A highly crystalline thermally conductive polysulfate ester and its preparation method and application

Abstract

The present invention provides a highly crystalline thermally conductive polysulfate ester, a preparation method thereof and an application thereof, belonging to the technical field of semiconductor materials. The preparation method includes: heating and reacting 4-cyanophenol with hydrazine hydrate, washing and vacuum drying after the reaction to obtain a first intermediate; adding the first intermediate to an ethanol solution, heating and reacting in an oxygen atmosphere, washing and vacuum drying after the reaction to obtain a second intermediate; reacting the second intermediate with a silylating agent, and purifying after the reaction to obtain a monomer containing a siloxane group; reacting the second intermediate with sulfuryl fluoride gas, and purifying after the reaction to obtain a monomer containing a sulfuryl fluoride group; polymerizing the monomer containing a siloxane group or the second intermediate with the monomer containing a sulfuryl fluoride group to obtain a highly crystalline polysulfate ester containing a tetrazine structure. The highly crystalline thermally conductive polysulfate ester prepared by the present invention has stable physical and chemical properties, high crystallinity, high thermal conductivity, and the preparation method is simple, efficient and low in cost.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor materials, and particularly relates to a highly crystalline heat-conducting polysulfonate and a preparation method and application thereof. Background Art

[0002] With the rapid development of fields such as electronic information technology, power equipment, new energy vehicles, 5G communication, and aerospace, the demand for highly heat-conducting electrical insulating materials is increasing day by day. High-crystalline resins have an ordered molecular structure and can improve the heat-conducting performance of materials by controlling the molecular arrangement, but most polymers have poor crystallinity.

[0003] Optimizing the crystalline structure of polymer resins from the molecular level to the macroscopic level is one of the effective methods to construct an efficient heat-conducting path. Ordinary polymer polymers are good thermal insulators with poor heat-conducting performance, and the thermal conductivity is only 0.1-0.5 W·m -1 ·K -1 .

[0004] Polysulfonate is a class of high-performance polymers with excellent heat resistance, chemical stability, and mechanical properties. Currently, there is an urgent need for a polysulfonate with high crystallinity and good heat conduction. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a highly crystalline heat-conducting polysulfonate with stable physical and chemical properties, high crystallinity, and high thermal conductivity, and a preparation method for the highly crystalline heat-conducting polysulfonate that is simple, efficient, and low-cost.

[0006] To solve the above technical problem, the present invention provides a highly crystalline heat-conducting polysulfonate, and its structural formula is:

[0007]

[0008] Wherein, n>1.

[0009] Further, the polysulfonate contains a tetrazine structure.

[0010] The present invention provides a preparation method for a highly crystalline heat-conducting polysulfonate, including the following steps:

[0011] React 4-cyanophenol with hydrazine hydrate by heating, and after the reaction is completed, wash and vacuum dry to obtain a first intermediate;

[0012] Add the first intermediate to an ethanol solution, and heat and react in an oxygen atmosphere. After the reaction is completed, wash and vacuum dry to obtain a second intermediate;

[0013] React the second intermediate with a silylating agent, and after the reaction is completed, purify to obtain a monomer containing a silyl ether group;

[0014] React the second intermediate with sulfuryl fluoride gas, and after the reaction is completed, purify to obtain a monomer containing a sulfuryl fluoride group;

[0015] Polymerize the monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group or the second intermediate and the monomer containing a sulfuryl fluoride group under catalytic conditions, and after the reaction is completed, precipitate in methanol to obtain a highly crystalline polysulfate ester containing a tetrazine structure.

[0016] Further, the temperature of the heating reaction of 4-cyanophenol with hydrazine hydrate is 50°C - 90°C.

[0017] Further, the silylating agent is trimethylchlorosilane, methyldiphenylchlorosilane or tert-butyldimethylchlorosilane.

[0018] Preferably, the silylating agent is tert-butyldimethylchlorosilane.

[0019] Further, the polymerization reaction of the monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group or the polymerization reaction of the second intermediate and the monomer containing a sulfuryl fluoride group adopts solution polymerization or melt polymerization.

[0020] Further, the temperature of the polymerization reaction is 20°C - 150 °C, and the reaction time is 1 h - 10 h.

[0021] Further, the molar ratio of the polymerization reaction of the monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group is 1:1 - 1:2, and the molar ratio of the polymerization reaction of the second intermediate and the monomer containing a sulfuryl fluoride group is 1:1 - 1:2.

[0022] The highly crystalline thermally conductive polysulfate ester prepared by the present invention can be used as a thermally conductive polymer material in semiconductor packaging materials.

[0023] A highly crystalline thermally conductive polysulfate ester provided by the present invention, because the polysulfate ester contains a tetrazine structure, not only has very high crystallinity and relatively high thermal conductivity, but also has relatively stable physical and chemical properties, high heat resistance and good mechanical properties. It can be used as a thermally conductive semiconductor polymer material in the semiconductor packaging field and has good application prospects.

[0024] Moreover, a preparation method of a highly crystalline thermally conductive polysulfate ester provided by the present invention prepares a highly crystalline thermally conductive polysulfate ester containing tetrazine-based functional groups through a six-valent sulfur fluoride exchange click polymerization method, so that the highly crystalline thermally conductive polysulfate ester has a relatively large thermal conductivity, and its thermal conductivity can reach 0.83 W·m -1 ·K -1As described above, it has good thermal conductivity and has excellent application prospects in the field of semiconductor packaging. Moreover, the preparation method of the present invention has a simple synthesis process that is easy to control, simple equipment, inexpensive and easily available raw materials, low preparation costs, high economic benefits, and is suitable for industrial scale production.

[0025] Meanwhile, the present invention provides a preparation method of a highly crystalline thermally conductive polysulfonate. The preparation method is diversified. During the synthesis reaction process, the polymerization reaction between monomers can be carried out by solution polymerization method or melt polymerization method, etc. The preparation methods are extensive, suitable for production by different enterprises under different conditions, and have high economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a flowchart of a preparation method of a highly crystalline thermally conductive polysulfonate provided by an embodiment of the present invention;

[0027] Figure 2 It is a nuclear magnetic resonance ( 1 1H NMR) spectrum of monomer A obtained in the preparation method of a highly crystalline thermally conductive polysulfonate provided by Embodiment 1 of the present invention;

[0028] Figure 3 It is a nuclear magnetic resonance ( 1 1H NMR) spectrum of monomer B obtained in the preparation method of a highly crystalline thermally conductive polysulfonate provided by Embodiment 1 of the present invention;

[0029] Figure 4 It is an X-ray diffraction (XRD) spectrum of the polysulfonate obtained by the preparation method of a highly crystalline thermally conductive polysulfonate provided by Embodiment 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0030] A highly crystalline thermally conductive polysulfonate provided by an embodiment of the present invention has the following structural formula:

[0031]

[0032] Among them, n > 1.

[0033] Among them, the highly crystalline thermally conductive polysulfonate contains a tetrazine structure. Therefore, it has high crystallinity, high thermal conductivity, relatively stable physical and chemical properties, high heat resistance, and good mechanical properties. As a thermally conductive semiconductor polymer material used in the field of semiconductor packaging, it has good application prospects.

[0034] See Figure 1 , a preparation method of a highly crystalline thermally conductive polysulfonate provided by the present invention includes the following steps:

[0035] Step 1) 4-cyanophenol is heated and reacted with hydrazine hydrate. After the reaction is completed, it is washed and vacuum dried to obtain a first intermediate.

[0036] Among them, using 4-cyanophenol as a raw material, it is heated and reacted with hydrazine hydrate at a temperature of 50 °C - 90 °C. The structure of the obtained first intermediate is shown in the following formula:

[0037]

[0038] Step 2) The first intermediate is dispersed in an ethanol solution, and then heated and stirred in an oxygen atmosphere for reaction. After the reaction is completed, it is filtered, washed and vacuum dried to prepare a second intermediate. The structure of the second intermediate is shown in the following formula:

[0039]

[0040] Step 3) The second intermediate is stirred and reacted with a silylating agent at room temperature. After the reaction is completed, it is purified to obtain a monomer containing a silyl ether group.

[0041] Among them, the silylating agent is trimethylchlorosilane, methyldiphenylchlorosilane or tert-butyldimethylchlorosilane.

[0042] As a specific embodiment of the present invention, the silylating agent is preferably tert-butyldimethylchlorosilane.

[0043] The structure of the obtained monomer containing a silyl ether group is shown in the following formula:

[0044]

[0045] Step 4) The second intermediate is stirred and reacted with sulfuryl fluoride gas at room temperature. After the reaction is completed, it is purified to obtain a monomer containing a sulfuryl fluoride group. The structure of the monomer containing a sulfuryl fluoride group is shown in the following formula:

[0046]

[0047] Step 5) The monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group are subjected to a polymerization reaction under catalytic conditions. After the reaction is completed, it is precipitated in methanol, and then the precipitate is vacuum dried to obtain a highly crystalline heat-conducting polysulfonate containing a tetrazine structure.

[0048] Or, the second intermediate and the monomer containing a sulfuryl fluoride group are polymerized under catalytic conditions. After the reaction is completed, it is precipitated in methanol, and then the precipitate is vacuum dried to obtain a highly crystalline heat-conducting polysulfonate containing a tetrazine structure.

[0049] Among them, the temperature of the above polymerization reaction is 20 °C - 150 °C, and the reaction time is 1 h - 10 h.

[0050] Among them, the molar ratio of the polymerization reaction between the monomer containing a silyl ether group and the monomer containing a sulfonyl fluoride group is 1:1 - 1:2.

[0051] Among them, the molar ratio of the polymerization reaction between the second intermediate and the monomer containing a sulfonyl fluoride group is 1:1 - 1:2.

[0052] Among them, the catalyst used in the polymerization reaction carried out under catalytic conditions is an alkaline substance such as inorganic base K2CO3 or organic base DBU.

[0053] Among them, the principles of the two synthesis processes of the above high-crystallinity thermally conductive polysulfate are shown in the following formula:

[0054]

[0055] Among them, n > 1.

[0056] As a specific embodiment of the present invention, the polymerization reaction between the monomer containing a silyl ether group and the monomer containing a sulfonyl fluoride group or the polymerization reaction between the second intermediate and the monomer containing a sulfonyl fluoride group can be carried out by solution polymerization.

[0057] As another specific embodiment of the present invention, the polymerization reaction between the monomer containing a silyl ether group and the monomer containing a sulfonyl fluoride group or the polymerization reaction between the second intermediate and the monomer containing a sulfonyl fluoride group can also be carried out by melt polymerization.

[0058] A preparation method of a high-crystallinity thermally conductive polysulfate provided by the present invention, a high-crystallinity thermally conductive polysulfate containing a tetrazine functional group prepared by a hexavalent sulfur fluoride exchange click polymerization method, is a red powder solid, has a high yield, and its yield can reach 83 - 96%. And this high-crystallinity thermally conductive polysulfate containing a tetrazine structure has a large thermal conductivity, and its thermal conductivity can reach 0.83 W·m -1 ·K -1 Above, it has good thermal conductivity and has a good application prospect in the field of semiconductor packaging.

[0059] Moreover, the preparation method of the high-crystallinity thermally conductive polysulfate provided by the present invention has a simple synthesis process that is easy to control, simple equipment, inexpensive and easily available raw materials, low preparation cost, high economic benefits, and is suitable for industrial scale production.

[0060] Since the high-crystallinity thermally conductive polysulfate prepared by the present invention not only has very high crystallinity and relatively high thermal conductivity, but also has relatively stable physical and chemical properties, high heat resistance and good mechanical properties, therefore, it can be used as a thermally conductive semiconductor polymer material for semiconductor packaging materials in the field of semiconductor packaging, and has a good application prospect.

[0061] The following is a specific description of a method for preparing a highly crystalline thermally conductive polysulfonate provided by the present invention through examples.

[0062] Example 1

[0063] The preparation of polysulfonate P-1 is as follows:

[0064] Step 1: The preparation of intermediate 2 is as follows:

[0065] 0.84 mol of 4-hydroxybenzonitrile and an excessive amount of 800 ml of hydrazine hydrate were mixed and heated at 90 °C for 12 hours. After natural cooling, it was washed several times with ethanol and then dried in a vacuum drying oven to obtain a light yellow powder (this light yellow powder is intermediate 1). Then, the above light yellow powder was dispersed in ethanol and reacted with oxygen for 48 hours. After filtering the suspension, it was washed with ethanol and recrystallized to obtain a dark red powder (this dark red powder is intermediate 2), and the yield was 72%.

[0066] Step 2: The preparation of monomer A is as follows:

[0067] 0.04 mol of intermediate 2 and 0.1 mol of imidazole were added to 100 ml of dichloromethane. Then, 0.1 mol of tert-butyldimethylchlorosilane was added to the above reaction solution. After stirring at room temperature for 24 hours, it was purified to obtain monomer A with a yield of 91%. The 1 1H NMR nuclear magnetic data is as Figure 2 shown, 1 1H NMR (400 MHz, CDCl3) δ 8.54 (s, 1H), 8.54 (s, 1H), 7.05 (s, 2H), 7.05 (s, 1H), 1.02 (s, 7H), 1.02 (s, 6H), 0.29 (s, 4H), 0.29 (s, 4H).

[0068] Step 3: The preparation of monomer B is as follows:

[0069] 0.04 mol of intermediate 2 and 0.1 mol of triethylamine were dissolved in 100 ml of dichloromethane. Then, the above mixed solution was stirred in a sulfuryl fluoride atmosphere for 24 hours and then purified to obtain monomer B with a yield of 84%. The 1 1H NMR nuclear magnetic data is as Figure 3 shown, 1H NMR (400 MHz, CDCl3) δ 8.82 (d, J = 8.0 Hz, 4H), 7.63 (d, J = 8.1 Hz, 4H).

[0070] Step 4: Preparation of polysulfate at room temperature, the specific steps are as follows:

[0071] Dissolve 2 mmol of monomer A and 2 mmol of monomer B in 10 mL of N-methylpyrrolidone. Then add 1 drop of organic base (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU), and stir the reaction at room temperature for 24 hours. Then drop the mixed solution into methanol to obtain a light red solid, which is the polysulfate prepared in this example, with a yield of 95%.

[0072] See Figure 4 , which is the XRD pattern of the polysulfate P-1 prepared in the example of the present invention. It can be seen from the data that the polysulfate P-1 has multiple sharp diffraction peaks, and the intensity of the peaks is relatively high, indicating that the polymer P-1 has high crystallinity.

[0073] Example 2

[0074] Preparation of polysulfate P-2, the specific steps are as follows:

[0075] The difference between this example and Example 1 is that 2 mmol of monomer A and 2 mmol of monomer B are heated to 130 °C, then 1 drop of organic base (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU) is added to the molten monomers, and the reaction is carried out at this temperature for 1 hour. Then 25 mL of N,N-dimethylformamide is added to dissolve the polymer, and the dissolved mixed solution is dropped into methanol to precipitate a light red solid, with a yield of 92%.

[0076] Example 3

[0077] Preparation of polysulfate P-3, the specific steps are as follows:

[0078] The difference between this example and Example 1 is that 2 mmol of intermediate 2 and 2 mmol of monomer B are dissolved in 50 mL of γ-butyrolactone, then 2 mmol of potassium carbonate is added, and the mixture is heated to 150 °C and reacted for 12 hours. After cooling to room temperature, potassium carbonate is removed by filtration, and the reaction solution is dropped into methanol, and then filtered and dried to obtain a light red solid, with a yield of 88%.

[0079] The thermal conductivity of the three polysulfates prepared in Examples 1-3 of the present invention was tested, and the specific steps are as follows:

[0080] Dissolve polysulfates P-1, P-2, and P-3 in DMF solution respectively. Then put the polysulfate solution into an oven to dry to obtain a polymer film. Use the H16946 thermal conductivity measuring instrument to test the heat flow of the corresponding film with an effective heat transfer area. Then calculate the corresponding thermal conductivity according to the thermal conductivity formula. The specific values are shown in Table 1 below:

[0081] Table 1

[0082]

[0083] As can be seen from the results in Table 1, the polysulfate containing a tetrazine structure synthesized in the embodiments of the present invention has high crystallinity and excellent thermal conductivity.

[0084] Finally, it should be noted that the above specific embodiments are only used to illustrate the technical solutions of the present invention rather than to limit them. Although the present invention has been described in detail with reference to the examples, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered by the scope of the claims of the present invention.

Claims

1. A highly crystalline thermally conductive polysulfate ester, characterized in that, The structural formula is as follows: where n > 1.

2. A preparation method of a highly crystalline heat-conducting polysulfonate, characterized in that, It includes the following steps: Step 1) React 4-cyanophenol with hydrazine hydrate by heating. After the reaction is completed, wash and vacuum dry to obtain the first intermediate; Step 2) Add the first intermediate to an ethanol solution and heat react in an oxygen atmosphere. After the reaction is completed, wash and vacuum dry to obtain the second intermediate; Step 3) React the second intermediate with a silylating agent. After the reaction is completed, purify to obtain a monomer containing a silyl ether group; Step 4) React the second intermediate with sulfuryl fluoride gas. After the reaction is completed, purify to obtain a monomer containing a sulfuryl fluoride group; Step 5) Polymerize the monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group or the second intermediate and the monomer containing a sulfuryl fluoride group under catalytic conditions. After the reaction is completed, precipitate in methanol to obtain a highly crystalline polysulfate ester containing a tetrazine structure.

3. The preparation method of the highly crystalline thermally conductive polysulfate according to claim 2, characterized in that, The temperature of the heating reaction of 4-cyanophenol and hydrazine hydrate is 50°C - 90°C.

4. The preparation method of the highly crystalline thermally conductive polysulfate according to claim 2, characterized in that, The silylating reagent is trimethylchlorosilane, methyldiphenylchlorosilane or tert-butyldimethylchlorosilane.

5. The preparation method of the highly crystalline heat-conducting polysulfonate according to claim 4, characterized in that, The silylating reagent is tert-butyldimethylchlorosilane.

6. The preparation method of the highly crystalline thermally conductive polysulfate according to claim 2, characterized in that, The polymerization reaction of the monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group or the polymerization reaction of the second intermediate and the monomer containing a sulfuryl fluoride group adopts solution polymerization or melt polymerization.

7. The preparation method of the highly crystalline heat-conducting polysulfate according to claim 6, characterized in that, The temperature of the polymerization reaction is 20°C - 150°C, and the reaction time is 1 h - 10 h.

8. The preparation method of the highly crystalline heat-conducting polysulfate according to claim 7, characterized in that, The molar ratio of the polymerization reaction of the monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group is 1:1 - 1:2, and the molar ratio of the polymerization reaction of the second intermediate and the monomer containing a sulfuryl fluoride group is 1:1 - 1:

2.

9. Application of a highly crystalline thermally conductive polysulfonate, characterized in that, Apply the highly crystalline thermally conductive polysulfate ester described in claim 1 as a thermally conductive polymer material to semiconductor packaging materials.

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