Preparation method of rubber vulcanization accelerator

Abstract

The invention discloses a preparation method of a rubber vulcanization accelerator, which is characterized in that BPP and bisphenol AF are subjected to a heating reaction under normal pressure in the presence of a solvent and alkali, and a rubber vulcanizing agent is prepared through a two-step reaction. According to the method, industrial products BPP and bisphenol AF are selected as raw materials, the method has the advantages that operation is easy, reagents are cheap and easy to obtain, and the method is environmentally friendly, the highest yield can reach 95%, and industrial production is facilitated.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemical synthesis, and specifically relates to a method for preparing a rubber vulcanization accelerator. Background Art

[0002] The rubber vulcanization accelerator produced with BPP and bisphenol AF as raw materials is a new rubber vulcanization accelerator, and there are few research reports related to it. According to our research, it has the following advantages:

[0003] 1. It can greatly accelerate the speed of rubber vulcanization;

[0004] 2. Compared with other vulcanization accelerators, it does not contain halogen, which greatly improves the quality of rubber.

[0005] Due to the unique advantages of the rubber vulcanization accelerator produced with BPP and bisphenol AF as raw materials, it is urgent to develop a method for synthesizing the rubber vulcanization accelerator. Summary of the invention

[0006] The object of the present invention is to provide a method for preparing a rubber vulcanization accelerator in view of the above-mentioned problems.

[0007] The present invention provides a method for preparing a rubber vulcanization accelerator, comprising the following steps:

[0008] Under normal pressure, BPP and bisphenol AF are heated to react in the presence of a solvent and an alkali to prepare a rubber vulcanization accelerator phosphonium salt in two steps. The reaction equation is shown in Formula 1:

[0009]

[0010] In some embodiments, the molar ratio of bisphenol AF to Na salt is not higher than 1:1. Preferably, the molar ratio of bisphenol AF to Na salt is 1:(1.1-2). The usage ratio of bisphenol AF to solvent is 1 mmol:(1-4) mL. Preferably, the usage ratio of bisphenol AF to solvent is 1 mmol:(1-1.5) mL.

[0011] In some embodiments, the sodium salt in Formula 1A is one or more of sodium hydroxide, sodium methoxide, sodium amide or sodium carbonate.

[0012] In some embodiments, the solvent in Formula 1A is one or more of water, methanol, ethanol, tert-butyl alcohol, ethylene glycol, or ethylene glycol dimethyl ether.

[0013] In some embodiments, the atmosphere of the heating reaction in Formula 1A is a protective atmosphere or an air atmosphere. Preferably, the atmosphere of the heating reaction is an air atmosphere, the reaction temperature is 40 to 150° C., and the reaction time is 8 h to 48 h.

[0014] In some embodiments, the intermediate A in Formula 1A is obtained by separation and purification, and the separation and purification steps are: removing the solvent by reduced pressure distillation and washing with water to obtain the intermediate A.

[0015] In some embodiments, the solvent in Formula 1B is one or more of water, methanol, ethanol, tert-butyl alcohol, ethylene glycol, or ethylene glycol dimethyl ether.

[0016] In some embodiments, the molar ratio of BPP to intermediate A in Formula 1B is not higher than 1:1. Preferably, the molar ratio of BPP to intermediate A is 1:(1.1-2). The usage ratio of BPP to solvent is 1 mmol:(1-4) mL. Preferably, the usage ratio of BPP to solvent is 1 mmol:(1-1.5) mL.

[0017] In some embodiments, the atmosphere of the heating reaction in Formula 1B is a protective atmosphere or an air atmosphere. Preferably, the atmosphere of the heating reaction is an air atmosphere, the reaction temperature is 40 to 150° C., and the reaction time is 8 h to 48 h.

[0018] In some embodiments, the vulcanization accelerator phosphonium salt in Formula 1B is obtained by separation and purification, and the separation and purification steps are: removing the solvent by reduced pressure distillation and washing with water to obtain the final product vulcanization accelerator phosphonium salt.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention uses industrial raw materials BPP and bisphenol AF as raw materials, heats and reacts in the presence of a solvent and an alkali, and prepares a rubber vulcanization accelerator phosphonium salt in two steps. The present invention has the advantages of no need for a catalyst, cheap and readily available raw materials, simple operation, green and environmental protection, etc., and is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a liquid chromatogram of the vulcanization accelerator phosphine in one embodiment. DETAILED DESCRIPTION

[0022] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0023] Embodiment 1:

[0024] A method for preparing a rubber vulcanization accelerator comprises the following steps:

[0025] S1. Under normal pressure, bisphenol A, sodium hydroxide and solvent water react to generate intermediate A, wherein the molar ratio of bisphenol AF to sodium hydroxide is 1:2, the concentration of bisphenol AF in solvent water is 1 mol / L, the atmosphere of the heating reaction is air atmosphere, the heating reaction temperature is 100°C; the heating reaction time is 8 hours, after the reaction is completed, the solvent must be removed by reduced pressure distillation, and the intermediate A can be obtained by washing with water;

[0026] S2. Under normal pressure, the intermediate, BPP and solvent water react to generate intermediate A, the molar ratio of BPP to intermediate A is 1:2, the concentration of BPP in the solvent is 1 mol / L, the atmosphere of the heating reaction is air atmosphere, the heating reaction temperature is 100°C; the heating reaction time is 8 hours, after the reaction is completed, the solvent must be removed by vacuum distillation, and the final product, vulcanization accelerator phosphonium salt, can be obtained by washing with water. Nuclear magnetic spectrum of vulcanization accelerator phosphonium salt Figure 1 as follows.

[0027] in, 1 H NMR(400MHz, Acetonitrile-d3)δ7.83(t,J=7.3Hz,3H),7.63(td,J=7.8,3.4Hz,6H),7.53(dd,J=12.7,7.7Hz,6H), 7.28 (d, J = 8.0 Hz, 1H), 7.17 (t, J = 7.7 Hz, 2H), 6.89 (d, J = 8.6 Hz, 6H), 6.51 (d, J = 8.8 Hz, 5H), 4.64 (d, J = 14.7 Hz, 2H).

[0028] The present invention uses industrial raw materials BPP and bisphenol AF as raw materials, heats and reacts in the presence of a solvent and an alkali, and prepares a rubber vulcanization accelerator phosphonium salt in two steps. The present invention has the advantages of no need for a catalyst, cheap and readily available raw materials, simple operation, green and environmental protection, etc., and is conducive to industrial production.

[0029] Finally, it should be noted that: technicians in this industry should understand that the present invention is not limited to the above-mentioned implementation cases. The above-mentioned embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which shall fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing a rubber vulcanization accelerator, characterized in that: The following steps are involved: Under normal pressure, BPP and bisphenol AF are heated to react in the presence of a solvent and an alkali to prepare a rubber vulcanization accelerator phosphonium salt in two steps. The reaction equation is shown in Formula 1:

2. The preparation method according to claim 1, characterized in that: The molar ratio of bisphenol AF to Na salt is not higher than 1:

1. Preferably, the molar ratio of bisphenol AF to Na salt is 1:(1.1-2). The usage ratio of bisphenol AF to solvent is 1 mmol:(1-4) mL. Preferably, the usage ratio of bisphenol AF to solvent is 1 mmol:(1-1.5) mL.

3. The preparation method according to claim 1, characterized in that: The sodium salt in Formula 1A is one or more of sodium hydroxide, sodium methoxide, sodium amide or sodium carbonate.

4. The preparation method according to claim 1, characterized in that: The solvent in Formula 1A is one or more of water, methanol, ethanol, tert-butyl alcohol, ethylene glycol or ethylene glycol dimethyl ether.

5. The preparation method according to claim 1, characterized in that: The atmosphere of the heating reaction in Formula 1A is a protective atmosphere or an air atmosphere. Preferably, the atmosphere of the heating reaction is an air atmosphere, the reaction temperature is 40 to 150° C., and the reaction time is 8 to 48 hours.

6. The preparation method according to claims 1 to 5, characterized in that: The intermediate A in Formula 1A is obtained by separation and purification, wherein the separation and purification steps are: removing the solvent by distillation under reduced pressure, and washing with water to obtain the intermediate A.

7. The preparation method according to claim 1, characterized in that: The solvent in Formula 1B is one or more of water, methanol, ethanol, tert-butyl alcohol, ethylene glycol or ethylene glycol dimethyl ether.

8. The preparation method according to claim 1, characterized in that: The molar ratio of BPP to intermediate A in Formula 1B is not higher than 1:

1. Preferably, the molar ratio of BPP to intermediate A is 1:(1.1-2). The usage ratio of BPP to solvent is 1 mmol:(1-4) mL. Preferably, the usage ratio of BPP to solvent is 1 mmol:(1-1.5) mL.

9. The preparation method according to claim 1, characterized in that: The atmosphere of the heating reaction in Formula 1B is a protective atmosphere or an air atmosphere. Preferably, the atmosphere of the heating reaction is an air atmosphere. The reaction temperature is 40 to 150° C. and the reaction time is 8 to 48 hours.

10. The preparation method according to claims 7 to 9, characterized in that: The vulcanization accelerator phosphonium salt in Formula 1B is obtained by separation and purification, and the separation and purification steps are: removing the solvent by reduced pressure distillation and washing with water to obtain the final product, the vulcanization accelerator phosphonium salt.

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