolysis of epichlorohydrin, etc., which leads to isotopic addition so that more chlorine is isomerized in the molecule, epoxy ring opening and branching cross-linking at high temperature, low conversion rate, making subsequent refined dechlorination difficult, high total chlorine and organic chlorine, low product yield, high raw material consumption, etc. The first purpose of the present invention is to provide a method for synthesizing phenol-biphenylene epoxy resin, aiming to provide a method for preparing phenol-biphenylene epoxy resin with high efficiency, high conversion and low chlorine content.

[0007] The second object of the present invention is to provide a phenol-biphenylene epoxy resin prepared by the preparation method and its application in electronic component packaging.

[0008] The phenol-biphenylene resin chain segment contains a rigid biphenyl group, and the chain segment structure greatly increases the difficulty of phenolic hydroxyl epoxidation treatment. To address this problem, most of the treatment ideas in the industry are to use relatively harsh conditions (such as high temperature) to react. Although this can obtain a good conversion rate and epoxidation degree, it will greatly increase the by-products and chlorine residues. That is, the phenol-biphenylene resin is difficult to epoxidize due to the special chain segment structure, and it is difficult to take into account the epoxidation degree, yield and chlorine content. After in-depth research, the present invention provides the following improvement scheme:

[0009] A method for synthesizing a phenol-biphenylene epoxy resin, comprising subjecting a phenol-biphenylene resin and epichlorohydrin to an etherification reaction with the aid of an auxiliary agent of formula 1, and then subjecting the phenol-biphenylene epoxy resin to a ring-closing reaction under an alkaline substance, negative pressure and a gradient temperature control mechanism, to obtain the phenol-biphenylene epoxy resin;

[0010] The gradient temperature control mechanism includes n insulation reaction platforms, wherein the temperature of the first insulation platform (also referred to as the first reaction process) is 35-45°C, and the temperature of the nth insulation platform (also referred to as the nth reaction process) is 50-60°C; n is an integer greater than or equal to 2;

[0011]

[0012] The m is an integer of 3-7.

[0013] The present invention innovatively performs etherification reaction in advance with the assistance of formula 1, and then assists it in participating in the subsequent closed-loop reaction. Not only that, it further innovatively cooperates with the subsequent negative pressure-gradient temperature control closed-loop treatment and the joint control of parameters, so that synergy can be achieved, and the epoxidation degree of phenol-biphenyl type resin can be significantly improved, the product yield can be improved, and the chlorine residue in the product can be significantly reduced. The process of the present invention can effectively reduce the occurrence of side reactions, reduce the generation of isomerized chlorine, and easily obtain products with high epoxy value, high yield, low total chlorine, and low organic chlorine content, which has a significant effect on improving the stability and heat resistance of the product and reducing the consumption of raw materials.

[0014] In the present invention, the phenol-biphenylene resin may be any phenol-biphenylene resin having a coupled structure of a phenol ring and a biphenyl ring segment, for example, it may be a polymer having a structural formula 2;

[0015]

[0016] The R1 and R2 are independently at least one of H, C1-C6 alkyl, C1-C6 alkoxy, and halogen; and the k is less than or equal to 10.

[0017] In the present invention, as a typical example, R1 and R2 can both be H.

[0018] In the present invention, the phenol-biphenylene type resin can be

[0019] (R3 is halogen or alkoxy) is obtained by conventional condensation treatment.

[0020] In the present invention, the molecular weight of the phenol-biphenylene type resin is a weight average molecular weight of 1000 to 3000 g / mol, preferably 1200 to 2500 g / mol.

[0021] In the present invention, the weight ratio of phenol-biphenylene resin to epichlorohydrin is 1:3 to 7, and more preferably 1:4 to 5. It is also understood that the molar ratio of the phenol-biphenylene resin to epichlorohydrin is 1:8 to 20, and more preferably 1:8 to 12.

[0022] The etherification assisted by Formula 1 and the subsequent closed-loop treatment are further coordinated with the gradient temperature-controlled closed-loop reaction idea, so that synergy can be achieved to solve the preparation problems caused by the rigid structure of biphenyl in the polymer chain, improve the epoxidation conversion rate, conversion efficiency and yield, and in addition, can unexpectedly significantly reduce the chlorine content in the product.

[0023] In the present invention, in the auxiliary agent of formula 1, m is 5 or 6. Studies have found that the use of this preferred auxiliary agent is helpful to further cooperate with the subsequent gradient ring-closing reaction idea, and can further synergistically improve the epoxidation modification efficiency and effect of phenol-biphenylene epoxy resin. In addition, it can also effectively reduce the chlorine content.

[0024] In the present invention, the weight of the auxiliary agent of formula 1 is 5-55% of epichlorohydrin, preferably 10-35%; more preferably 12-25%.

[0025] In the present invention, the solvent in the etherification reaction stage is at least one of anhydrous ethanol, benzene, chloroform and dichloromethane;

[0026] Preferably, the solvent accounts for 20-70% by weight of the auxiliary agent of formula 1, preferably 20-45%; more preferably 25-35%.

[0027] In the present invention, the temperature in the etherification reaction stage is 30 to 55°C;

[0028] Preferably, the etherification reaction time is 0.5 to 3 hours.

[0029] In the present invention, after the etherification reaction, the pressure of the reaction system is controlled to negative pressure, and alkaline substances are continuously added under negative pressure, and gradient temperature control treatment is performed during the process;

[0030] In the present invention, the negative pressure is less than 1 atm.

[0031] In the present invention, the alkaline substance is at least one of a hydroxide and an alcoholate of an alkali metal;

[0032] Preferably, the alkaline substance is 4-40% by weight of the phenol-biphenylene resin; preferably 15-30%.

[0033] The alkaline substance is used in the form of an aqueous solution.

[0034] In the present invention, on the basis of the etherification and ring-closing reaction assisted by the auxiliary agent of formula 1, a gradient temperature-controlled ring-closing reaction idea is further combined, which is conducive to achieving synergy and solving the problem that phenol-biphenyl type resin is difficult to epoxidize. It can not only improve the reaction conversion rate, but also unexpectedly reduce the chlorine residue.

[0035] In the present invention, considering the preparation effect and process simplicity, in the gradient temperature control mechanism, n is 2 to 4, and the temperature difference between each insulation platform is 3 to 10°C;

[0036] Preferably, n is 3, the temperature of the first insulation platform is 40-45°C, and the temperature difference of each insulation platform is between 5-6°C.

[0037] Preferably, the insulation time of each insulation platform is 0.5 to 3 hours.

[0038] Further preferably, the closed-loop reaction stage includes a first reaction process, a second reaction process and a third reaction process, wherein the temperature T1 of the first reaction process is 40-45°C, and the time t1 is 0.5-1.5h; the temperature T2 of the second reaction process is 5-6°C higher than T1, and the time t2 is 1.5-2.5h; the temperature T3 of the third reaction process is 5-6°C higher than T2, and the time t3 is 0.5-3h. Studies have found that under this heat preservation reaction mechanism, the conversion rate and yield of the product can be further improved, and the chlorine content can be further reduced.

[0039] Preferably, the alkaline substance is continuously added to the reaction system at a nearly uniform speed during the gradient temperature control stage.

[0040] For example, when three-stage gradient temperature control is adopted, in the first reaction process, the alkaline substance 1 introduced accounts for 20-30wt% of the total weight of the alkaline substances, the alkaline substance 2 introduced in the second reaction process accounts for 40-60wt% of the total weight of the alkaline substances, and the remaining alkaline substance 3 is introduced in the third insulation process.

[0041] Preferably, after the alkaline substance is added, the reaction can be selectively continued at the temperature of the nth stage for 0.5 to 1.5 hours.

[0042] In the present invention, the phenol-biphenylene epoxy resin can be purified from the reaction system based on known process ideas.

[0043] For example, after the ring-closing reaction of the present invention, epichlorohydrin is recovered to obtain a concentrate; an organic solvent is added to the concentrate to dissolve it, and an alkali is added to purify it, and then it is washed with water and distilled to obtain a refined phenol-biphenyl type epoxy resin.

[0044] The invention also provides a phenol-biphenylene type epoxy resin prepared by the method.

[0045] The invention also provides an application of the phenol-biphenylene epoxy resin prepared by the method, which is used as a packaging material for electronic components.

[0046] In the present invention, the polymer prepared by the preparation method has good epoxy degree and low chlorine content, and is particularly suitable for the use requirements of electronic packaging materials.

[0047] Beneficial Effects

[0048] The present invention innovatively performs an etherification reaction in advance with the assistance of formula 1, and then assists it in the subsequent closed-loop reaction. Not only that, it further innovatively cooperates with the subsequent negative pressure-gradient temperature control closed-loop treatment and the joint control of parameters, so that synergy can be achieved, and the epoxidation reaction process can be effectively improved. In addition, the chain extension and branching reactions can be reduced, and the branching steric hindrance effect can be effectively avoided to hinder the closed-loop reaction. The method described in the present invention can significantly improve the epoxidation degree of phenol-biphenyl type resin, improve the product yield, and significantly reduce the chlorine residue in the product. In addition, the present invention can also obtain a better epoxidation effect in a shorter time.

[0049] The synthesis process of the phenol-biphenylene epoxy resin provided by the invention has a product yield of ≥95%, a total chlorine content of <600ppm, and an organic chlorine content of <100ppm, which is equivalent to the quality of imported ultra-high purity products.

[0050] In the present invention, the preferred auxiliary agent of formula 1 (m=5 or 6) and / or the three-stage temperature control mechanism are used to further achieve process synergy, further improve the conversion rate and yield of the product, and further reduce the chlorine content. DETAILED DESCRIPTION

[0051] A typical phenol-biphenylene type resin epoxidation method of the present invention (also understood as a method for synthesizing phenol-biphenylene type epoxy resin) comprises the following steps:

[0052] Step (1):

[0053] Etherify phenol-biphenylene resin, epichlorohydrin, an auxiliary agent of formula 1 and anhydrous ethanol;

[0054] Step (2):

[0055] A basic catalyst is added under negative pressure, and a gradient temperature increase mode is adopted to carry out the ring-closing reaction.

[0056] Step (3):

[0057] After the ring-closing reaction, epichlorohydrin is recovered to obtain a concentrate, an organic solvent is added to the concentrate to dissolve it, a base is added to purify it, and then it is washed with water and distilled to remove by-product alkali salts, solvents, etc. to obtain a phenol-biphenylene epoxy resin.

[0058] The auxiliary agent of formula 1 may be, for example, a compound of the following structure:

[0059]

[0060] Formula 1-a (in Formula 1, m=5)

[0061] Preferably, the additive of formula 1 is 5-55% of the mass of the epichlorohydrin, preferably 10-35%; more preferably 12-25%.

[0062] Preferably, the amount of anhydrous ethanol used is 20-70% of the mass of the auxiliary agent of formula 1, preferably 20-45%; more preferably 25-35%.

[0063] In the present invention, the phenol-biphenylene type resin may be a known substance, for example, a substance having a structural formula 2-a may be used:

[0064]

[0065] In formula 2-a, n is less than or equal to 10;

[0066] In the following cases, as typical examples, unless otherwise stated, the phenol-biphenylene resins mentioned in the following cases are all provided by Baling Petrochemical, which are specifically polymers formed by condensation of phenol and biphenyl compounds such as (4,4'-chloromethylbiphenyl or 4,4'-methoxymethylbiphenyl) (the polymerization position is mainly at the ortho position of phenol), with a weight average molecular weight (M w ) is between 1200 and 2500 g / mol.

[0067] Yield calculation method: the percentage of actual product mass to theoretical product mass.

[0068] Preferably, the molar ratio of phenol-biphenylene type resin to epichlorohydrin is 1:8-20; more preferably 1:8-12.

[0069] In the present invention, the base is at least one of an alkali metal hydroxide and an alkali metal alkoxide; preferably at least one of sodium hydroxide and potassium hydroxide;

[0070] Preferably, the reaction base is 4-40% by weight of the phenol-biphenylene resin; preferably 15-30%.

[0071] The reaction base can be an aqueous solution of base, and its concentration is not particularly required. For example, it can be above 1 wt % to saturation concentration, preferably 40 to 55 wt %.

[0072] In the present invention, the ring-closing reaction temperature is preferably 40-60° C. The intramolecular ring-closing reaction process adopts a gradient temperature increase method: for example, the first stage reaction: at 40-45° C., the reaction time is 0.5 to 1.5 hours; the second stage reaction: at 45-50° C., the reaction time is 1.5 to 2.5 hours; the third stage reaction: at 50-55° C., the reaction time is 1.5 to 2.5 hours.

[0073] In step 3, the epichlorohydrin is recovered at a temperature of 100-200°C, preferably 100-130°C.

[0074] In step 3, the epichlorohydrin is recovered at a negative pressure of 0.07 to 0.1 MPa.

[0075] In step 3, the closed-loop product is recovered and mixed with a fat-soluble solvent to obtain an oil phase loaded with the product, and then a refining reaction is performed.

[0076] In step 3, the refined alkali is at least one of an alkali metal hydroxide and an alcoholate;

[0077] In step 3, the solvent is a non-polar or weakly polar substance, preferably at least one of toluene, ethylbenzene, xylene, methyl ethyl ketone, and methyl isobutyl ketone.

[0078] In step 3, the refined alkali is 0.1-2% by weight of the phenol-biphenylene resin, preferably 0.3-1.2%.

[0079] In step 3, the refined alkali can be an aqueous solution of alkali, and its concentration has no particular requirement, for example, it can be above 1 wt.% to saturation concentration, preferably 10 to 30 wt.%.

[0080] In step 3, the temperature of the refining reaction is 50-85°C, preferably 55-75°C;

[0081] In step 3, the purification reaction time is 1 to 4 hours.

[0082] The oil phase is then washed with water and concentrated. During the concentration and solvent removal, the negative pressure is 0.02-0.1 MPa, preferably 0.07-0.08 MPa. The temperature is 120-180° C. and the time is 0.5-1 h. Thus, a refined phenol-biphenylene epoxy resin is obtained.

[0083] In the present invention, the synthesized phenol-biphenylene epoxy resin has a structural formula of Formula A, for example, as a typical example.

[0084]

[0085] As a typical example, the reaction principle of the above synthesis method is, for example:

[0086] The first step of etherification reaction:

[0087]

[0088] The second step of ring closure reaction:

[0089]

[0090] The following are more specific implementation cases, specifically:

[0091] Embodiment 1:

[0092] Step (1):

[0093] In a four-necked flask equipped with a stirrer, a thermometer, a condenser and a reflux device, 65 g of phenol-biphenyl type resin, 285 g of epichlorohydrin, 42 g of formula 1-a and 12 g of anhydrous ethanol were added in sequence, nitrogen protection was turned on, the temperature was raised to 40°C, and the etherification reaction was carried out for 1 hour.

[0094] Step (2):

[0095] Then turn on the vacuum with a negative pressure of 0.08 MPa, and start to uniformly add 30 g of 45% sodium hydroxide (reaction base) solution over four hours, and perform gradient temperature control during this period, wherein the first reaction temperature (T1) is 40°C, and the insulation time t1 is 1 hour; the second reaction temperature T2 is 46°C, and the insulation time t2 is 2 hours; the third reaction temperature T3 is 52°C, and the insulation time t3 is 1 hour. After the addition of the alkali solution is completed, it is maintained at T3 for 1 hour.

[0096] Step (3):

[0097] After the closed-loop treatment in step (2) is completed, epichlorohydrin is removed at 120°C and a negative pressure of 0.085 MPa. Subsequently, 260 g of methyl isobutyl ketone (refining solvent) is added, and after complete dissolution, 3 g of 20% sodium hydroxide (refining alkali) is added at 70°C under normal pressure, and the refining reaction is carried out for 2.5 hours. Then, the mixture is washed with water, concentrated and desolventized, and the negative pressure is 0.09 MPa, the temperature is 140°C, and the time is 45 minutes. After naturally cooling to room temperature, a phenol-biphenyl type epoxy resin is obtained.

[0098] The indicators of the obtained product are as follows: yield: 98%; epoxy value: 0.38 mol / 100 g; total chlorine: 590 ppm; organic chlorine: 62 ppm.

[0099] Embodiment 2:

[0100] The method of Example 1 is followed, except that the auxiliary agent of Formula 1 is changed to Formula 1-b, which is a compound in which m=6 in the auxiliary agent of Formula 1, and has the structural formula: The rest is the same as in Example 1, and the sample is obtained after naturally cooling to room temperature.

[0101] The indicators of the obtained product are as follows: yield: 94%; epoxy value: 0.37 mol / 100 g; total chlorine: 593 ppm; organic chlorine: 85 ppm.

[0102] Embodiment 3:

[0103] The method of Example 1 is followed, except that the auxiliary agent of Formula 1 is changed to Formula 1-c, which is a compound in which m=4 in the auxiliary agent of Formula 1, and has the structural formula:

[0104] The rest is the same as in Example 1, and the sample is obtained after naturally cooling to room temperature.

[0105] The indicators of the obtained product are as follows: yield: 80%; epoxy value: 0.31 mol / 100 g; total chlorine: 1025 ppm; organic chlorine: 349 ppm.

[0106] Embodiment 4:

[0107] According to the method of Example 1, the difference is that the gradient temperature control mechanism of step 2 is changed, and the distinguishing feature is that:

[0108] The first stage reaction temperature T1 is 45°C, t1 is 1 hour; the second stage reaction temperature T2 is 50°C, t2 is 2 hours; the third stage reaction temperature T3 is 55°C, t3 is 1 hour, the alkali is added within 4 hours, and then the temperature T3 is maintained for 1 hour. The rest is the same as Example 1, and the sample is obtained after natural cooling to room temperature.

[0109] The indicators of the obtained product are as follows: yield: 97%; epoxy value: 0.35 mol / 100 g; total chlorine: 597 ppm; organic chlorine: 78 ppm.

[0110] Embodiment 5:

[0111] The method of Example 1 is followed, except that: the alkali solution is added dropwise at a constant speed of 4 hours, and two temperature control processes are performed during the addition process, wherein the first stage reaction temperature is 43°C, and the temperature is maintained for 2 hours; the second stage reaction temperature is 58°C, and the temperature is maintained for 2 hours; the alkali is added within 4 hours, and then maintained for 1 hour. The rest is the same as Example 1, and the sample is obtained after natural cooling to room temperature.

[0112] The indicators of the obtained product are as follows: yield: 95%; epoxy value: 0.36 mol / 100 g; total chlorine: 589 ppm; organic chlorine: 65 ppm.

[0113] Embodiment 6:

[0114] The method of Example 5 was followed, except that the refining solvent in step 3 was changed. In Example 6, the refining solvent was xylene. The rest was the same as in Example 5, and the sample was obtained after naturally cooling to room temperature.

[0115] The indicators of the obtained product are as follows: yield: 96%; epoxy value: 0.36 mol / 100 g; total chlorine: 596 ppm; organic chlorine: 75 ppm.

[0116] Comparative Example 1

[0117] The method of Example 1 was followed, except that the step-by-step temperature control was not adopted. In Comparative Example 1, the reaction temperature was maintained at 55°C, and the total reaction time was the same as that of Example 1 (5 h). The rest was the same as that of Example 1, and the sample was obtained after natural cooling to room temperature.

[0118] The indicators of the obtained product are as follows: yield: 67%; epoxy value: 0.31 mol / 100 g; total chlorine: 1246 ppm; organic chlorine: 240 ppm.

[0119] Comparative Example 2

[0120] The method of Example 1 is followed, except that the auxiliary agent of Formula 1 is not added. The rest is the same as Example 1, and the sample is obtained after naturally cooling to room temperature.

[0121] The indicators of the obtained product are as follows: yield: 48%; epoxy value: 0.32 mol / 100g; total chlorine: 3100 ppm; organic chlorine: 2058 ppm.

[0122] Comparative Example 3

[0123] The method of Example 1 is followed, except that the auxiliary agent is different. In Comparative Example 3, the auxiliary agent used is a chain polyethylene glycol dialkyl ether. The rest is the same as Example 1, and the sample is obtained after naturally cooling to room temperature.

[0124] The indicators of the obtained product are as follows: yield: 61%; epoxy value: 0.33 mol / 100 g; total chlorine: 2769 ppm; organic chlorine: 846 ppm.

[0125] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for synthesizing a phenol-biphenylene epoxy resin, characterized in that: The phenol-biphenylene type resin and epichlorohydrin are subjected to an etherification reaction with the aid of an auxiliary agent of formula 1, and then a ring-closing reaction is carried out under alkaline substances, negative pressure and gradient temperature control mechanism to obtain the phenol-biphenylene type epoxy resin; The gradient temperature control mechanism includes n insulation reaction platforms, wherein the temperature of the first insulation platform is 35-45°C, and the temperature of the nth insulation platform is 50-60°C; n is an integer greater than or equal to 2; The m is an integer of 3-7.

2. The method for synthesizing the phenol-biphenylene epoxy resin according to claim 1, wherein: The phenol-biphenylene type resin is a polymer having a structural formula 2; The R1 and R2 are independently at least one of H, C1-C6 alkyl, C1-C6 alkoxy, and halogen; and the k is less than or equal to 10.

3. The method for synthesizing the phenol-biphenylene type epoxy resin according to claim 2, wherein: The molecular weight of the phenol-biphenylene resin is a weight average molecular weight of 1000 to 3000 g / mol, preferably 1200 to 2500 g / mol.

4. The method for synthesizing a phenol-biphenylene epoxy resin according to claim 1, wherein: The molar ratio of the phenol-biphenylene resin to epichlorohydrin is 1:8-20, and more preferably 1:8-12.

5. The method for synthesizing the phenol-biphenylene type epoxy resin according to claim 1, wherein: In the auxiliary agent of formula 1, m is 5 or 6; Preferably, the weight of the auxiliary agent of formula 1 is 5-55% of epichlorohydrin, preferably 10-35%; more preferably 12-25%.

6. The method for synthesizing the phenol-biphenylene epoxy resin according to claim 1, wherein: The solvent in the etherification reaction stage is at least one of anhydrous ethanol, benzene, chloroform and dichloromethane; Preferably, the solvent accounts for 20-70% by weight of the auxiliary agent of formula 1, preferably 20-45%; more preferably 25-35%.

7. The method for synthesizing a phenol-biphenylene epoxy resin according to claim 1, wherein: The temperature of the etherification reaction stage is 30-55°C; Preferably, the etherification reaction time is 0.5 to 3 hours.

8. The method for synthesizing phenol-biphenylene epoxy resin according to claim 1, characterized in that: After the etherification reaction, the pressure of the reaction system is controlled to negative pressure, and alkaline substances are continuously added under negative pressure, and gradient temperature control is performed during the process; Preferably, the negative pressure is less than 1 atm.

9. The method for synthesizing a phenol-biphenylene epoxy resin according to claim 1 or 8, wherein: The alkaline substance is at least one of a hydroxide and an alcoholate of an alkali metal; Preferably, the alkaline substance is 4-40% by weight of the phenol-biphenylene resin; preferably 15-30%; Preferably, the alkaline substance is used in the form of an aqueous solution.

10. The method for synthesizing a phenol-biphenylene epoxy resin according to claim 1 or 8, wherein: In the gradient temperature control mechanism, n is 2 to 4, and the temperature difference between each insulation platform is 3 to 10°C; Preferably, n is 3, the temperature of the first insulation platform is 40-45°C, and the temperature difference of each insulation platform is between 5-6°C; It comprises n heat preservation reaction platforms, wherein the temperature of the first heat preservation platform is 35-45° C., and the temperature of the nth heat preservation platform is 50-60° C.; n is an integer greater than or equal to 2; Preferably, the insulation time of each insulation platform is 0.5 to 3 hours.

11. The method for synthesizing a phenol-biphenylene epoxy resin according to claim 10, wherein: The closed-loop reaction stage includes a first reaction process, a second reaction process and a third reaction process, wherein the temperature T1 of the first reaction process is 40-45°C, and the time t1 is 0.5-1.5h; the temperature T2 of the second reaction process is 5-6°C higher than T1, and the time t2 is 1.5-2.5h; the temperature T3 of the third reaction process is 5-6°C higher than T2, and the time t3 is 0.5-3h; Preferably, the alkaline substance is continuously added to the reaction system at a nearly uniform speed during the gradient temperature control stage; wherein, during the first reaction process, the alkaline substance introduced accounts for 20-30wt% of the total weight of the alkaline substances, during the second reaction process, the alkaline substance introduced accounts for 40-60wt% of the total weight of the alkaline substances, and the remaining alkaline substance 3 is introduced during the third insulation process; Preferably, after the alkaline substance is added, the reaction is continued at the temperature of the third stage for 0.5 to 1.5 hours.

12. The method for synthesizing phenol-biphenylene epoxy resin according to claim 1, characterized in that: After the ring-closing reaction, epichlorohydrin is recovered to obtain a concentrate; an organic solvent is added to the concentrate to dissolve it, and an alkali is added to purify it, and then it is washed with water and distilled to obtain a refined phenol-biphenyl type epoxy resin.

13. A phenol-biphenylene type epoxy resin prepared by the method according to any one of claims 1 to 12.

14. Use of a phenol-biphenylene epoxy resin prepared by the method according to any one of claims 1 to 12, characterized in that: It is used as packaging material for electronic components.

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