High-crystallinity heat-conducting polysulfate as well as preparation method and application thereof

Abstract

The invention provides high-crystallinity heat-conducting polysulfate and a preparation method and application thereof, and belongs to the technical field of semiconductor materials.The preparation method comprises the steps that 4-cyanophenol and hydrazine hydrate are subjected to a heating reaction, and after the reaction is finished, washing and vacuum drying are conducted to prepare a first intermediate; adding the first intermediate into an ethanol solution, carrying out a heating reaction in an oxygen atmosphere, and after the reaction is finished, carrying out washing and vacuum drying to prepare a second intermediate; reacting the second intermediate with a silanizing agent, and purifying after the reaction is finished to obtain a monomer containing a silyl ether group; reacting the second intermediate with sulfuryl fluoride gas, and purifying after the reaction to obtain a monomer containing a sulfuryl fluoride group; and carrying out polymerization reaction on the monomer containing the silyl ether group or the second intermediate and the monomer containing the sulfuryl fluoride group to obtain the high-crystallinity polysulfate containing the tetrazine structure. The prepared high-crystallinity heat-conducting polysulfate is stable in physical and chemical properties, high in crystallinity and high in heat 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 to a highly crystalline heat-conducting polysulfate ester, a preparation method thereof, and an 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. Highly 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 a thermal conductivity of only 0.1-0.5 W·m -1 ·K -1 .

[0004] Polysulfate ester is a type of high-performance polymer with excellent heat resistance, chemical stability, and mechanical properties. Currently, there is an urgent need for a polysulfate ester 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 polysulfate ester with stable physical and chemical properties, high crystallinity, and high thermal conductivity, and a preparation method for the highly crystalline heat-conducting polysulfate ester that is simple, efficient, and low-cost.

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

[0007] wherein, n>1.

[0008] Furthermore, the polysulfate ester contains a tetrazine structure.

[0009] The present invention provides a preparation method for a highly crystalline heat-conducting polysulfate ester, including the following steps: Heating 4-cyanophenol and hydrazine hydrate to react, and after the reaction is completed, washing and vacuum drying to obtain a first intermediate; Adding the first intermediate to an ethanol solution, heating and reacting in an oxygen atmosphere, and after the reaction is completed, washing and vacuum drying to obtain a second intermediate; Reacting the second intermediate with a silylating agent, and after the reaction is completed, purifying to obtain a monomer containing a silyl ether group; Reacting the second intermediate with sulfuryl fluoride gas, and after the reaction is completed, purifying to obtain a monomer containing a sulfuryl fluoride group; The monomer containing a silyl ether group and the monomer containing a sulfonyl fluoride group or the second intermediate and the monomer containing a sulfonyl fluoride group are polymerized under catalytic conditions, and after the reaction is completed, precipitation is carried out in methanol to obtain a highly crystalline polysulfate containing a tetrazine structure.

[0010] Furthermore, the temperature of the heating reaction between 4-cyanophenol and hydrazine hydrate is 50°C - 90°C.

[0011] Furthermore, the silylating agent is trimethylchlorosilane, methyldiphenylchlorosilane or tert-butyldimethylchlorosilane.

[0012] Preferably, the silylating agent is tert-butyldimethylchlorosilane.

[0013] Furthermore, the polymerization reaction of the monomer containing a silyl ether group and the monomer containing a sulfonyl fluoride group or the polymerization reaction of the second intermediate and the monomer containing a sulfonyl fluoride group adopts solution polymerization or melt polymerization.

[0014] Furthermore, the temperature of the polymerization reaction is 20°C - 150°C, and the reaction time is 1 h - 10 h.

[0015] Furthermore, the molar ratio of the polymerization reaction of the monomer containing a silyl ether group and the monomer containing a sulfonyl fluoride group is 1:1 - 1:2, and the molar ratio of the polymerization reaction of the second intermediate and the monomer containing a sulfonyl fluoride group is 1:1 - 1:2.

[0016] The highly crystalline thermally conductive polysulfate prepared by the present invention can be used as a thermally conductive polymer material in semiconductor packaging materials.

[0017] A highly crystalline thermally conductive polysulfate provided by the present invention, because the polysulfate 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.

[0018] Moreover, a preparation method of a highly crystalline thermally conductive polysulfate provided by the present invention prepares a highly crystalline thermally conductive polysulfate containing tetrazine-based functional groups through a sulfur(VI) fluoride exchange click polymerization method, so that the highly crystalline thermally conductive polysulfate has a relatively large thermal conductivity, and its thermal conductivity can reach 0.83 W·m -1 ·K -1 Above, it has good thermal conductivity and has good application prospects in the semiconductor packaging field. Moreover, the preparation method of the present invention has a simple synthesis process and is easy to control, the equipment is simple, the raw materials are cheap and easy to obtain, the preparation cost is low, the economic benefit is high, and it is suitable for industrial scale production.

[0019] Meanwhile, the present invention provides a method for preparing 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 method is relatively wide, suitable for production by different enterprises under different conditions, and has high economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a flowchart of a method for preparing a highly crystalline thermally conductive polysulfonate provided by an embodiment of the present invention; Figure 2 It is a nuclear magnetic resonance ( 1 H NMR) spectrum of monomer A obtained in the method for preparing a highly crystalline thermally conductive polysulfonate provided by Example 1 of the present invention; Figure 3 It is a nuclear magnetic resonance ( 1 H NMR) spectrum of monomer B obtained in the method for preparing a highly crystalline thermally conductive polysulfonate provided by Example 1 of the present invention; Figure 4 It is an X-ray diffraction (XRD) pattern of the polysulfonate obtained in the method for preparing a highly crystalline thermally conductive polysulfonate provided by Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] A highly crystalline thermally conductive polysulfonate provided by an embodiment of the present invention has the following structural formula:

[0022] Wherein, n > 1.

[0023] Among them, the highly crystalline thermally conductive polysulfonate contains a tetrazine structure. Therefore, it has very high crystallinity and relatively high thermal conductivity, and also has relatively stable physical and chemical properties, high heat resistance and good mechanical properties. As a thermally conductive semiconductor polymer material, it has good application prospects in the field of semiconductor packaging.

[0024] See Figure 1 , a method for preparing a highly crystalline thermally conductive polysulfonate provided by the present invention includes the following steps: Step 1) Heat 4-cyanophenol and hydrazine hydrate to react. After the reaction is completed, wash and vacuum dry to obtain a first intermediate.

[0025] Among them, using 4-cyanophenol as a raw material, react with hydrazine hydrate at a temperature of 50°C - 90°C. The structure of the obtained first intermediate is shown as follows:

[0026] Step 2) Disperse the first intermediate in an ethanol solution, and then heat and stir the reaction in an oxygen atmosphere. After the reaction is completed, filter, wash, and vacuum dry to obtain the second intermediate. The structure of the second intermediate is shown in the following formula:

[0027] Step 3) Stir and react the second intermediate with a silylating agent at room temperature. After the reaction is completed, purify to obtain a monomer containing a silyl ether group.

[0028] Among them, the silylating agent is trimethylchlorosilane, methyldiphenylchlorosilane, or tert-butyldimethylchlorosilane.

[0029] As a specific embodiment of the present invention, the silylating agent is preferably tert-butyldimethylchlorosilane.

[0030] The structure of the obtained monomer containing a silyl ether group is shown in the following formula:

[0031] Step 4) Stir and react the second intermediate with sulfuryl fluoride gas at room temperature. After the reaction is completed, purify 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:

[0032] Step 5) Carry out a polymerization reaction on the monomer containing a silyl ether group and the monomer containing a sulfuryl fluoride group under catalytic conditions. After the reaction is completed, precipitate in methanol, and then vacuum dry the precipitate to obtain a highly crystalline thermally conductive polysulfonate containing a tetrazine structure.

[0033] Or, carry out a polymerization reaction on the second intermediate and the monomer containing a sulfuryl fluoride group under catalytic conditions. After the reaction is completed, precipitate in methanol, and then vacuum dry the precipitate to obtain a highly crystalline thermally conductive polysulfonate containing a tetrazine structure.

[0034] Among them, the temperature of the above polymerization reaction is 20°C - 150°C, and the reaction time is 1h - 10h.

[0035] Among them, the molar ratio of the monomer containing a silyl ether group to the monomer containing a sulfuryl fluoride group in the polymerization reaction is 1:1 - 1:2.

[0036] Among them, the molar ratio of the second intermediate to the monomer containing a sulfuryl fluoride group in the polymerization reaction is 1:1 - 1:2.

[0037] Among them, the catalyst used in the polymerization reaction carried out under catalytic conditions is an inorganic base K 2 CO 3 or an organic base such as DBU and other basic substances.

[0038] Among them, the principles of the two synthesis processes of the above-mentioned highly crystalline thermally conductive polysulfonate are shown in the following formula:

[0039] Among them, n > 1.

[0040] As a specific embodiment of the present invention, the polymerization reaction of the monomer containing a siloxane 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 can be carried out by solution polymerization.

[0041] As another specific embodiment of the present invention, the polymerization reaction of the monomer containing a siloxane 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 can also be carried out by melt polymerization.

[0042] A preparation method of a highly crystalline thermally conductive polysulfonate provided by the present invention, a highly crystalline thermally conductive polysulfonate containing a tetrazine functional group prepared by a sulfur(VI) fluoride exchange click polymerization method, is a red powder solid, has a high yield, and its yield can reach 83 - 96%. And this highly crystalline thermally conductive polysulfonate 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 good application prospects in the field of semiconductor packaging.

[0043] Moreover, the preparation method of the highly crystalline thermally conductive polysulfonate provided by the present invention has a simple synthesis process that is easy to control, simple equipment, cheap and easily available raw materials, low preparation cost, high economic benefits, and is suitable for industrial scale production.

[0044] Since the highly crystalline thermally conductive polysulfonate prepared by the present invention not only has high crystallinity and 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 good application prospects.

[0045] Next, a preparation method of a highly crystalline thermally conductive polysulfonate provided by the present invention will be specifically described through examples.

[0046] Example 1 The preparation of polysulfonate P-1 is specifically carried out as follows: Step 1: The preparation of intermediate 2 is specifically carried out as follows: 0.84 mol of 4-hydroxybenzonitrile was mixed with an excess of 800 mL of hydrazine hydrate and heated at 90 °C for 12 h. 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 h. After filtering the suspension, it was washed with ethanol and recrystallized to obtain a dark red powder (this dark red powder is Intermediate 2), yield: 72%.

[0047] Step 2: Preparation of monomer A, the specific steps are as follows: 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 h, monomer A was obtained after purification, with a yield of 91%. The 1 1H NMR spectroscopic data are as Figure 2 follows 1 1H NMR (400 MHz, CDCl 3 ) 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).

[0048] Step 3: Preparation of monomer B, the specific steps are as follows: 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 h and then purified to obtain monomer B, with a yield of 84%. The 1 1H NMR spectroscopic data are as Figure 3 follows, 1H NMR (400 MHz, CDCl3) δ 8.82 (d, J = 8.0 Hz, 4H), 7.63 (d, J = 8.1 Hz, 4H).

[0049] Step 4: Preparation of polysulfate at room temperature, the specific steps are as follows: 2 mmol of monomer A and 2 mmol of monomer B were dissolved in 10 mL of N-methylpyrrolidone. Subsequently, 1 drop of organic base (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU) was added and the mixture was stirred at room temperature for 24 h. Then, the mixed solution was dropped into methanol to obtain a light red solid, which is the polysulfate prepared in this example, with a yield of 95%.

[0050] SeeFigure 4 , which is the XRD pattern of the polysulfonate P-1 prepared in the embodiment of the present invention. It can be seen from the data that the polysulfonate P-1 has multiple sharp diffraction peaks and the peak intensity is relatively high, indicating that the polymer P-1 has high crystallinity.

[0051] Example 2 The preparation of polysulfonate P-2 is as follows: The difference between this example and Example 1 is that after heating 2 mmol of monomer A and 2 mmol of monomer B to 130 °C, 1 drop of organic base (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU) is added to the molten monomers and reacted at this temperature for 1 hour. Subsequently, 25 mL of N,N-dimethylformamide is added to dissolve the polymer, and the dissolved mixture is dropped into methanol to precipitate a light red solid with a yield of 92%.

[0052] Example 3 The preparation of polysulfonate P-3 is as follows: 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, 2 mmol of potassium carbonate is added, and then 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. After suction filtration and drying, a light red solid is obtained with a yield of 88%.

[0053] The thermal conductivity of the three polysulfonates prepared in Examples 1-3 of the present invention was tested as follows: Polysulfonates P-1, P-2, and P-3 were respectively dissolved in DMF solution, and then the polysulfonate solution was placed in an oven to dry to obtain a polymer film. The heat flow of the corresponding film was tested for the effective heat transfer area using an H16946 thermal conductivity measuring instrument. Subsequently, the corresponding thermal conductivity was calculated according to the thermal conductivity formula, and the specific values are shown in Table 1 below: Table 1

[0054] It can be seen from the results in Table 1 that the polysulfonates containing tetrazine structures synthesized in the examples of the present invention have high crystallinity and excellent thermal conductivity.

[0055] Finally, it should be noted that the above specific embodiments are only used to illustrate the technical solutions of the present invention and are not intended 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, characterized in that: The structural formula is: Where n>1.

2. The highly crystalline thermally conductive polysulfate according to claim 1, characterized in that: The polysulfate contains a tetrazine structure.

3. A method for preparing a highly crystalline thermally conductive polysulfate, characterized in that: The steps include: The first intermediate is prepared by heating 4-cyanophenol and hydrazine hydrate to react, and washing and vacuum drying after the reaction is completed; The first intermediate is added to an ethanol solution, heated in an oxygen atmosphere for reaction, and after the reaction is completed, the second intermediate is washed and vacuum dried to obtain the second intermediate; The second intermediate is reacted with a silanizing agent, and after the reaction is completed, the monomer containing a silicon ether group is purified; The second intermediate is reacted with sulfuryl fluoride gas, and after the reaction is completed, the monomer containing the sulfuryl fluoride group is purified; The monomer containing silicon ether group and the monomer containing sulfuryl fluoride group or the second intermediate and the monomer containing sulfuryl fluoride group are polymerized under catalytic conditions, and after the reaction is completed, the monomer is precipitated in methanol to obtain a highly crystalline polysulfate containing a tetrazine structure.

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

5. The method for preparing the highly crystalline thermally conductive polysulfate according to claim 3, characterized in that: The silanization agent is trimethylchlorosilane, methyldiphenylchlorosilane or tert-butyldimethylchlorosilane.

6. The method for preparing the highly crystalline thermally conductive polysulfate according to claim 5, characterized in that: The silanization agent is tert-butyldimethylsilyl chloride.

7. The method for preparing the highly crystalline thermally conductive polysulfate according to claim 3, characterized in that: The polymerization reaction of the monomer containing a silicon 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.

8. The method for preparing the highly crystalline thermally conductive polysulfate according to claim 7, characterized in that: The polymerization reaction temperature is 20°C-150°C, and the reaction time is 1h-10h.

9. The method for preparing the highly crystalline thermally conductive polysulfate according to claim 8, characterized in that: The molar ratio of the monomer containing a silicon ether group to the monomer containing a sulfuryl fluoride group in the polymerization reaction is 1:1-1:2, and the molar ratio of the second intermediate to the monomer containing a sulfuryl fluoride group in the polymerization reaction is 1:1-1:

2.

10. An application of a highly crystalline thermally conductive polysulfate, characterized in that: The highly crystalline thermally conductive polysulfate is used as a thermally conductive polymer material for semiconductor packaging materials.

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