阅读说明：本技术 一种橡塑制品发泡用复合发泡剂 (Composite foaming agent for foaming rubber and plastic products ) 是由 不公告发明人 于 2021-08-13 设计创作，主要内容包括：本发明公开一种橡塑制品发泡用复合发泡剂,包括助剂和主剂,所述助剂包括如下重量份原料：15-30份二氧化硅,50-70份无水乙醇,15-25份去离子水,5-10份乙烯基三甲氧基硅烷,20-30份司盘80,3-8份液体石蜡,10-15份2-丙烯酰胺-2-甲基丙磺酸,2-5份丙烯酰胺,1-3份N,N-亚甲基双丙烯酰胺；主剂能够赋予其优异的耐热性能,赋予制备出的发泡剂在高温下使用性能,当主剂受热分解时能够产生氮气、水和二硫化物等物质,产生发泡性能,而且通过与助剂的协同增效作用,能够进一步促进橡塑制品发泡。(The invention discloses a composite foaming agent for foaming a rubber and plastic product, which comprises an auxiliary agent and a main agent, wherein the auxiliary agent comprises the following raw materials in parts by weight: 15-30 parts of silicon dioxide, 50-70 parts of absolute ethyl alcohol, 15-25 parts of deionized water, 5-10 parts of vinyl trimethoxy silane, 20-30 parts of span 80, 3-8 parts of liquid paraffin, 10-15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2-5 parts of acrylamide and 1-3 parts of N, N-methylene bisacrylamide; the main agent can endow the rubber-plastic product with excellent heat resistance, the prepared foaming agent has service performance at high temperature, substances such as nitrogen, water, disulfide and the like can be generated when the main agent is heated and decomposed to generate foaming performance, and the foaming of the rubber-plastic product can be further promoted through the synergistic interaction with the auxiliary agent.)

1. The composite foaming agent for foaming the rubber and plastic product is characterized by comprising an auxiliary agent and a main agent, wherein the auxiliary agent comprises the following raw materials in parts by weight: 15-30 parts of silicon dioxide, 50-70 parts of absolute ethyl alcohol, 15-25 parts of deionized water, 5-10 parts of vinyl trimethoxy silane, 20-30 parts of span 80, 3-8 parts of liquid paraffin, 10-15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2-5 parts of acrylamide and 1-3 parts of N, N-methylene bisacrylamide;

the auxiliary agent is prepared by the following steps:

step S1, adding absolute ethyl alcohol and deionized water into a beaker, dropwise adding 10% by mass of dilute hydrochloric acid to adjust the pH until the pH =4-5, adding nano-silica, stirring at a constant speed and performing ultrasound for 20min, then adding vinyl trimethoxy silane, continuously stirring for 30min, transferring the mixture into a three-neck flask, heating to 60-65 ℃, stirring at a constant speed and reacting for 4h, taking out after the reaction is finished, washing with absolute ethyl alcohol for three times, and drying to obtain treated nano-silica;

step S2, adding the processed nano silicon dioxide prepared in the step S1 into a three-neck flask, sequentially adding span 80 and liquid paraffin, and heating in a water bath at 45-50 ℃ to prepare a first solution; dropwise adding a sodium hydroxide solution with the mass fraction of 30% into 2-acrylamide-2-methylpropanesulfonic acid to adjust the pH until the pH is =7, adding acrylamide, magnetically stirring for 30min, then adding N, N-methylene bisacrylamide, continuously stirring for 30min to prepare a second solution, dropwise adding the second solution into the first solution while stirring, controlling the dropwise adding time to be 15min, magnetically stirring at the rotating speed of 400 plus 500r/min after the dropwise adding is finished, dropwise adding the mixed solution a while stirring, introducing nitrogen, reacting for 6h, performing suction filtration after the reaction is finished, and washing with absolute ethyl alcohol for three times to prepare the assistant.

2. The composite foaming agent for foaming rubber and plastic products as claimed in claim 1, wherein the mixed solution a is prepared by mixing potassium persulfate, sodium bisulfite and deionized water according to a molar ratio of 1: 10, and the amount of the mixed solution a is 10% of the weight of the treated nano silica.

3. The composite foaming agent for foaming rubber and plastic products as claimed in claim 1, wherein the main agent is prepared by the following steps

Step S11, adding chlorosulfonic acid into a three-neck flask, heating in a water bath at 50-60 ℃, dropwise adding molten o-nitrochlorobenzene, controlling the dropwise adding time to be 30min, heating to 110 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 4h, cooling to room temperature after the reaction is finished, pouring the prepared reaction liquid into ice water, crystallizing, filtering, washing to obtain a crude product, adding the prepared crude product into petroleum ether, heating in a water bath at 50-55 ℃, preserving the temperature for 10min to obtain a solution A, transferring the solution A into a separating funnel, standing for layering, collecting supernatant, crystallizing, filtering, and repeating for three times to obtain an intermediate 1;

step S12, adding hydrazine hydrate into a three-neck flask filled with deionized water, placing the three-neck flask in a water bath at 0-10 ℃, slowly dropwise adding the intermediate 1 prepared in the step S11, controlling the dropwise adding time to be 15min, heating to 20-30 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 2h, monitoring the reaction progress by using TLC (thin layer chromatography) in the reaction process, preparing a mixed solution B after the reaction is finished, pouring the mixed solution B into ice water, filtering, washing with water and drying to prepare a crude product, carrying out column separation on the crude product, mixing an eluent by using petroleum ether and ethyl acetate according to the volume ratio of 50: 1, and then carrying out rotary evaporation to remove the solvent to prepare an intermediate 2;

and step S13, adding the intermediate 2 and deionized water into a three-neck flask, uniformly stirring at a rotation speed of 250r/min for 30min at a constant speed of 150-.

4. The composite foaming agent for foaming rubber and plastic products as claimed in claim 3, wherein the amount ratio of chlorosulfonic acid to o-nitrochlorobenzene is controlled to be 100 g: 35g in step S11, the amount ratio of hydrazine hydrate, intermediate 1 and deionized water is controlled to be 5 g: 10 g: 50mL in step S12, and the amount ratio of intermediate 2, sodium cyanate and deionized water is controlled to be 5 g: 1 g: 10mL in step S13.

5. The composite foaming agent for foaming rubber and plastic products as claimed in claim 1, wherein the composite foaming agent is prepared by the following method:

the main agent and the auxiliary agent are mixed according to the weight ratio of 10: 1.

Technical Field

The invention belongs to a foaming agent, and particularly relates to a composite foaming agent for foaming a rubber and plastic product.

Background

Foamed plastic parts are manufactured using a foaming agent that is mixed into or dissolved in the plastic and generates or releases a gas in the plastic. In this case, the gas may be generated by decomposition or reaction of the blowing agent or components within the blowing agent. The release of gas is typically initiated and/or caused by heat and/or a chemical reaction.

Upon foaming, the plastic part undergoes a reduction in weight per unit volume, that is, a reduction in density. The weight reduction corresponds to the percentage of gas-containing, rather than plastic material, in the foamed plastic part, essentially the ratio of the pore volume to the total volume of the plastic part.

Chinese patent CN102471514B is a method for manufacturing foamed plastic parts, in which a blowing agent composition is introduced into a plastic matrix and pores are formed in the plastic matrix by releasing at least carbon dioxide gas from the blowing agent composition, the blowing agent composition comprising at least one carbon dioxide carrier selected from carbonates, bicarbonates and carbamates of alkali metals, alkaline earth metals, aluminum, transition metals and/or ammonium, and at least one acid carrier, but the blowing agent prepared by the invention has insignificant foaming effect and single components, cannot produce synergistic effect between the components, and cannot be used at high temperature.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a composite foaming agent for foaming rubber and plastic products.

The purpose of the invention can be realized by the following technical scheme:

the composite foaming agent for foaming the rubber and plastic product comprises an auxiliary agent and a main agent, wherein the auxiliary agent comprises the following raw materials in parts by weight: 15-30 parts of silicon dioxide, 50-70 parts of absolute ethyl alcohol, 15-25 parts of deionized water, 5-10 parts of vinyl trimethoxy silane, 20-30 parts of span 80, 3-8 parts of liquid paraffin, 10-15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2-5 parts of acrylamide and 1-3 parts of N, N-methylene bisacrylamide;

the auxiliary agent is prepared by the following steps:

step S1, adding absolute ethyl alcohol and deionized water into a beaker, dropwise adding 10% by mass of dilute hydrochloric acid to adjust the pH until the pH is 4-5, adding nano-silica, stirring at a constant speed and performing ultrasound for 20min, then adding vinyl trimethoxy silane, continuously stirring for 30min, transferring to a three-neck flask, heating to 60-65 ℃, stirring at a constant speed and reacting for 4h, taking out after the reaction is finished, washing with absolute ethyl alcohol for three times, and drying to obtain treated nano-silica;

step S2, adding the processed nano silicon dioxide prepared in the step S1 into a three-neck flask, sequentially adding span 80 and liquid paraffin, and heating in a water bath at 45-50 ℃ to prepare a first solution; dropwise adding a sodium hydroxide solution with the mass fraction of 30% into 2-acrylamide-2-methylpropanesulfonic acid to adjust the pH until the pH is 7, adding acrylamide, magnetically stirring for 30min, then adding N, N-methylene bisacrylamide, continuously stirring for 30min to prepare a second solution, dropwise adding the second solution into the first solution while stirring, controlling the dropwise adding time to be 15min, magnetically stirring at the rotation speed of 400 plus 500r/min after the dropwise adding is finished, dropwise adding the mixed solution a while stirring, introducing nitrogen, reacting for 6h, performing suction filtration after the reaction is finished, and washing with absolute ethyl alcohol for three times to prepare the assistant.

According to the invention, the nano-silica is subjected to surface treatment modification through vinyl trimethoxy silane, the defect of easy agglomeration is improved, the treated nano-silica, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid are mixed, and an addition reaction is carried out among the treated nano-silica, the treated acrylamide and the 2-acrylamide-2-methylpropanesulfonic acid to prepare the auxiliary agent, wherein the auxiliary agent is an expandable microsphere.

Further, the mixed solution a is formed by mixing potassium persulfate, sodium bisulfite and deionized water according to a molar ratio of 1: 10, and the dosage of the mixed solution a is 10% of the weight of the treated nano silicon dioxide.

Further, the main agent is prepared by the following steps

Step S11, adding chlorosulfonic acid into a three-neck flask, heating in a water bath at 50-60 ℃, dropwise adding molten o-nitrochlorobenzene, controlling the dropwise adding time to be 30min, heating to 110 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 4h, cooling to room temperature after the reaction is finished, pouring the prepared reaction liquid into ice water, crystallizing, filtering, washing to obtain a crude product, adding the prepared crude product into petroleum ether, heating in a water bath at 50-55 ℃, preserving the temperature for 10min to obtain a solution A, transferring the solution A into a separating funnel, standing for layering, collecting supernatant, crystallizing, filtering, and repeating for three times to obtain an intermediate 1;

step S12, adding hydrazine hydrate into a three-neck flask filled with deionized water, placing the three-neck flask in a water bath at 0-10 ℃, slowly dropwise adding the intermediate 1 prepared in the step S11, controlling the dropwise adding time to be 15min, heating to 20-30 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 2h, monitoring the reaction progress by using TLC (thin layer chromatography) in the reaction process, preparing a mixed solution B after the reaction is finished, pouring the mixed solution B into ice water, filtering, washing with water and drying to prepare a crude product, carrying out column separation on the crude product, mixing an eluent by using petroleum ether and ethyl acetate according to the volume ratio of 50: 1, and then carrying out rotary evaporation to remove the solvent to prepare an intermediate 2;

and step S13, adding the intermediate 2 and deionized water into a three-neck flask, uniformly stirring at a rotation speed of 250r/min for 30min at a constant speed of 150-.

In step S1, chlorosulfonic acid and o-nitrochlorobenzene are mixed, and chlorosulfonic acid and o-nitrochlorobenzene react to generate an intermediate 1, and the reaction process is as follows:

in step S2, hydrazine hydrate and intermediate 1 are mixed in deionized water, and hydrazine hydrate and intermediate 1 can react to generate intermediate 2, and the reaction process is as follows:

in step S3, mixing the intermediate 2 and sodium cyanate in deionized water, adding dilute hydrochloric acid to adjust an acidic system, enabling the intermediate 2 and the sodium cyanate to react to generate a product C, and then purifying to obtain a main agent, wherein the reaction is as follows:

further, the dosage ratio of chlorosulfonic acid to o-nitrochlorobenzene in the step S11 is controlled to be 100 g: 35g, the dosage ratio of hydrazine hydrate, intermediate 1 and deionized water in the step S12 is controlled to be 5 g: 10 g: 50mL, and the dosage ratio of intermediate 2, sodium cyanate and deionized water in the step S13 is controlled to be 5 g: 1 g: 10 mL.

Further, the composite foaming agent is prepared by the following method:

the main agent and the auxiliary agent are mixed according to the weight ratio of 10: 1.

The invention has the beneficial effects that:

(1) the invention relates to a composite foaming agent for foaming a rubber and plastic product, which comprises an auxiliary agent and a main agent, wherein the auxiliary agent is prepared by firstly carrying out surface treatment modification on nano silicon dioxide through vinyl trimethoxy silane to overcome the defect of easy agglomeration of the nano silicon dioxide, then mixing the treated nano silicon dioxide, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, and carrying out addition reaction on the treated nano silicon dioxide, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid to prepare the auxiliary agent.

(2) The invention also prepares a main agent, chlorosulfonic acid and o-nitrochlorobenzene are mixed in step S1, chlorosulfonic acid and o-nitrochlorobenzene react to generate an intermediate 1, hydrazine hydrate and the intermediate 1 are mixed in deionized water in step S2, hydrazine hydrate and the intermediate 1 react to generate an intermediate 2, the intermediate 2 and sodium cyanate are mixed in deionized water in step S3, dilute hydrochloric acid is added to adjust an acidic system, the intermediate 2 and sodium cyanate can react to generate a product C, the intermediate 2 is modified by sodium cyanate and hydrochloric acid to prepare a main agent, which can endow the main agent with excellent heat resistance and endow the prepared foaming agent with service performance at high temperature, when the main agent is heated and decomposed, substances such as nitrogen, water, disulfide and the like can be generated, foaming performance is generated, and the foaming of the rubber and plastic product can be further promoted through the synergistic interaction with the auxiliary agent.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The composite foaming agent for foaming the rubber and plastic product comprises an auxiliary agent and a main agent, wherein the auxiliary agent comprises the following raw materials in parts by weight: 15 parts of silicon dioxide, 50 parts of absolute ethyl alcohol, 15 parts of deionized water, 5 parts of vinyl trimethoxy silane, 20 parts of span 80, 3 parts of liquid paraffin, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2 parts of acrylamide and 1 part of N, N-methylene bisacrylamide;

the auxiliary agent is prepared by the following steps:

step S1, adding absolute ethyl alcohol and deionized water into a beaker, dropwise adding 10% by mass of dilute hydrochloric acid to adjust the pH until the pH is 4, adding nano-silica, stirring at a constant speed and performing ultrasound for 20min, then adding vinyl trimethoxy silane, continuously stirring for 30min, transferring the mixture into a three-neck flask, heating to 60 ℃, stirring at a constant speed and reacting for 4h, taking out after the reaction is finished, washing with absolute ethyl alcohol for three times, and drying to obtain treated nano-silica;

step S2, adding the processed nano silicon dioxide prepared in the step S1 into a three-neck flask, sequentially adding span 80 and liquid paraffin, and heating in a water bath at 50 ℃ to prepare a first solution; dropwise adding a sodium hydroxide solution with the mass fraction of 30% into 2-acrylamide-2-methylpropanesulfonic acid to adjust the pH until the pH is 7, adding acrylamide, magnetically stirring for 30min, then adding N, N-methylene bisacrylamide, continuously stirring for 30min to prepare a second solution, dropwise adding the second solution into the first solution while stirring, controlling the dropwise adding time to be 15min, magnetically stirring at the rotating speed of 400r/min after the dropwise adding is finished, dropwise adding the mixed solution a while stirring, introducing nitrogen, reacting for 6h, performing suction filtration after the reaction is finished, and washing with absolute ethyl alcohol for three times to prepare the assistant.

The mixed solution a is formed by mixing potassium persulfate, sodium bisulfite and deionized water according to the molar ratio of 1: 10, and the dosage of the mixed solution a is 10 percent of the weight of the treated nano silicon dioxide.

The main agent comprises the following steps

Step S11, adding chlorosulfonic acid into a three-neck flask, heating in a water bath at 50 ℃, dropwise adding molten o-nitrochlorobenzene, controlling the dropwise adding time to be 30min, heating to 110 ℃ after dropwise adding, stirring at a constant speed at the temperature, reacting for 4h, cooling to room temperature after the reaction is finished, pouring the prepared reaction liquid into ice water, crystallizing, filtering, and washing to obtain a crude product, adding the prepared crude product into petroleum ether, heating in a water bath at 55 ℃, keeping the temperature for 10min at the temperature to obtain a solution A, transferring the solution A into a separating funnel, standing for layering, collecting supernatant, crystallizing, filtering, and repeating for three times to obtain an intermediate 1, wherein the dosage ratio of chlorosulfonic acid to o-nitrochlorobenzene is controlled to be 100 g: 35 g;

step S12, adding hydrazine hydrate into a three-neck flask filled with deionized water, placing the three-neck flask in a water bath at 10 ℃, slowly dropwise adding the intermediate 1 prepared in the step S11, controlling the dropwise adding time to be 15min, heating to 20 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 2h, monitoring the reaction progress by using TLC (thin layer chromatography) in the reaction process, preparing a mixed solution B after the reaction is finished, pouring the mixed solution B into ice water, filtering, washing and drying to prepare a crude product, carrying out column separation on the crude product, mixing an eluent by petroleum ether and ethyl acetate according to a volume ratio of 50: 1, then carrying out rotary evaporation to remove a solvent to prepare an intermediate 2, and controlling the using amount ratio of the hydrazine hydrate, the intermediate 1 and the deionized water to be 5 g: 10 g: 50 mL;

step S13, adding the intermediate 2 and deionized water into a three-neck flask, uniformly stirring at a rotation speed of 150r/min for 30min, controlling the stirring temperature to be 25 ℃, dropwise adding 30% by mass of dilute hydrochloric acid after stirring to adjust the pH until the pH is 3, then adding sodium cyanate, magnetically stirring and reacting, monitoring the reaction progress by using TLC in the reaction process, adding dilute hydrochloric acid to neutralize the residual sodium cyanate after the reaction is finished to obtain a product C, pouring the product C into ice water, filtering, washing with water, drying, recrystallizing with ethanol to obtain a main agent, and controlling the dosage ratio of the intermediate 2, the sodium cyanate and the deionized water to be 5 g: 1 g: 10mL in the step S13.

Example 2

The composite foaming agent for foaming the rubber and plastic product comprises an auxiliary agent and a main agent, wherein the auxiliary agent comprises the following raw materials in parts by weight: 20 parts of silicon dioxide, 55 parts of absolute ethyl alcohol, 18 parts of deionized water, 6 parts of vinyl trimethoxy silane, 25 parts of span 80, 5 parts of liquid paraffin, 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 3 parts of acrylamide and 2 parts of N, N-methylene bisacrylamide;

the auxiliary agent is prepared by the following steps:

step S1, adding absolute ethyl alcohol and deionized water into a beaker, dropwise adding 10% by mass of dilute hydrochloric acid to adjust the pH until the pH is 4, adding nano-silica, stirring at a constant speed and performing ultrasound for 20min, then adding vinyl trimethoxy silane, continuously stirring for 30min, transferring the mixture into a three-neck flask, heating to 60 ℃, stirring at a constant speed and reacting for 4h, taking out after the reaction is finished, washing with absolute ethyl alcohol for three times, and drying to obtain treated nano-silica;

step S2, adding the processed nano silicon dioxide prepared in the step S1 into a three-neck flask, sequentially adding span 80 and liquid paraffin, and heating in a water bath at 50 ℃ to prepare a first solution; dropwise adding a sodium hydroxide solution with the mass fraction of 30% into 2-acrylamide-2-methylpropanesulfonic acid to adjust the pH until the pH is 7, adding acrylamide, magnetically stirring for 30min, then adding N, N-methylene bisacrylamide, continuously stirring for 30min to prepare a second solution, dropwise adding the second solution into the first solution while stirring, controlling the dropwise adding time to be 15min, magnetically stirring at the rotating speed of 400r/min after the dropwise adding is finished, dropwise adding the mixed solution a while stirring, introducing nitrogen, reacting for 6h, performing suction filtration after the reaction is finished, and washing with absolute ethyl alcohol for three times to prepare the assistant.

The mixed solution a is formed by mixing potassium persulfate, sodium bisulfite and deionized water according to the molar ratio of 1: 10, and the dosage of the mixed solution a is 10% of the weight of the treated nano silicon dioxide.

The main agent comprises the following steps

Step S11, adding chlorosulfonic acid into a three-neck flask, heating in a water bath at 50 ℃, dropwise adding molten o-nitrochlorobenzene, controlling the dropwise adding time to be 30min, heating to 110 ℃ after dropwise adding, stirring at a constant speed at the temperature, reacting for 4h, cooling to room temperature after the reaction is finished, pouring the prepared reaction liquid into ice water, crystallizing, filtering, and washing to obtain a crude product, adding the prepared crude product into petroleum ether, heating in a water bath at 55 ℃, keeping the temperature for 10min at the temperature to obtain a solution A, transferring the solution A into a separating funnel, standing for layering, collecting supernatant, crystallizing, filtering, and repeating for three times to obtain an intermediate 1, wherein the dosage ratio of chlorosulfonic acid to o-nitrochlorobenzene is controlled to be 100 g: 35 g;

step S12, adding hydrazine hydrate into a three-neck flask filled with deionized water, placing the three-neck flask in a water bath at 10 ℃, slowly dropwise adding the intermediate 1 prepared in the step S11, controlling the dropwise adding time to be 15min, heating to 20 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 2h, monitoring the reaction progress by using TLC (thin layer chromatography) in the reaction process, preparing a mixed solution B after the reaction is finished, pouring the mixed solution B into ice water, filtering, washing and drying to prepare a crude product, carrying out column separation on the crude product, mixing an eluent by petroleum ether and ethyl acetate according to a volume ratio of 50: 1, then carrying out rotary evaporation to remove a solvent to prepare an intermediate 2, and controlling the using amount ratio of the hydrazine hydrate, the intermediate 1 and the deionized water to be 5 g: 10 g: 50 mL;

step S13, adding the intermediate 2 and deionized water into a three-neck flask, uniformly stirring at a rotation speed of 150r/min for 30min, controlling the stirring temperature to be 25 ℃, dropwise adding 30% by mass of dilute hydrochloric acid after stirring to adjust the pH until the pH is 3, then adding sodium cyanate, magnetically stirring and reacting, monitoring the reaction progress by using TLC in the reaction process, adding dilute hydrochloric acid to neutralize the residual sodium cyanate after the reaction is finished to obtain a product C, pouring the product C into ice water, filtering, washing with water, drying, recrystallizing with ethanol to obtain a main agent, and controlling the dosage ratio of the intermediate 2, the sodium cyanate and the deionized water to be 5 g: 1 g: 10mL in the step S13.

Example 3

The composite foaming agent for foaming the rubber and plastic product comprises an auxiliary agent and a main agent, wherein the auxiliary agent comprises the following raw materials in parts by weight: 25 parts of silicon dioxide, 60 parts of absolute ethyl alcohol, 20 parts of deionized water, 8 parts of vinyl trimethoxy silane, 28 parts of span 80, 6 parts of liquid paraffin, 14 parts of 2-acrylamide-2-methylpropanesulfonic acid, 4 parts of acrylamide and 2 parts of N, N-methylene bisacrylamide;

the auxiliary agent is prepared by the following steps:

step S1, adding absolute ethyl alcohol and deionized water into a beaker, dropwise adding 10% by mass of dilute hydrochloric acid to adjust the pH until the pH is 4, adding nano-silica, stirring at a constant speed and performing ultrasound for 20min, then adding vinyl trimethoxy silane, continuously stirring for 30min, transferring the mixture into a three-neck flask, heating to 60 ℃, stirring at a constant speed and reacting for 4h, taking out after the reaction is finished, washing with absolute ethyl alcohol for three times, and drying to obtain treated nano-silica;

step S2, adding the processed nano silicon dioxide prepared in the step S1 into a three-neck flask, sequentially adding span 80 and liquid paraffin, and heating in a water bath at 50 ℃ to prepare a first solution; dropwise adding a sodium hydroxide solution with the mass fraction of 30% into 2-acrylamide-2-methylpropanesulfonic acid to adjust the pH until the pH is 7, adding acrylamide, magnetically stirring for 30min, then adding N, N-methylene bisacrylamide, continuously stirring for 30min to prepare a second solution, dropwise adding the second solution into the first solution while stirring, controlling the dropwise adding time to be 15min, magnetically stirring at the rotating speed of 400r/min after the dropwise adding is finished, dropwise adding the mixed solution a while stirring, introducing nitrogen, reacting for 6h, performing suction filtration after the reaction is finished, and washing with absolute ethyl alcohol for three times to prepare the assistant.

The mixed solution a is formed by mixing potassium persulfate, sodium bisulfite and deionized water according to the molar ratio of 1: 10, and the dosage of the mixed solution a is 10% of the weight of the treated nano silicon dioxide.

The main agent comprises the following steps

Step S11, adding chlorosulfonic acid into a three-neck flask, heating in a water bath at 50 ℃, dropwise adding molten o-nitrochlorobenzene, controlling the dropwise adding time to be 30min, heating to 110 ℃ after dropwise adding, stirring at a constant speed at the temperature, reacting for 4h, cooling to room temperature after the reaction is finished, pouring the prepared reaction liquid into ice water, crystallizing, filtering, and washing to obtain a crude product, adding the prepared crude product into petroleum ether, heating in a water bath at 55 ℃, keeping the temperature for 10min at the temperature to obtain a solution A, transferring the solution A into a separating funnel, standing for layering, collecting supernatant, crystallizing, filtering, and repeating for three times to obtain an intermediate 1, wherein the dosage ratio of chlorosulfonic acid to o-nitrochlorobenzene is controlled to be 100 g: 35 g;

step S12, adding hydrazine hydrate into a three-neck flask filled with deionized water, placing the three-neck flask in a water bath at 10 ℃, slowly dropwise adding the intermediate 1 prepared in the step S11, controlling the dropwise adding time to be 15min, heating to 20 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 2h, monitoring the reaction progress by using TLC (thin layer chromatography) in the reaction process, preparing a mixed solution B after the reaction is finished, pouring the mixed solution B into ice water, filtering, washing and drying to prepare a crude product, carrying out column separation on the crude product, mixing an eluent by petroleum ether and ethyl acetate according to a volume ratio of 50: 1, then carrying out rotary evaporation to remove a solvent to prepare an intermediate 2, and controlling the using amount ratio of the hydrazine hydrate, the intermediate 1 and the deionized water to be 5 g: 10 g: 50 mL;

step S13, adding the intermediate 2 and deionized water into a three-neck flask, uniformly stirring at a rotation speed of 150r/min for 30min, controlling the stirring temperature to be 25 ℃, dropwise adding 30% by mass of dilute hydrochloric acid after stirring to adjust the pH until the pH is 3, then adding sodium cyanate, magnetically stirring and reacting, monitoring the reaction progress by using TLC in the reaction process, adding dilute hydrochloric acid to neutralize the residual sodium cyanate after the reaction is finished to obtain a product C, pouring the product C into ice water, filtering, washing with water, drying, recrystallizing with ethanol to obtain a main agent, and controlling the dosage ratio of the intermediate 2, the sodium cyanate and the deionized water to be 5 g: 1 g: 10mL in the step S13.

Example 4

The composite foaming agent for foaming the rubber and plastic product comprises an auxiliary agent and a main agent, wherein the auxiliary agent comprises the following raw materials in parts by weight: 30 parts of silicon dioxide, 70 parts of absolute ethyl alcohol, 25 parts of deionized water, 10 parts of vinyl trimethoxy silane, 30 parts of span 80, 8 parts of liquid paraffin, 15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 5 parts of acrylamide and 3 parts of N, N-methylene bisacrylamide;

the auxiliary agent is prepared by the following steps:

step S1, adding absolute ethyl alcohol and deionized water into a beaker, dropwise adding 10% by mass of dilute hydrochloric acid to adjust the pH until the pH is 4, adding nano-silica, stirring at a constant speed and performing ultrasound for 20min, then adding vinyl trimethoxy silane, continuously stirring for 30min, transferring the mixture into a three-neck flask, heating to 60 ℃, stirring at a constant speed and reacting for 4h, taking out after the reaction is finished, washing with absolute ethyl alcohol for three times, and drying to obtain treated nano-silica;

step S2, adding the processed nano silicon dioxide prepared in the step S1 into a three-neck flask, sequentially adding span 80 and liquid paraffin, and heating in a water bath at 50 ℃ to prepare a first solution; dropwise adding a sodium hydroxide solution with the mass fraction of 30% into 2-acrylamide-2-methylpropanesulfonic acid to adjust the pH until the pH is 7, adding acrylamide, magnetically stirring for 30min, then adding N, N-methylene bisacrylamide, continuously stirring for 30min to prepare a second solution, dropwise adding the second solution into the first solution while stirring, controlling the dropwise adding time to be 15min, magnetically stirring at the rotating speed of 400r/min after the dropwise adding is finished, dropwise adding the mixed solution a while stirring, introducing nitrogen, reacting for 6h, performing suction filtration after the reaction is finished, and washing with absolute ethyl alcohol for three times to prepare the assistant.

The mixed solution a is formed by mixing potassium persulfate, sodium bisulfite and deionized water according to the molar ratio of 1: 10, and the dosage of the mixed solution a is 10% of the weight of the treated nano silicon dioxide.

The main agent comprises the following steps

Step S11, adding chlorosulfonic acid into a three-neck flask, heating in a water bath at 50 ℃, dropwise adding molten o-nitrochlorobenzene, controlling the dropwise adding time to be 30min, heating to 110 ℃ after dropwise adding, stirring at a constant speed at the temperature, reacting for 4h, cooling to room temperature after the reaction is finished, pouring the prepared reaction liquid into ice water, crystallizing, filtering, and washing to obtain a crude product, adding the prepared crude product into petroleum ether, heating in a water bath at 55 ℃, keeping the temperature for 10min at the temperature to obtain a solution A, transferring the solution A into a separating funnel, standing for layering, collecting supernatant, crystallizing, filtering, and repeating for three times to obtain an intermediate 1, wherein the dosage ratio of chlorosulfonic acid to o-nitrochlorobenzene is controlled to be 100 g: 35 g;

step S12, adding hydrazine hydrate into a three-neck flask filled with deionized water, placing the three-neck flask in a water bath at 10 ℃, slowly dropwise adding the intermediate 1 prepared in the step S11, controlling the dropwise adding time to be 15min, heating to 20 ℃ after the dropwise adding is finished, stirring at a constant speed and reacting for 2h, monitoring the reaction progress by using TLC (thin layer chromatography) in the reaction process, preparing a mixed solution B after the reaction is finished, pouring the mixed solution B into ice water, filtering, washing and drying to prepare a crude product, carrying out column separation on the crude product, mixing an eluent by petroleum ether and ethyl acetate according to a volume ratio of 50: 1, then carrying out rotary evaporation to remove a solvent to prepare an intermediate 2, and controlling the using amount ratio of the hydrazine hydrate, the intermediate 1 and the deionized water to be 5 g: 10 g: 50 mL;

step S13, adding the intermediate 2 and deionized water into a three-neck flask, uniformly stirring at a rotation speed of 150r/min for 30min, controlling the stirring temperature to be 25 ℃, dropwise adding 30% by mass of dilute hydrochloric acid after stirring to adjust the pH until the pH is 3, then adding sodium cyanate, magnetically stirring and reacting, monitoring the reaction progress by using TLC in the reaction process, adding dilute hydrochloric acid to neutralize the residual sodium cyanate after the reaction is finished to obtain a product C, pouring the product C into ice water, filtering, washing with water, drying, recrystallizing with ethanol to obtain a main agent, and controlling the dosage ratio of the intermediate 2, the sodium cyanate and the deionized water to be 5 g: 1 g: 10mL in the step S13.

Comparative example 1

In comparison with example 1, no auxiliary was added in this comparative example.

Comparative example 2

This comparative example is the us suwei B430 blowing agent in the market.

The foaming properties of examples 1 to 4 and comparative examples 1 to 2 were tested and the results are shown in the following table:

the foaming agents prepared in examples 1-4 and comparative examples 1-2 and other auxiliary agents and other raw materials are respectively added into polystyrene plastics, the foaming materials are prepared through processes of mixing, open mixing, mould pressing, foaming and the like, the density is tested according to GB/T6343-2009, and the results are shown in the following table;

from the above table, it can be seen that the densities of examples 1-4 are from 0.250 to 0.252g/cm³Comparative examples 1 to 2 had densities of 0.315 to 0.356g/cm³(ii) a Therefore, when the main agent is heated and decomposed, substances such as nitrogen, water, disulfide and the like can be generated, foaming performance is generated, and the rubber and plastic product can be further promoted to foam through the synergistic interaction with the auxiliary agent.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.