A friction-reducing wear-resistant bis-amine benzoxazine resin, and a preparation method and application thereof

Abstract

The application provides a kind of antifriction wear-resistant double amine benzoxazine resin and its preparation method and application, belong to thermosetting resin technical field;The application is prepared with 4,4'-ethylenediamine as amine source, by adjusting the length of flexible segment a kind of double amine benzoxazine resin;The double amine benzoxazine resin has excellent thermal stability and friction performance, the friction coefficient is as low as 0.06~0.1, the wear rate is 4.5~8.0*10 ‑5 mm 3 / Nm, and still remains good antifriction wear resistance under high load and high speed;The double amine benzoxazine resin has low polymerization temperature and very excellent thermal, mechanical and friction performance;The preparation method of the double amine benzoxazine resin is simple, the yield is high, the requirement to equipment is lower, easy to realize large-scale production, has good practicability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of thermosetting resin, and particularly relates to a friction-reducing and wear-resistant diamine benzoxazine resin as well as a preparation method and application thereof. BACKGROUND

[0002] Friction and wear are ubiquitous in industrial production and daily life. Polymer materials are used as key lubricating materials for bearings, gears, hydraulic components and the like to reduce friction and control wear due to their self-lubricating, light weight, insulating and other characteristics. With the progress of science and technology and the development of industry, the service conditions of friction components are increasingly harsh, which poses a severe challenge to the performance of these lubricating materials.

[0003] Compared with widely used resin matrices such as phenolic resin, epoxy resin and bismaleimide, benzoxazine resin as a new type of high-performance thermosetting resin has the advantages of low cost, excellent flame retardancy, thermal stability, low dielectric constant, relatively high carbon yield and flexible molecular design. At the same time, the thermal activation ring-opening synthesis process of benzoxazine resin can be carried out without adding any curing agent, and the curing shrinkage is almost zero. The excellent comprehensive performance of benzoxazine resin makes it suitable for some forming processes such as mold pressing, laminating and resin transfer molding, and thus it is used in the production fields of corrosion-resistant and burn-resistant materials, mechanical manufacturing parts, aerospace materials and vacuum pump rotor blades. However, the development of most polymer materials is often restricted by low temperature, high crosslinking density and high brittleness, which cannot meet the requirements of high load, high speed and high temperature in some harsh environments. As an organic polymer material, benzoxazine resin is no exception. Although traditional diamine benzoxazine resin (PH-ddm) as a representative commercial benzoxazine resin has a very wide application in industrial production and mechanical manufacturing, it has the disadvantages of high polymerization temperature, high brittleness and high crosslinking density, which limits its use in friction-reducing and wear-resistant polymer matrices.

[0004] At present, there is no report on the research of regulating the structure of benzoxazine resin from the perspective of molecular design, improving the overall performance and realizing good friction-reducing and wear-resistant properties. Therefore, it is of great significance to design and develop flexible, temperature-resistant and excellent tribological performance benzoxazine resin materials by utilizing the flexibility of benzoxazine resin molecular design, so as to broaden its application in the field of tribology. SUMMARY

[0005] In view of some deficiencies in the prior art, the present application provides a friction-reducing and wear-resistant diamine benzoxazine resin as well as a preparation method and application thereof. The diamine benzoxazine resin is prepared by adjusting the length of flexible segments with 4,4'-ethylenedianiline as an amine source. The diamine benzoxazine resin has excellent thermal stability and friction performance, and the friction coefficient is as low as 0.06-0.1, and the wear rate is 4.5-8.0*10-5 mm 3 / Nm, and still maintains good friction-reducing and wear-resisting properties under high load and high speed; the diamine benzoxazine resin has low polymerization temperature and very excellent thermal, mechanical and friction properties; the preparation method of the diamine benzoxazine resin is simple, has high yield, requires low equipment, is easy to realize large-scale production, and has good practicability.

[0006] In order to achieve the above technical purposes, the present application adopts the following technical means:

[0007] The present application first provides a friction-reducing and wear-resisting diamine benzoxazine resin, and the molecular chemical structure formula of the diamine benzoxazine resin is:

[0008]

[0009] Among them, (A)-(E) are any one of:

[0010]

[0011] The present application also provides a preparation method of the above-mentioned diamine benzoxazine resin, and the preparation method comprises:

[0012] 4,4'-ethylenedianiline, a phenolic compound and polyformaldehyde are mixed, then a low-polarity solvent is added thereto, and after being uniformly mixed, heating reaction is carried out, and after the reaction is completed, filtration, washing, rotary evaporation and drying are carried out to obtain a solid product, i.e. a diamine benzoxazine monomer; then the diamine benzoxazine monomer is subjected to heat pressing and curing to obtain a diamine benzoxazine resin.

[0013] Preferably, the structure formula of the phenolic compound is (A)-(E) are any one of:

[0014]

[0015] Preferably, the molar ratio of 4,4'-ethylenedianiline, the phenolic compound and polyformaldehyde is 1:2:4-1:2:6.

[0016] Preferably, the molar ratio of 4,4'-ethylenedianiline, the phenolic compound and polyformaldehyde is 1:2:4.4.

[0017] Preferably, the low-polarity solvent comprises one or a mixture of several of toluene, xylene and dioxane.

[0018] Preferably, the heating reaction is carried out at 80-130 DEG C for 6-8 h.

[0019] Preferably, the heat-pressing curing condition is: pressing at 180-240℃ under a pressure of 3-7Mpa for 8-10h.

[0020] The application also provides application of the above-mentioned bis-amine benzoxazine resin in the field of friction-reducing and wear-resisting.

[0021] Preferably, the application includes production of sliding bearing or transmission / motion part of high-temperature bushing in heavy-load and high-speed working conditions. Compared with the prior art, the application has the beneficial effects that:

[0022] The application synthesizes a novel bis-amine benzoxazine monomer containing flexible connecting segment by using 4,4'-ethylenedianiline as amine source, and then heat-presses and cures the bis-amine benzoxazine monomer to obtain the bis-amine benzoxazine resin. Compared with traditional commercial bis-amine benzoxazine resin (PH-ddm), the bis-amine benzoxazine resin of the application lengthens the flexible bridge chain between benzene rings, so that the flowability of polymer chain is enhanced, thereby improving the thermal stability and tribological property of the resin.

[0023] Compared with traditional benzoxazine resin, the bis-amine benzoxazine resin of the application has more excellent thermal stability and lower polymerization temperature, and has a friction coefficient as low as 0.06-0.1 and a wear rate of 4.5-8.0*10 -5 mm 3 / Nm, and still maintains good friction-reducing and wear-resisting property under high load and high speed. The friction coefficient of traditional commercial bis-amine benzoxazine resin (PH-ddm) is 0.35, and the wear rate is 8.5*10 -4 mm 3 / Nm. In comparison, the bis-amine benzoxazine resin of the application exhibits excellent friction-reducing and wear-resisting property, which provides necessary conditions for its use as a polymer lubricating material.

[0024] The bis-amine benzoxazine resin of the application has simple synthesis process, high yield (about 88%), and low requirement for equipment, and is suitable for large-scale production. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 It is a nuclear magnetic resonance hydrogen spectrum of bis-amine benzoxazine monomer.

[0026] Figure 2 It is an infrared spectrum of bis-amine benzoxazine monomer.

[0027] Figure 3 It is a DSC spectrum of bis-amine benzoxazine monomer.

[0028] Figure 4 It is a TGA spectrum of bis-amine benzoxazine resin.

[0029] Figure 5 It is a friction coefficient diagram of bis-amine benzoxazine resin.

[0030] Figure 6 The friction coefficient and wear rate diagram of the bis-amine benzoxazine resin. DETAILED DESCRIPTION

[0031] The application will be further described below in conjunction with the drawings and specific examples, but the scope of protection of the application is not limited thereto.

[0032] The reaction equation of the reaction is:

[0033]

[0034] The structure of the phenolic compound is which includes any one of A to E:

[0035]

[0036] Example 1: Preparation of bis-amine benzoxazine resin

[0037] In this example, 4,4'-vinyl diphenylamine is used as the amine source and phenol is used as the phenol source to prepare bis-amine benzoxazine resin, and the structure of the bis-amine benzoxazine resin is:

[0038]

[0039] The equation of the reaction is:

[0040]

[0041] The specific preparation steps are as follows:

[0042] 1.06 g (0.005 mol) of 4,4'-vinyl diphenylamine, 0.94 g (0.010 mol) of phenol and 0.622 g (0.022 mol) of polyformaldehyde are added into a 100 mL round-bottom flask and mixed, then 50 mL of toluene solution is added thereto, a condenser tube is connected, and the reaction is stirred at 120°C for 6 h. After the reaction is completed, it is cooled to room temperature, the solvent is removed by rotary evaporation to obtain a crude product, and then the bis-amine benzoxazine monomer is obtained by recrystallization with ethanol, and the yield is 88%.

[0043] The bis-amine benzoxazine monomer is heat-pressed and cured, and the conditions are: pressing at 180°C and a pressure of 5 MPa for 9 h to obtain the bis-amine benzoxazine resin.

[0044] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the bis-amine benzoxazine monomer is shown in the figure, and it can be seen from the figure that the chemical shifts of about 5.4 ppm and 4.6 ppm are characteristic peaks of the oxazine ring. Figure 2The infrared spectrum of the diamine benzoxazine monomer is shown in the figure, from which it can be seen that 945 and 1229 cm -1 are characteristic absorption peaks of the benzoxazine ring. In combination Figure 1 and 2 It can be seen that the diamine benzoxazine monomer is successfully synthesized in this embodiment.

[0045] Figure 3 The DSC spectrum of the diamine benzoxazine monomer is shown in the figure, from which it can be seen that the curing exothermic peak temperature of the benzoxazine monomer is 227.5°C, which indicates that the diamine benzoxazine resin prepared by the present application has a lower polymerization temperature.

[0046] Figure 4 The TGA spectrum of the diamine benzoxazine resin is shown in the figure, from which it can be seen that the temperature at which the benzoxazine resin loses 10% of its weight is 392°C, and the carbon residue rate at 800°C is 51%, which indicates that the diamine benzoxazine resin prepared by the present application has high thermal stability.

[0047] Figure 5 The friction coefficient graph of the diamine benzoxazine resin is shown in the figure, from which it can be seen that the average friction coefficient of the benzoxazine resin in the stable stage is as low as 0.06.

[0048] Figure 6 The friction coefficient and wear rate graph of the diamine benzoxazine resin is shown in the figure, from which it can be seen that the wear rate of the benzoxazine resin is 4.5*10 -5 mm 3 / Nm. The friction coefficient of the commercial diamine benzoxazine resin PH-ddm is 0.35, and the wear rate is 8.5*10 -4 mm 3 / Nm. In comparison, the diamine benzoxazine resin of the present application exhibits excellent friction reduction and wear resistance, with a wear rate that is an order of magnitude lower than that of the commercial diamine benzoxazine, which provides the necessary conditions for its use as a polymer lubricating material.

[0049] Example 2: Preparation of diamine benzoxazine resin

[0050] In this embodiment, 4,4'-ethylenedianiline is used as the amine source and 4-chlorophenol is used as the phenol source to prepare a diamine benzoxazine resin, and the structural formula of the diamine benzoxazine resin is:

[0051]

[0052] The specific preparation steps are as follows:

[0053] 1.06 g (0.005 mol) of 4,4'-ethylenedianiline, 1.29 g (0.010 mol) of 4-chlorophenol and 0.60 g (0.020 mol) of paraformaldehyde were mixed in a 100 ml round-bottom flask, then 50 mL of toluene solution was added thereto, a condenser tube was connected, and the reaction was stirred at 130°C for 6 h. After the reaction was completed, it was cooled to room temperature, and the solvent was removed by rotary evaporation to obtain a crude product, which was then recrystallized with ethanol to obtain a bisamine benzoxazine monomer, with a yield of 88%.

[0054] The bisamine benzoxazine monomer was heat-pressed and cured to obtain a bisamine benzoxazine resin under the condition of 240°C and a pressure of 3 MPa for 8 h.

[0055] The bisamine benzoxazine monomer was heat-pressed and cured to obtain a bisamine benzoxazine resin.

[0056] It was tested that the bisamine benzoxazine monomer prepared in this embodiment had a curing exothermic peak temperature of 230.4°C, and the further cured and crosslinked bisamine benzoxazine resin had a temperature of 394°C at 10% of thermal weight loss, a carbon residue rate of 54% at 800°C in an inert gas atmosphere, a friction coefficient of 0.096, and a wear rate of 6.9 x 10 -5 mm 3 / Nm.

[0057] Example 3: Preparation of a bisamine benzoxazine resin

[0058] In this embodiment, 4,4'-ethylenedianiline was used as an amine source, and 4-methylphenol was used as a phenol source to prepare a bisamine benzoxazine resin, and the structural formula of the bisamine benzoxazine resin was as follows:

[0059]

[0060] The specific preparation steps were as follows:

[0061] 1.06 g (0.005 mol) of 4,4'-ethylenedianiline, 1.29 g (0.010 mol) of 4-chlorophenol and 0.60 g (0.020 mol) of paraformaldehyde were mixed in a 100 ml round-bottom flask, then 50 mL of toluene solution was added thereto, a condenser tube was connected, and the reaction was stirred at 130°C for 6 h. After the reaction was completed, it was cooled to room temperature, and the solvent was removed by rotary evaporation to obtain a crude product, which was then recrystallized with ethanol to obtain a bisamine benzoxazine monomer, with a yield of 88%.

[0062] The bisamine benzoxazine monomer was heat-pressed and cured to obtain a bisamine benzoxazine resin under the condition of 240°C and a pressure of 3 MPa for 8 h.

[0063] The diamine benzoxazine monomer prepared in this embodiment has a curing exothermic peak temperature of 232.8°C. The further cured and crosslinked diamine benzoxazine resin has a temperature of 397°C at 10% thermal weight loss, a carbon residue rate of 56% at 800°C in an inert gas atmosphere, a friction coefficient of 0.08, and a wear rate of 7.2 x 10 -5 mm 3 / Nm.

[0064] Example 4: Preparation of a diamine benzoxazine resin

[0065] In this embodiment, 4,4'-ethylenedianiline is used as the amine source and 4-fluorophenol is used as the phenol source to prepare a diamine benzoxazine resin, which has the following structural formula:

[0066]

[0067] The specific preparation steps are as follows:

[0068] 1.06 g (0.005 mol) of 4,4'-ethylenedianiline, 1.12 g (0.010 mol) of 4-fluorophenol, and 0.84 g (0.028 mol) of polyformaldehyde are added to a 100 ml round-bottom flask and mixed, then 50 mL of a toluene solution is added thereto, a condenser tube is connected, and stirring is performed at 90°C for 8 h. After the reaction is completed, the reaction solution is cooled to room temperature, and the solvent is removed by rotary evaporation to obtain a crude product. Then, the diamine benzoxazine monomer is obtained by recrystallization with ethanol, and the yield is 86%.

[0069] The diamine benzoxazine monomer is heat-pressed and cured to obtain a diamine benzoxazine resin under the condition of 190°C and a pressure of 6 MPa for 9 h.

[0070] The diamine benzoxazine monomer prepared in this embodiment has a curing exothermic peak temperature of 235.8°C. The further cured and crosslinked diamine benzoxazine resin has a temperature of 403°C at 10% thermal weight loss, a carbon residue rate of 58% at 800°C in an inert gas atmosphere, a friction coefficient of 0.07, and a wear rate of 6.3 x 10 -5 mm 3 / Nm.

[0071] Example 5: Preparation of a diamine benzoxazine resin

[0072] In this embodiment, 4,4'-ethylenedianiline is used as the amine source and 4-cyanophenol is used as the phenol source to prepare a diamine benzoxazine resin, which has the following structural formula:

[0073]

[0074] The specific preparation steps are as follows:

[0075] 1.06 g (0.005 mol) of 4,4'-ethylenedianiline, 1.19 g (0.010 mol) of 4-cyanophenol and 0.90 g (0.030 mol) of paraformaldehyde were mixed in a 100 mL round-bottom flask, and then 50 mL of a toluene solution was added thereto, a condenser tube was connected, and the reaction was stirred at 80°C for 8 hours. After the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed by rotary evaporation to obtain a crude product, which was recrystallized with ethanol to obtain a bisamine benzoxazine monomer, with a yield of 88%.

[0076] The bisamine benzoxazine monomer was heat-pressed and cured to obtain a bisamine benzoxazine resin by pressing at 180°C and a pressure of 7 MPa for 10 hours.

[0077] The bisamine benzoxazine monomer prepared in the embodiment was tested, and the exothermic peak temperature of the cured bisamine benzoxazine monomer was 236.8°C. The bisamine benzoxazine resin after further curing and crosslinking had a temperature of 406°C at 10% of thermal weight loss, a carbon residue rate of 59% at 800°C in an inert gas atmosphere, a friction coefficient of 0.1, and a wear rate of 8.0*10 -5 mm 3 / Nm.

[0078] In summary, the bisamine benzoxazine resin is prepared by using 4,4'-ethylenedianiline as an amine source and adjusting the length of a flexible chain segment. The bisamine benzoxazine resin has excellent thermal stability and friction performance, a friction coefficient as low as 0.06-0.1, a wear rate of 4.5-8.0*10 -5 mm 3 / Nm, and still maintains good friction-reducing and wear-resistant properties under high load and high speed. The bisamine benzoxazine resin has a low polymerization temperature and very excellent thermal, mechanical and friction performance. The preparation method of the bisamine benzoxazine resin is simple, has a high yield, has low requirements for equipment, is easy to realize large-scale production, and has good practicability.

[0079] The embodiment is a preferred embodiment of the present application, but the present application is not limited to the above-mentioned embodiments. Any obvious improvements, replacements or modifications made by those skilled in the art without departing from the essential content of the present application are within the protection scope of the present application.

Claims

1. A reduced friction, wear resistant bis-amine benzoxazine resin characterized by, The diamine benzoxazine resin is obtained by hot-pressing curing of the diamine benzoxazine monomer, and the diamine benzoxazine monomer has a molecular chemical structural formula as shown in the following formula: In the formula, R is any one of Cl, CH3, F or CN.

2. The process for the preparation of the bis-aminobenzoxazine resin according to claim 1, characterized in that, The preparation method comprises the following steps: 4, 4'-ethylenedianiline, phenolic compound, paraformaldehyde are mixed, then a low-polarity solvent is added, and after uniform mixing, heating reaction is carried out, after the reaction is completed, filtration, washing, rotary evaporation and drying are carried out to obtain a solid product, i.e. the diamine benzoxazine monomer; then the diamine benzoxazine monomer is subjected to hot-pressing curing to obtain the diamine benzoxazine resin; the structural formula of the 4, 4'-ethylenedianiline is as shown in the following formula:

3. The process for the preparation of a bis-amine benzoxazine resin according to claim 2, characterized in that, The phenolic compound has a structural formula R is any one of CI, CH3, F or CN.

4. The method for preparing the diamine benzoxazine resin according to claim 2, characterized in that, The molar ratio of 4, 4'-ethylenedianiline, phenolic compound and paraformaldehyde is 1:2:(4-6).

5. The method for preparing the diamine benzoxazine resin according to claim 4, characterized in that, The molar ratio of 4, 4'-ethylenedianiline, phenolic compound and paraformaldehyde is 1:2:4.

4.

6. The method for preparing the diamine benzoxazine resin according to claim 2, characterized in that, The low-polarity solvent comprises one or a mixture of several of toluene, xylene and dioxane.

7. The method for preparing the diamine benzoxazine resin according to claim 2, characterized in that, The heating reaction is carried out at 80-130 DEG C for 6-8 hours.

8. The method for preparing the diamine benzoxazine resin according to claim 2, characterized in that, The hot-pressing curing is carried out at 180-240 DEG C under a pressure of 3-7 MPa for 8-10 hours.

9. The diamine benzoxazine resin according to claim 1 is applied in the field of friction-reducing and wear-resistant.

10. Use according to claim 9, characterized in that, The application comprises production of transmission components such as sliding bearings or high-temperature bushings under heavy-load and high-speed working conditions.

11. Use of bis-aminobenzoxazine resins in the field of friction and wear reduction, characterized in that, The diamine benzoxazine resin is obtained by hot-pressing curing of the diamine benzoxazine monomer, and the diamine benzoxazine monomer has a molecular chemical structural formula as shown in the following formula:

12. Use according to claim 11, characterized in that, The application comprises production of transmission components such as sliding bearings or high-temperature bushings under heavy-load and high-speed working conditions.

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