Phenol-biphenylene type epoxy resin and synthesis and application thereof

Abstract

The present application belongs to the field of polymer synthesis, and specifically discloses a synthesis method of phenol- biphenylene type epoxy resin. The phenol- biphenylene type resin and epichlorohydrin are subjected to etherification reaction with the assistance of an additive of formula 1, and then subjected to ring closure reaction 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 heat preservation reaction platforms, wherein 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 present application also includes the prepared phenol- biphenylene type epoxy resin and its application in electronic device capping. The method can effectively improve the epoxidation conversion rate and efficiency of the phenol- biphenylene type epoxy resin, and also effectively reduce the chlorine content.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of special epoxy resin preparation, in particular to a preparation method of epoxy resin containing biphenyl structure. BACKGROUND

[0002] At present, the most commonly used in electronic device packaging is o-cresol novolac epoxy resin (ECN), due to the high water absorption and melt viscosity of the resin, which limits its application in large scale integrated circuits, people have carried out a variety of new epoxy resin development. The performance of epoxy resin is closely related to its molecular backbone structure, by introducing some special structural units in the molecular backbone of the resin, different performance of epoxy resin can be obtained. In order to meet the requirements of the continuous development of electronic packaging on epoxy resin, researchers have developed a series of epoxy resin with high temperature resistance, low moisture absorption and other high performance, mainly including low stress, high temperature resistance, low moisture absorption epoxy resin with biphenyl, fluorene, naphthalene ring, dicyclopentadiene as the backbone structure. The biphenyl type epoxy resin skeleton introduces biphenyl group, which has the characteristics of low melt viscosity, low moisture absorption, high heat resistance and high flame retardance, and has excellent application prospect in the field of electronic packaging materials, and becomes the research hotspot. Foreign countries have completed the industrial production and application of the product, the total chlorine content of the synthesized product is < 750 ppm, the organic chlorine content of high purity product is 200-300 ppm, and the organic chlorine content of ultra high purity product is 100-200 ppm.

[0003] Because the chlorine atoms in the epoxy resin will be slowly released during use, causing metal circuit corrosion, thereby shortening the service life of electronic components. With the increasing demand of people for electronic appliances, as the basic resin of electronic appliance industry, the purity requirement is also higher and higher, and the lower the residual chlorine content is the better. The existence of chlorine ion in epoxy resin is related to the reaction process. In the synthesis process of epoxy resin, in addition to the normal reaction, there is also a side reaction, and the chlorine ion is mainly derived from the side reaction, so controlling the side reaction is the main factor to reduce the chlorine ion, which is the key of process control.

[0004] Up to now, the domestic biphenyl type epoxy resin mainly focuses on the theoretical research stage of colleges and universities, and a few enterprises are in the experimental exploration stage. But due to the high chlorine content of the synthesized product, it is difficult to meet the performance requirements of downstream customers, and no industrialized product has been formed.

[0005] Therefore, it is urgent to develop low chlorine biphenyl type epoxy resin for the packaging material of high-end electronic components, to solve the domestic technology. SUMMARY

[0006] In view of the problems of high etherification temperature, long reaction time, hydrolysis of epichlorohydrin and the like existing in the current mainstream process, i.e., the reduced pressure azeotropy process, which leads to more isomerization of chlorine in the molecule due to the isomerization addition, crosslinking of the branched chain of the epoxy group at high temperature, low conversion rate, difficulty in subsequent refining and dechlorination, high total chlorine and organic chlorine, low product yield, high raw material consumption and the like, the first object of the present application is to provide a synthesis method of phenol- biphenylene type epoxy resin, aiming to provide a preparation method of high-efficiency, high-conversion and low-chlorine-content phenol-biphenylene type epoxy resin.

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

[0008] The phenol-biphenylene type resin segment contains a rigid biphenyl group, and the segment structure greatly increases the difficulty of phenolic hydroxyl epoxidation treatment, in view of this problem, the treatment ideas in the industry are to carry out the reaction under relatively harsh conditions (such as high temperature), so that good conversion rate and epoxidation degree can be obtained, but the by-products and chlorine residues are greatly increased, that is, in view of the difficulty of epoxidation caused by the special segment structure of the phenol-biphenylene type resin, and the problem of difficulty in considering the epoxidation degree, yield and chlorine content, the present application provides the following improvement scheme after in-depth research:

[0009] A synthesis method of phenol-biphenylene type epoxy resin, which comprises the following steps: performing etherification reaction on phenol-biphenylene type resin and epichlorohydrin with the aid of an auxiliary of formula 1, and then performing closed loop reaction under alkaline substance, negative pressure and gradient temperature control mechanism to obtain the phenol-biphenylene type epoxy resin;

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

[0011]

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

[0013] The etherification reaction is innovatively carried out in advance with the aid of formula 1, and the aid is further used in the subsequent ring closure reaction, and further, the subsequent negative pressure-gradient temperature control ring closure treatment and parameter joint control are innovatively matched, so that the synergy can be realized, the phenol- biphenylene type resin epoxidation degree can be significantly improved, the product yield can be improved, and the chlorine residues in the product can be significantly reduced. The process can effectively reduce the occurrence of side reactions, reduce the generation of isomerization chlorine, and easily obtain a product with high epoxy value, high yield, low total chlorine and low organic chlorine content, which has obvious effects on improving the stability and heat resistance of the product and reducing the consumption of raw materials.

[0014] In the application, the phenol-biphenylene type resin can be any phenol-biphenylene type resin with phenol ring and biphenyl ring segment coupling structure, for example, it can be a polymer with the structure of formula 2.

[0015]

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

[0017] In the application, as a typical embodiment, R1 and R2 can both be H.

[0018] In the application, the phenol-biphenylene type resin can be obtained by

[0019] The conventional condensation treatment is carried out (R3 is halogen or alkoxy).

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

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

[0022] The etherification assisted by formula 1 and the subsequent ring closure treatment are further matched with the gradient temperature control ring closure reaction idea, so that the synergy can be realized, the preparation problem caused by the biphenyl rigid structure in the polymer chain can be solved, the epoxidation conversion rate, conversion efficiency and yield can be improved, and the chlorine content in the product can be unexpectedly and significantly reduced.

[0023] In the present application, in the auxiliary agent of formula 1, m is 5 or 6. Research has found that the use of the preferred auxiliary agent helps to further cooperate with the subsequent gradient closed loop reaction idea, which can further synergistically improve the epoxy modification efficiency and effect of the phenol- biphenyl type epoxy resin, and in addition, can effectively reduce the chlorine content.

[0024] In the present application, the auxiliary agent of formula 1 is 5-55% of the weight of the epoxy chloropropane, preferably 10-35%, and further preferably 12-25%.

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

[0026] Preferably, the solvent is 20-70% of the weight of the auxiliary agent of formula 1, preferably 20-45%, and further preferably 25-35%.

[0027] In the present application, the temperature in the etherification reaction stage is 30-55°C.

[0028] Preferably, the etherification reaction time is 0.5-3h.

[0029] In the present application, after the etherification reaction, the pressure of the reaction system is controlled to be negative, and the basic substance is continuously added under negative pressure, and gradient temperature control is performed during the process.

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

[0031] In the present application, the basic substance is at least one of an alkali metal hydroxide and an alkoxide.

[0032] Preferably, the basic substance is 4-40% of the weight of the phenol-biphenyl type resin, preferably 15-30%.

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

[0034] In the present application, based on the etherification and ring closure reaction assisted by the auxiliary agent of formula 1, the gradient temperature control ring closure reaction idea is further cooperated, which is conducive to realizing synergy and solving the problem of difficult epoxy modification of the phenol-biphenyl type resin, not only improving the reaction conversion rate, but also unexpectedly reducing the chlorine residue.

[0035] In the present application, considering the preparation effect and process simplicity, in the gradient temperature control mechanism, n is 2-4, and the temperature difference between each holding platform is 3-10°C.

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

[0037] Preferably, the holding time of each holding platform is 0.5-3h.

[0038] Further preferably, the closed-loop reaction stage comprises 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℃, and the time t1 is 0.5-1.5h; the temperature T2 of the second reaction process is 5-6℃ higher than T1, and the time t2 is 1.5-2.5h; the temperature T3 of the third reaction process is 5-6℃ higher than T2, and the time t3 is 0.5-3h. It is found that under this holding 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 in a nearly uniform speed in the gradient temperature control stage.

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

[0041] Preferably, after the addition of the alkaline substance is completed, the reaction can be optionally continued at the temperature of the nth stage for 0.5-1.5h.

[0042] In the present application, the phenol-cyclobisphenyl type epoxy resin can be refined from the reaction system based on known process ideas.

[0043] For example, after the closed-loop reaction of the present application, epichlorohydrin is recovered to obtain a concentrate; the concentrate is dissolved by adding an organic solvent and refined by adding alkali, and then treated by water washing and distillation to obtain the refined phenol-cyclobisphenyl type epoxy resin.

[0044] The present application also provides a phenol-cyclobisphenyl type epoxy resin prepared by the method.

[0045] The present application also provides the application of the phenol-cyclobisphenyl type epoxy resin prepared by the method, which is used for the packaging material of electronic components.

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

[0047] Advantages

[0048] The etherification reaction is innovatively carried out in advance with the assistance of the auxiliary of formula 1, and the auxiliary is further used in the subsequent ring closing reaction, and further, the subsequent negative pressure-gradient temperature control ring closing treatment and the joint control of parameters are innovatively matched, so that the etherification reaction process can be effectively improved, the chain increasing and branch chain reaction can be reduced, and the branch chain steric hindrance effect hindering the ring closing reaction can be effectively avoided. The method can significantly improve the epoxidation degree of the phenol- biphenylene type resin, improve the product yield, and significantly reduce the chlorine residue in the product. In addition, the method can also obtain better epoxidation effect in a shorter time.

[0049] The synthesis process of the phenol-biphenylene type epoxy resin provided by the application has a product yield of greater than or equal to 95%, a total chlorine content of less than 600 ppm, and an organic chlorine content of less than 100 ppm, and the quality is equivalent to that of imported ultra-high purity products.

[0050] In the application, the preferred auxiliary of formula 1 (m=5 or 6) is used, and / or a three-stage temperature control mechanism is used, so that the process can be further coordinated, the conversion rate and yield of the product can be further improved, and the chlorine content can be further reduced. DETAILED DESCRIPTION

[0051] A typical phenol-biphenylene type resin epoxidation method (which can also be understood as a synthesis method of a phenol-biphenylene type epoxy resin) provided by the application comprises the following steps:

[0052] Step (1):

[0053] Etherification is performed on phenol-biphenylene type resin, epichlorohydrin, the auxiliary of formula 1, and anhydrous ethanol.

[0054] Step (2):

[0055] An alkaline catalyst is added under negative pressure, and a gradient temperature rising mode is adopted to perform 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 dissolve the concentrate, an alkali is added for refining, and then water washing, distillation to remove by-products such as alkali salt and solvent, and the like are performed to obtain a phenol-biphenylene type epoxy resin.

[0058] The auxiliary of formula 1 can be, for example, a compound with the following structure

[0059]

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

[0061] Preferably, the amount of the epoxy chloropropane is 5-55%, preferably 10-35%, and more preferably 12-25% by weight of the phenol-biphenylene resin.

[0062] Preferably, the amount of the anhydrous ethanol is 20-70%, preferably 20-45%, and more preferably 25-35% by weight of the phenol-biphenylene resin.

[0063] In the present application, the phenol-biphenylene resin can be a known material, for example, a material having the structure of Formula 2-a can be used:

[0064]

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

[0066] In the following cases, as a typical example, the phenol-biphenylene resin mentioned in the following cases is provided by Balin Petrochemical, which is a polymer (polymerization sites are mainly at the ortho position of the phenol) formed by condensation of phenol and biphenyl compounds such as (4,4'-chloromethyl biphenyl or 4,4'-methoxymethyl biphenyl), and the weight average molecular weight (Mw) is 1200-2500 g / mol. w

[0067] The yield is calculated as the percentage of the actual product mass to the theoretical product mass.

[0068] Preferably, the molar ratio of the phenol-biphenylene resin to the epoxy chloropropane is 1:8-20, and more preferably 1:8-12.

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

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

[0071] The reaction base can be an aqueous solution of a base, and the concentration thereof is not particularly limited, for example, it can be 1 wt.% or more to a saturated concentration, and preferably 40-55 wt.%.

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

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

[0074] In step 3, the recovered epichlorohydrin has a negative pressure of 0.07-0.1 MPa.

[0075] In step 3, the recovered closed-loop product is 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 refining base is at least one of alkali hydroxides and alcoholates.

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

[0078] In step 3, the refining base is 0.1-2% of the weight of the phenol-biphenylene type resin, preferably 0.3-1.2%.

[0079] In step 3, the refining base can be an aqueous alkali solution, and the concentration is not particularly limited, for example, it can be 1 wt.% or more to saturated concentration, preferably 10-30 wt.%.

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

[0081] In step 3, the refining reaction has a time of 1-4 h.

[0082] Subsequently, the oil phase is washed with water and concentrated, and the concentration is performed under a negative pressure of 0.02-0.1 MPa, preferably 0.07-0.08 MPa, at a temperature of 120-180°C for 0.5-1 h, to obtain a refined phenol-biphenylene type epoxy resin.

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

[0084]

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

[0086] First step: etherification reaction:

[0087]

[0088] Second step: ring closure reaction:

[0089]

[0090] The following is a more specific implementation case, specifically:

[0091] Example 1:

[0092] Step (1):

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

[0094] Step (2):

[0095] Then vacuum was started, the negative pressure was 0.08 MPa, 30 g of 45% sodium hydroxide (reaction base) solution was added at a constant speed for 4 hours, and gradient temperature control was performed during this period, wherein the first reaction temperature (T1) was 40°C, the holding time t1 was 1 hour; the second reaction temperature T2 was 46°C, the holding time t2 was 2 hours; the third reaction temperature T3 was 52°C, the holding time t3 was 1 hour, and after the alkali solution was added, it was maintained at T3 for 1 h.

[0096] Step (3):

[0097] After the ring closure treatment of step (2) was completed, 260 g of methyl isobutyl ketone (refining solvent) was added at 120°C and a negative pressure of 0.085 MPa to remove the epichlorohydrin. Then 3 g of 20% sodium hydroxide (refining base) was added at 70°C under normal pressure, and the refining reaction was carried out for 2.5 h. Then it was washed with water, concentrated to remove the solvent, the negative pressure was 0.09 MPa, the temperature was 140°C, the time was 45 min, and after natural cooling to room temperature, the phenol-biphenyl type epoxy resin was obtained.

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

[0099] Example 2:

[0100] According to the method of Example 1, the difference is that the formula 1 additive is changed to formula 1-b, which is a compound of formula 1 additive with m = 6, and the structural formula is: The rest is the same as Example 1, and the sample is obtained after natural cooling to room temperature.

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

[0102] Example 3:

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

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

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

[0106] Example 4:

[0107] The method of Example 1 is followed, except that the temperature control mechanism in Step 2 is changed, and the distinguishing features are:

[0108] The first segment reaction temperature T1 is 45°C, and t1 is 1 hour; the second segment reaction temperature T2 is 50°C, and t2 is 2 hours; the third segment reaction temperature T3 is 55°C, and t3 is 1 hour, and the base is added within 4 hours, and then T3 temperature 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 product obtained has the following indicators: yield: 97%; epoxy value: 0.35 mol / 100g; total chlorine: 597 ppm; organic chlorine: 78 ppm.

[0110] Example 5:

[0111] The method of Example 1 is followed, except that the base solution is added at a uniform rate over 4 hours, and two temperature control processes are performed during the addition, in which the first segment reaction temperature is 43°C, and the temperature is maintained for 2 hours; the second segment reaction temperature is 58°C, and the temperature is maintained for 2 hours; the base 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 product obtained has the following indicators: yield: 95%; epoxy value: 0.36 mol / 100g; total chlorine: 589 ppm; organic chlorine: 65 ppm.

[0113] Example 6:

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

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

[0116] Comparative Example 1

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

[0118] The product obtained had the following specifications: yield: 67%; epoxy value: 0.31 mol / 100g; total chlorine: 1246 ppm; organic chlorine: 240 ppm.

[0119] Comparative Example 2

[0120] The method of Example 1 was followed, except that the additive of Example 1 was not added. The rest was the same as Example 1, and the sample was obtained after natural cooling to room temperature.

[0121] The product obtained had the following specifications: 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 was followed, except that the additive was different. In Comparative Example 3, the additive used was a chain polyethylene glycol dialkyl ether. The rest was the same as Example 1, and the sample was obtained after natural cooling to room temperature.

[0124] The product obtained had the following specifications: yield: 61%; epoxy value: 0.33 mol / 100g; total chlorine: 2769 ppm; organic chlorine: 846 ppm.

[0125] The above only describes preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, modifications or substitutions can be made to the technical solutions described in the foregoing embodiments, or some technical features can be replaced by equivalent features, by those skilled in the art, without departing from the spirit and principles of the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A method for synthesizing a phenol-biphenyl-type epoxy resin, characterized in that, The phenol-biphenyl-type resin and epichlorohydrin were subjected to an etherification reaction with the aid of the additive in Formula 1, and then a ring-closure reaction was carried out under alkaline substances, negative pressure and gradient temperature control mechanism to obtain the phenol-biphenyl-type epoxy resin. The gradient temperature control mechanism includes n insulated reaction platforms, where the temperature of the first insulated platform is 35~45℃, and the temperature of the nth insulated platform is 50~60℃; n is an integer greater than or equal to 2. Formula 1 The m mentioned is an integer from 3 to 7; The phenol-biphenyl type resin is a polymer having the structural formula 2; Formula 2 R1 and R2 are individually at least one of H, C1-C6 alkyl, C1-C6 alkoxy, and halogen; k is less than or equal to 10; The additive in Formula 1 is 5-55% of the weight of epichlorohydrin.

2. The method for synthesizing phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, The phenol-biphenyl type resin has a weight average molecular weight of 1000~3000 g / mol.

3. The method for synthesizing phenol-biphenyl type epoxy resin as described in claim 2, characterized in that, The phenol-biphenyl type resin has a weight-average molecular weight of 1200~2500 g / mol.

4. The method for synthesizing phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, The molar ratio of the phenol-biphenyl resin to epichlorohydrin is 1:8~20.

5. The method for synthesizing phenol-biphenyl type epoxy resin as described in claim 4, characterized in that, The molar ratio of the phenol-biphenyl type resin to epichlorohydrin is 1:8~12.

6. The method for synthesizing phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, In the additive of Formula 1, m is 5 or 6.

7. The method for synthesizing phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, The additive in Formula 1 is 10-35% of the weight of epichlorohydrin.

8. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 7, characterized in that, The additive in Formula 1 is 12-25% of the weight of epichlorohydrin.

9. The method for synthesizing phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, The solvent in the etherification reaction stage is at least one of anhydrous ethanol, benzene, chloroform, and dichloromethane; The solvent is 20-70% of the weight of the additive in Formula 1.

10. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 9, characterized in that, The solvent is 20-45% of the weight of the additive in Formula 1.

11. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 10, characterized in that, The solvent is 25-35% of the weight of the additive in Formula 1.

12. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, The temperature during the etherification reaction stage is 30~55℃; The etherification reaction takes 0.5 to 3 hours.

13. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, After the etherification reaction, the pressure of the reaction system is controlled to a negative pressure, and an alkaline substance is continuously added under the negative pressure, while gradient temperature control is performed during the process; The negative pressure is less than 1 atm.

14. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, The alkaline substance is at least one of alkali metal hydroxides and alcohols; The alkaline substance is 4-40% of the weight of the phenol-biphenyl resin; The alkaline substance is used in the form of an aqueous solution.

15. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 1, characterized in that, In the gradient temperature control mechanism, n is 2 to 4, and the temperature difference between each insulation platform is 3 to 10℃. The insulation time for each insulation platform is 0.5~3 hours.

16. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 15, characterized in that, The closed-loop reaction stage includes a first reaction process, a second reaction process, and a third reaction process. In the first reaction process, the temperature T1 is 40~45℃ and the time t1 is 0.5~1.5h. In the second reaction process, the temperature T2 is 5~6℃ higher than T1 and the time t2 is 1.5~2.5h. In the third reaction process, the temperature T3 is 5~6℃ higher than T2 and the time t3 is 0.5~3h.

17. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 16, characterized in that, The alkaline substance is continuously added to the reaction system at a uniform rate during the gradient temperature control stage; wherein, in the first reaction process, the alkaline substance introduced accounts for 20-30 wt% of the total weight of the alkaline substance, in the second reaction process, the alkaline substance introduced accounts for 40-60 wt% of the total weight of the alkaline substance, and the remaining alkaline substance 3 is introduced in the third heat preservation process.

18. The method for synthesizing the phenol-biphenyl type epoxy resin as described in claim 17, characterized in that, After the alkaline substance is added, continue the reaction at the temperature of the third stage for 0.5 to 1.5 hours.

19. The method for synthesizing the phenol-biphenyl type epoxy resin as described in 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 alkali is added for purification. After washing with water and distillation, purified phenol-biphenyl type epoxy resin is obtained.

20. A phenol-biphenyl type epoxy resin prepared by the method according to any one of claims 1 to 19.

21. The application of a phenol-biphenylene epoxy resin prepared by the method according to any one of claims 1 to 19, characterized in that, It is used as a packaging material for electronic components.

Images