阅读说明：本技术 一种水溶性橡塑再生塑化软化剂及其制备方法 (Water-soluble rubber-plastic regeneration plasticizing softener and preparation method thereof ) 是由 不公告发明人 于 2021-08-19 设计创作，主要内容包括：本发明公开一种水溶性橡塑再生塑化软化剂及其制备方法,包括如下重量份原料：35-50份主剂,5-10份水溶性粒子,10-15份石油树脂,25-35份去离子水,1-3份乳化剂；第一步、将石油树脂加入反应釜中加热熔化,以50-80r/min的转速磁力搅拌,之后在90-100℃下保温备用；第二步、将乳化剂加入去离子水中,完全溶解后加入熔化后的石油树脂中,以100-150r/min的转速磁力搅拌,之后依次加入主剂和水溶性粒子,继续搅拌30min,制得水溶性橡塑再生塑化软化剂；将中间体1按照3∶1的重量比与共聚物混合均匀,制得主剂,该主剂能够溶于水,而且具有优异的塑化软化性能。(The invention discloses a water-soluble rubber-plastic regenerated plasticizing softener and a preparation method thereof, wherein the water-soluble rubber-plastic regenerated plasticizing softener comprises the following raw materials in parts by weight: 35-50 parts of main agent, 5-10 parts of water-soluble particles, 10-15 parts of petroleum resin, 25-35 parts of deionized water and 1-3 parts of emulsifier; firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50-80r/min, and then preserving heat at 90-100 ℃ for later use; secondly, adding an emulsifier into deionized water, adding the emulsifier into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100-150r/min, sequentially adding a main agent and water-soluble particles, and continuously stirring for 30min to obtain a water-soluble rubber-plastic regenerated plasticizing softener; the intermediate 1 and the copolymer are uniformly mixed according to the weight ratio of 3: 1 to prepare the main agent, and the main agent can be dissolved in water and has excellent plasticizing and softening properties.)

1. The water-soluble rubber-plastic regeneration plasticizing softener is characterized by comprising the following raw materials in parts by weight: 35-50 parts of main agent, 5-10 parts of water-soluble particles, 10-15 parts of petroleum resin, 25-35 parts of deionized water and 1-3 parts of emulsifier;

the water-soluble rubber-plastic regeneration plasticizing softener comprises the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50-80r/min, and then preserving heat at 90-100 ℃ for later use;

and secondly, adding the emulsifier into deionized water, adding the emulsifier into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100-150r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

2. The water-soluble rubber-plastic regenerated plasticizing softener according to claim 1, wherein the emulsifier is sodium petroleum sulfonate.

3. The water-soluble rubber-plastic regenerated plasticizing softener according to claim 1, characterized in that the main agent is prepared by the following steps:

step S1, adding methyldiethanolamine into a four-neck flask, placing the flask in a water bath at 10-25 ℃, standing for 15min, uniformly stirring, dropwise adding ethyl formate, controlling the dropwise adding time to be 10min, heating to 60 ℃ after the dropwise adding is finished, stirring at constant speed at the temperature, reacting for 2h, tracking the reaction process with thin layer chromatography during the reaction process, distilling under reduced pressure to remove generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 deg.C, stirring at constant speed at the temperature, reacting for 1h, distilling under reduced pressure, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 deg.C, stirring at constant speed at the temperature and reacting for 0.5h to prepare an intermediate 1, wherein the molar ratio of the total amount of the methyldiethanolamine to the ethyl formate is controlled to be 1: 1.2, and the molar ratio of the three times of addition of the ethyl formate is controlled to be 1: 0.1;

step S2, adding polyethylene glycol monomethyl ether and acrylic acid into a three-neck flask, heating in a water bath at 45-50 ℃ and magnetically stirring for 30min, then sequentially adding hydroquinone and toluenesulfonic acid, then heating to 100-110 ℃, reacting for 5h in vacuum at the temperature to obtain a primary material, dripping the prepared primary material into a beaker filled with deionized water, controlling the dropping time to be 10min, heating to 80 ℃ after the dropping is finished, sequentially adding sodium allylsulfonate and aqueous solution of ammonium persulfate with the mass fraction of 10%, magnetically stirring and reacting for 6h, then dropwise adding aqueous solution of sodium hydroxide with the mass fraction of 15% to adjust the pH until the pH is =7-8, and preparing a copolymer, wherein the weight ratio of polyethylene glycol monomethyl ether, acrylic acid, hydroquinone and toluenesulfonic acid is controlled to be 4: 3: 2, the weight ratio of sodium allylsulfonate and ammonium persulfate is 10: 0.1, and the weight sum of the sodium allylsulfonate and the ammonium persulfate is 10% of the initial material weight;

and step S3, uniformly mixing the prepared intermediate 1 and the copolymer according to the weight ratio of 3: 1 to prepare the main agent.

4. The water-soluble rubber-plastic regenerated plasticizing softener according to claim 1, characterized in that the water-soluble particles are prepared by the following method:

step S11, adding carrageenan into a beaker filled with deionized water, heating in a water bath at 60-80 ℃ and magnetically stirring until the carrageenan is dissolved, performing suction filtration to prepare a carrageenan solution, dropwise adding a barium chloride solution with the concentration of 0.5mol/L into the carrageenan solution, controlling the dropwise adding time to be 5min, uniformly mixing after the dropwise adding is finished, performing suction filtration, washing a suction filtration product for three times by using absolute ethyl alcohol to prepare the carrageenan after primary treatment, and controlling the dosage ratio of the carrageenan, the deionized water and the barium chloride solution to be 5 g: 500 mL: 0.2 g;

step S12, adding the carrageenan after the primary treatment into deionized water, heating in a water bath at 60-80 ℃ and magnetically stirring until the carrageenan is dissolved, adding a 5% hydrogen peroxide aqueous solution by mass fraction, cooling to 50 ℃ after the carrageenan is completely added, preserving heat for 4 hours at the temperature, then dropwise adding a 10% sodium hydroxide aqueous solution by mass fraction to adjust the pH until the system is neutral, performing rotary evaporation, suction filtration and drying to obtain the carrageenan after the treatment, and controlling the dosage ratio of the carrageenan after the primary treatment, the deionized water and the hydrogen peroxide aqueous solution to be 5 g: 100 mL: 500 mL;

step S13, adding the processed carrageenan and aluminum tripolyphosphate into a three-neck flask, adding N, N-dimethylformamide, magnetically stirring at the rotation speed of 150 plus 200r/min for 30min, heating to 45-60 ℃, adding phosphorus pentoxide, stirring at a constant speed at the temperature, reacting for 4h to obtain a reaction liquid, performing suction filtration on the reaction liquid to obtain a filter cake, performing vacuum drying at 50 ℃ for 10h to obtain water-soluble particles, and controlling the dosage ratio of the processed carrageenan, the aluminum tripolyphosphate, the N, N-dimethylformamide and the phosphorus pentoxide to be 2 g: 2.5 g: 100 mL: 1 g.

5. The preparation method of the water-soluble rubber-plastic regenerated plasticizing softener according to claim 1, characterized by comprising the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50-80r/min, and then preserving heat at 90-100 ℃ for later use;

and secondly, adding the emulsifier into deionized water, adding the emulsifier into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100-150r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

Technical Field

The invention belongs to the field of development and utilization of waste resources, and particularly relates to a water-soluble rubber-plastic regeneration plasticizing softener and a preparation method thereof.

Background

The current methods for producing reclaimed rubber mainly comprise two methods: one is the traditional high-temperature high-pressure dynamic desulfurization method; the other method is a normal-pressure high-temperature twin-screw plasticizing desulfurization method which is just in a popularization state, and the two processes both need to use a regenerated plasticizing softener.

The currently used regeneration plasticizing softener is mainly prepared from coal tar (liquid at normal temperature and solid at normal temperature), pine tar, aromatic oil, tall oil, mixed aromatic oil, tasteless pine tar and other raw materials, and the rubber regeneration plasticizing softener has the main characteristics of low price, good softening effect and partial auxiliary desulfurization effect. However, most raw materials are derived from byproducts of other product production, and the difference of regions, the difference of individual manufacturers and the influence of production batches cause the great difference of the internal components and the composition structure of the softeners, so that the softeners are lack of standards; and the second one is that the controllability of secondary pollution generated in the rubber high-temperature, high-pressure regeneration and plasticizing processes is poor because the internal components of most byproducts have great uncertainty.

However, the plasticizing softener used in the market at present cannot soften rubber and plastic products and has good water solubility, so that the application field of the rubber and plastic products is influenced.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a water-soluble rubber-plastic regeneration plasticizing softener and a preparation method thereof.

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

a water-soluble rubber-plastic regeneration plasticizing softener comprises the following raw materials in parts by weight: 35-50 parts of main agent, 5-10 parts of water-soluble particles, 10-15 parts of petroleum resin, 25-35 parts of deionized water and 1-3 parts of emulsifier;

the water-soluble rubber-plastic regeneration plasticizing softener comprises the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50-80r/min, and then preserving heat at 90-100 ℃ for later use;

and secondly, adding the emulsifier into deionized water, adding the emulsifier into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100-150r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

Further, the emulsifier is petroleum sodium sulfonate.

Further, the main agent is prepared by the following steps:

step S1, adding methyldiethanolamine into a four-neck flask, placing the flask in a water bath at 10-25 ℃, standing for 15min, uniformly stirring, dropwise adding ethyl formate, controlling the dropwise adding time to be 10min, heating to 60 ℃ after the dropwise adding is finished, stirring at constant speed at the temperature, reacting for 2h, tracking the reaction process with thin layer chromatography during the reaction process, distilling under reduced pressure to remove generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 deg.C, stirring at constant speed at the temperature, reacting for 1h, distilling under reduced pressure, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 deg.C, stirring at constant speed at the temperature and reacting for 0.5h to prepare an intermediate 1, wherein the molar ratio of the total amount of the methyldiethanolamine to the ethyl formate is controlled to be 1: 1.2, and the molar ratio of the three times of addition of the ethyl formate is controlled to be 1: 0.1;

step S2, adding polyethylene glycol monomethyl ether and acrylic acid into a three-neck flask, heating in a water bath at 45-50 ℃ and magnetically stirring for 30min, then sequentially adding hydroquinone and toluenesulfonic acid, then heating to 100-110 ℃, reacting for 5h in vacuum at the temperature to obtain a primary material, dripping the prepared primary material into a beaker filled with deionized water, controlling the dropping time to be 10min, heating to 80 ℃ after the dropping is finished, sequentially adding sodium allylsulfonate and aqueous solution of ammonium persulfate with the mass fraction of 10%, magnetically stirring and reacting for 6h, then dropwise adding aqueous solution of sodium hydroxide with the mass fraction of 15% to adjust the pH until the pH is 7-8, and preparing a copolymer, wherein the weight ratio of polyethylene glycol monomethyl ether, acrylic acid, hydroquinone and toluenesulfonic acid is controlled to be 4: 3: 2, the weight ratio of sodium allylsulfonate and ammonium persulfate is 10: 0.1, and the weight sum of the sodium allylsulfonate and the ammonium persulfate is 10% of the weight of the initial material;

and step S3, uniformly mixing the prepared intermediate 1 and the copolymer according to the weight ratio of 3: 1 to prepare the main agent.

Mixing methyldiethanolamine and ethyl formate in step S1, reacting the methyldiethanolamine and the ethyl formate to generate an intermediate 1, wherein the intermediate 1 is actually hydroxyalkyl formamide, the method does not need to add a solvent and a catalyst in a batch feeding mode, has simple and environment-friendly production process, can mix the prepared intermediate 1 with water and play a role in plasticizing and softening rubber and plastic products, mixing polyethylene glycol monomethyl ether and acrylic acid in step S2, adding hydroquinone as a polymerization inhibitor, reacting the polyethylene glycol monomethyl ether and the acrylic acid to synthesize a macromonomer, then copolymerizing the macromonomer with the acrylic acid to generate a copolymer, the copolymer contains the side chain of the polyethylene glycol monomethyl ether, further endowing the prepared polymer with water solubility, then uniformly mixing the intermediate 1 with the copolymer according to the weight ratio of 3: 1 to prepare a main agent, and the main agent can be dissolved in water, and has excellent plasticizing and softening performance.

Further, the water-soluble particles are prepared by the following method:

step S11, adding carrageenan into a beaker filled with deionized water, heating in a water bath at 60-80 ℃ and magnetically stirring until the carrageenan is dissolved, performing suction filtration to prepare a carrageenan solution, dropwise adding a barium chloride solution with the concentration of 0.5mol/L into the carrageenan solution, controlling the dropwise adding time to be 5min, uniformly mixing after the dropwise adding is finished, performing suction filtration, washing a suction filtration product for three times by using absolute ethyl alcohol to prepare the carrageenan after primary treatment, and controlling the dosage ratio of the carrageenan, the deionized water and the barium chloride solution to be 5 g: 500 mL: 0.2 g;

step S12, adding the carrageenan after the primary treatment into deionized water, heating in a water bath at 60-80 ℃ and magnetically stirring until the carrageenan is dissolved, adding a 5% hydrogen peroxide aqueous solution by mass fraction, cooling to 50 ℃ after the carrageenan is completely added, preserving heat for 4 hours at the temperature, then dropwise adding a 10% sodium hydroxide aqueous solution by mass fraction to adjust the pH until the system is neutral, performing rotary evaporation, suction filtration and drying to obtain the carrageenan after the treatment, and controlling the dosage ratio of the carrageenan after the primary treatment, the deionized water and the hydrogen peroxide aqueous solution to be 5 g: 100 mL: 500 mL;

step S13, adding the processed carrageenan and aluminum tripolyphosphate into a three-neck flask, adding N, N-dimethylformamide, magnetically stirring at the rotation speed of 150 plus 200r/min for 30min, heating to 45-60 ℃, adding phosphorus pentoxide, stirring at a constant speed at the temperature, reacting for 4h to obtain a reaction liquid, performing suction filtration on the reaction liquid to obtain a filter cake, performing vacuum drying at 50 ℃ for 10h to obtain water-soluble particles, and controlling the dosage ratio of the processed carrageenan, the aluminum tripolyphosphate, the N, N-dimethylformamide and the phosphorus pentoxide to be 2 g: 2.5 g: 100 mL: 1 g.

The carrageenan is used as a bio-based material, has excellent water absorption and retention, is suitable for bridges of aqueous matrixes and insoluble fillers, is subjected to primary treatment in step S11 and then is classified, is degraded in deionized water in step S12 through 5% aqueous hydrogen peroxide, and is added with N, N-dimethylformamide in step S13, and is subjected to chemical reaction in the preparation process, so that water-soluble particles are prepared, and the technical problem that the filler particles are insoluble in water is solved.

A preparation method of a water-soluble rubber-plastic regeneration plasticizing softener comprises the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50-80r/min, and then preserving heat at 90-100 ℃ for later use;

and secondly, adding the emulsifier into deionized water, adding the emulsifier into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100-150r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

The invention has the beneficial effects that:

(1) the invention relates to a water-soluble rubber-plastic regeneration plasticizing softener, which takes a main agent, water-soluble particles and the like as raw materials, wherein the main agent is prepared by mixing methyldiethanolamine and ethyl formate in step S1 and reacting the methyldiethanolamine and the ethyl formate to generate an intermediate 1, wherein the intermediate 1 is actually hydroxyalkyl formamide, the water-soluble rubber-plastic regeneration plasticizing softener is prepared by adding the solvent and the catalyst in batches without adding solvents and catalysts, the production process is simple and environment-friendly, the prepared intermediate 1 can be mixed with water and can play a plasticizing and softening role on rubber-plastic products, polyethylene glycol monomethyl ether and acrylic acid are mixed in step S2, hydroquinone is added as a polymerization inhibitor, the polyethylene glycol monomethyl ether and the acrylic acid react to synthesize a macromonomer, and then the macromonomer can be copolymerized with the acrylic acid to generate a copolymer which contains the side chain of the polyethylene glycol monomethyl ether and can further endow the prepared polymer with water solubility, and then uniformly mixing the intermediate 1 and the copolymer according to the weight ratio of 3: 1 to prepare a main agent, wherein the main agent can be dissolved in water and has excellent plasticizing and softening properties.

(2) The invention also prepares water-soluble particles, in the preparation process, after the carrageenan is subjected to primary treatment in step S11, the carrageenan is classified, then in step S12, the carrageenan subjected to primary treatment is degraded in deionized water through 5% aqueous hydrogen peroxide, and finally in step S13, the carrageenan and the aluminum tripolyphosphate subjected to the treatment are added into N, N-dimethylformamide, and the carrageenan and the aluminum tripolyphosphate subjected to the treatment in the preparation process are subjected to chemical reaction to prepare the water-soluble particles, so that the technical problem that the filler particles are insoluble in water is solved.

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

A water-soluble rubber-plastic regeneration plasticizing softener comprises the following raw materials in parts by weight: 35 parts of main agent, 5 parts of water-soluble particles, 10 parts of petroleum resin, 25 parts of deionized water and 1 part of petroleum sodium sulfonate;

the water-soluble rubber-plastic regeneration plasticizing softener comprises the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50r/min, and then preserving heat at 90 ℃ for later use;

and secondly, adding the petroleum sodium sulfonate into deionized water, adding the petroleum sodium sulfonate into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

The main agent is prepared by the following steps:

step S1, adding methyldiethanolamine into a four-neck flask, placing the four-neck flask in a 10 ℃ water bath, standing for 15min, uniformly stirring and dropwise adding ethyl formate, controlling the dropwise adding time to be 10min, heating to 60 ℃ after dropwise adding, uniformly stirring and reacting for 2h at the temperature, tracking the reaction process by using a thin-layer chromatography in the reaction process, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 1h at the temperature, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 0.5h at the temperature to obtain an intermediate 1, controlling the molar ratio of the total amount of the methyldiethanolamine to the ethyl formate to be 1: 1.2, and controlling the molar ratio of the ethyl formate to be 1: 0.1;

step S2, adding polyethylene glycol monomethyl ether and acrylic acid into a three-neck flask, heating in a water bath at 45 ℃ and magnetically stirring for 30min, then sequentially adding hydroquinone and toluenesulfonic acid, then heating to 100 ℃, reacting for 5h in vacuum at the temperature to obtain a primary material, dripping the prepared primary material into a beaker filled with deionized water, controlling the dropping time to be 10min, heating to 80 ℃ after the dropping is finished, sequentially adding sodium allylsulfonate and aqueous solution of ammonium persulfate with the mass fraction of 10%, magnetically stirring and reacting for 6h, then dropwise adding aqueous solution of sodium hydroxide with the mass fraction of 15% to adjust the pH until the pH is 7, and preparing a copolymer, wherein the weight ratio of polyethylene glycol monomethyl ether, acrylic acid, hydroquinone and toluenesulfonic acid is controlled to be 4: 3: 2, the weight ratio of sodium allylsulfonate and ammonium persulfate is 10: 0.1, and the weight sum of the sodium allylsulfonate and the ammonium persulfate is 10% of the initial material weight;

and step S3, uniformly mixing the prepared intermediate 1 and the copolymer according to the weight ratio of 3: 1 to prepare the main agent.

The water-soluble particles are prepared by the following method:

step S11, adding carrageenan into a beaker filled with deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, performing suction filtration to prepare a carrageenan solution, dropwise adding a barium chloride solution with the concentration of 0.5mol/L into the carrageenan solution, controlling the dropwise adding time to be 5min, uniformly mixing after the dropwise adding is finished, performing suction filtration, washing a suction filtration product for three times by using absolute ethyl alcohol to prepare the carrageenan after primary treatment, and controlling the dosage ratio of the carrageenan, the deionized water and the barium chloride solution to be 5 g: 500 mL: 0.2 g;

step S12, adding the carrageenan after the primary treatment into deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, adding a 5% aqueous hydrogen peroxide solution, cooling to 50 ℃ after complete addition, preserving heat for 4 hours at the temperature, then dropwise adding a 10% aqueous sodium hydroxide solution to adjust the pH until the system is neutral, performing rotary evaporation, suction filtration and drying to obtain the carrageenan after the treatment, and controlling the dosage ratio of the carrageenan after the primary treatment, the deionized water and the aqueous hydrogen peroxide solution to be 5 g: 100 mL: 500 mL;

step S13, adding the processed carrageenan and aluminum tripolyphosphate into a three-neck flask, adding N, N-dimethylformamide, magnetically stirring at a rotating speed of 150r/min for 30min, heating to 45 ℃, adding phosphorus pentoxide, stirring at a constant speed at the temperature, reacting for 4h to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filter cake, carrying out vacuum drying at 50 ℃ for 10h to obtain water-soluble particles, and controlling the dosage ratio of the processed carrageenan, the aluminum tripolyphosphate, the N, N-dimethylformamide and the phosphorus pentoxide to be 2 g: 2.5 g: 100 mL: 1 g.

Example 2

A water-soluble rubber-plastic regeneration plasticizing softener comprises the following raw materials in parts by weight: 40 parts of main agent, 8 parts of water-soluble particles, 12 parts of petroleum resin, 28 parts of deionized water and 2 parts of petroleum sodium sulfonate;

the water-soluble rubber-plastic regeneration plasticizing softener comprises the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50r/min, and then preserving heat at 90 ℃ for later use;

and secondly, adding the petroleum sodium sulfonate into deionized water, adding the petroleum sodium sulfonate into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

The main agent is prepared by the following steps:

step S1, adding methyldiethanolamine into a four-neck flask, placing the four-neck flask in a 10 ℃ water bath, standing for 15min, uniformly stirring and dropwise adding ethyl formate, controlling the dropwise adding time to be 10min, heating to 60 ℃ after dropwise adding, uniformly stirring and reacting for 2h at the temperature, tracking the reaction process by using a thin-layer chromatography in the reaction process, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 1h at the temperature, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 0.5h at the temperature to obtain an intermediate 1, controlling the molar ratio of the total amount of the methyldiethanolamine to the ethyl formate to be 1: 1.2, and controlling the molar ratio of the ethyl formate to be 1: 0.1;

step S2, adding polyethylene glycol monomethyl ether and acrylic acid into a three-neck flask, heating in a water bath at 45 ℃ and magnetically stirring for 30min, then sequentially adding hydroquinone and toluenesulfonic acid, then heating to 100 ℃, reacting for 5h in vacuum at the temperature to obtain a primary material, dripping the prepared primary material into a beaker filled with deionized water, controlling the dropping time to be 10min, heating to 80 ℃ after the dropping is finished, sequentially adding sodium allylsulfonate and aqueous solution of ammonium persulfate with the mass fraction of 10%, magnetically stirring and reacting for 6h, then dropwise adding aqueous solution of sodium hydroxide with the mass fraction of 15% to adjust the pH until the pH is 7, and preparing a copolymer, wherein the weight ratio of polyethylene glycol monomethyl ether, acrylic acid, hydroquinone and toluenesulfonic acid is controlled to be 4: 3: 2, the weight ratio of sodium allylsulfonate and ammonium persulfate is 10: 0.1, and the weight sum of the sodium allylsulfonate and the ammonium persulfate is 10% of the initial material weight;

and step S3, uniformly mixing the prepared intermediate 1 and the copolymer according to the weight ratio of 3: 1 to prepare the main agent.

The water-soluble particles are prepared by the following method:

step S11, adding carrageenan into a beaker filled with deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, performing suction filtration to prepare a carrageenan solution, dropwise adding a barium chloride solution with the concentration of 0.5mol/L into the carrageenan solution, controlling the dropwise adding time to be 5min, uniformly mixing after the dropwise adding is finished, performing suction filtration, washing a suction filtration product for three times by using absolute ethyl alcohol to prepare the carrageenan after primary treatment, and controlling the dosage ratio of the carrageenan, the deionized water and the barium chloride solution to be 5 g: 500 mL: 0.2 g;

step S12, adding the carrageenan after the primary treatment into deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, adding a 5% aqueous hydrogen peroxide solution, cooling to 50 ℃ after complete addition, preserving heat for 4 hours at the temperature, then dropwise adding a 10% aqueous sodium hydroxide solution to adjust the pH until the system is neutral, performing rotary evaporation, suction filtration and drying to obtain the carrageenan after the treatment, and controlling the dosage ratio of the carrageenan after the primary treatment, the deionized water and the aqueous hydrogen peroxide solution to be 5 g: 100 mL: 500 mL;

step S13, adding the processed carrageenan and aluminum tripolyphosphate into a three-neck flask, adding N, N-dimethylformamide, magnetically stirring at a rotating speed of 150r/min for 30min, heating to 45 ℃, adding phosphorus pentoxide, stirring at a constant speed at the temperature, reacting for 4h to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filter cake, carrying out vacuum drying at 50 ℃ for 10h to obtain water-soluble particles, and controlling the dosage ratio of the processed carrageenan, the aluminum tripolyphosphate, the N, N-dimethylformamide and the phosphorus pentoxide to be 2 g: 2.5 g: 100 mL: 1 g.

Example 3

A water-soluble rubber-plastic regeneration plasticizing softener comprises the following raw materials in parts by weight: 45 parts of main agent, 8 parts of water-soluble particles, 14 parts of petroleum resin, 30 parts of deionized water and 2 parts of petroleum sodium sulfonate;

the water-soluble rubber-plastic regeneration plasticizing softener comprises the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50r/min, and then preserving heat at 90 ℃ for later use;

and secondly, adding the petroleum sodium sulfonate into deionized water, adding the petroleum sodium sulfonate into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

The main agent is prepared by the following steps:

step S1, adding methyldiethanolamine into a four-neck flask, placing the four-neck flask in a 10 ℃ water bath, standing for 15min, uniformly stirring and dropwise adding ethyl formate, controlling the dropwise adding time to be 10min, heating to 60 ℃ after dropwise adding, uniformly stirring and reacting for 2h at the temperature, tracking the reaction process by using a thin-layer chromatography in the reaction process, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 1h at the temperature, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 0.5h at the temperature to obtain an intermediate 1, controlling the molar ratio of the total amount of the methyldiethanolamine to the ethyl formate to be 1: 1.2, and controlling the molar ratio of the ethyl formate to be 1: 0.1;

step S2, adding polyethylene glycol monomethyl ether and acrylic acid into a three-neck flask, heating in a water bath at 45 ℃ and magnetically stirring for 30min, then sequentially adding hydroquinone and toluenesulfonic acid, then heating to 100 ℃, reacting for 5h in vacuum at the temperature to obtain a primary material, dripping the prepared primary material into a beaker filled with deionized water, controlling the dropping time to be 10min, heating to 80 ℃ after the dropping is finished, sequentially adding sodium allylsulfonate and aqueous solution of ammonium persulfate with the mass fraction of 10%, magnetically stirring and reacting for 6h, then dropwise adding aqueous solution of sodium hydroxide with the mass fraction of 15% to adjust the pH until the pH is 7, and preparing a copolymer, wherein the weight ratio of polyethylene glycol monomethyl ether, acrylic acid, hydroquinone and toluenesulfonic acid is controlled to be 4: 3: 2, the weight ratio of sodium allylsulfonate and ammonium persulfate is 10: 0.1, and the weight sum of the sodium allylsulfonate and the ammonium persulfate is 10% of the initial material weight;

and step S3, uniformly mixing the prepared intermediate 1 and the copolymer according to the weight ratio of 3: 1 to prepare the main agent.

The water-soluble particles are prepared by the following method:

step S11, adding carrageenan into a beaker filled with deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, performing suction filtration to prepare a carrageenan solution, dropwise adding a barium chloride solution with the concentration of 0.5mol/L into the carrageenan solution, controlling the dropwise adding time to be 5min, uniformly mixing after the dropwise adding is finished, performing suction filtration, washing a suction filtration product for three times by using absolute ethyl alcohol to prepare the carrageenan after primary treatment, and controlling the dosage ratio of the carrageenan, the deionized water and the barium chloride solution to be 5 g: 500 mL: 0.2 g;

step S12, adding the carrageenan after the primary treatment into deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, adding a 5% aqueous hydrogen peroxide solution, cooling to 50 ℃ after complete addition, preserving heat for 4 hours at the temperature, then dropwise adding a 10% aqueous sodium hydroxide solution to adjust the pH until the system is neutral, performing rotary evaporation, suction filtration and drying to obtain the carrageenan after the treatment, and controlling the dosage ratio of the carrageenan after the primary treatment, the deionized water and the aqueous hydrogen peroxide solution to be 5 g: 100 mL: 500 mL;

step S13, adding the processed carrageenan and aluminum tripolyphosphate into a three-neck flask, adding N, N-dimethylformamide, magnetically stirring at a rotating speed of 150r/min for 30min, heating to 45 ℃, adding phosphorus pentoxide, stirring at a constant speed at the temperature, reacting for 4h to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filter cake, carrying out vacuum drying at 50 ℃ for 10h to obtain water-soluble particles, and controlling the dosage ratio of the processed carrageenan, the aluminum tripolyphosphate, the N, N-dimethylformamide and the phosphorus pentoxide to be 2 g: 2.5 g: 100 mL: 1 g.

Example 4

A water-soluble rubber-plastic regeneration plasticizing softener comprises the following raw materials in parts by weight: 50 parts of a main agent, 10 parts of water-soluble particles, 15 parts of petroleum resin, 35 parts of deionized water and 3 parts of petroleum sodium sulfonate;

the water-soluble rubber-plastic regeneration plasticizing softener comprises the following steps:

firstly, adding petroleum resin into a reaction kettle for heating and melting, magnetically stirring at a rotating speed of 50r/min, and then preserving heat at 90 ℃ for later use;

and secondly, adding the petroleum sodium sulfonate into deionized water, adding the petroleum sodium sulfonate into the melted petroleum resin after complete dissolution, magnetically stirring at the rotating speed of 100r/min, sequentially adding the main agent and the water-soluble particles, and continuously stirring for 30min to obtain the water-soluble rubber-plastic regenerated plasticizing softener.

The main agent is prepared by the following steps:

step S1, adding methyldiethanolamine into a four-neck flask, placing the four-neck flask in a 10 ℃ water bath, standing for 15min, uniformly stirring and dropwise adding ethyl formate, controlling the dropwise adding time to be 10min, heating to 60 ℃ after dropwise adding, uniformly stirring and reacting for 2h at the temperature, tracking the reaction process by using a thin-layer chromatography in the reaction process, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 1h at the temperature, then carrying out reduced pressure distillation, removing generated ethanol, cooling to room temperature, adding ethyl formate again, heating to 60 ℃, uniformly stirring and reacting for 0.5h at the temperature to obtain an intermediate 1, controlling the molar ratio of the total amount of the methyldiethanolamine to the ethyl formate to be 1: 1.2, and controlling the molar ratio of the ethyl formate to be 1: 0.1;

step S2, adding polyethylene glycol monomethyl ether and acrylic acid into a three-neck flask, heating in a water bath at 45 ℃ and magnetically stirring for 30min, then sequentially adding hydroquinone and toluenesulfonic acid, then heating to 100 ℃, reacting for 5h in vacuum at the temperature to obtain a primary material, dripping the prepared primary material into a beaker filled with deionized water, controlling the dropping time to be 10min, heating to 80 ℃ after the dropping is finished, sequentially adding sodium allylsulfonate and aqueous solution of ammonium persulfate with the mass fraction of 10%, magnetically stirring and reacting for 6h, then dropwise adding aqueous solution of sodium hydroxide with the mass fraction of 15% to adjust the pH until the pH is 7, and preparing a copolymer, wherein the weight ratio of polyethylene glycol monomethyl ether, acrylic acid, hydroquinone and toluenesulfonic acid is controlled to be 4: 3: 2, the weight ratio of sodium allylsulfonate and ammonium persulfate is 10: 0.1, and the weight sum of the sodium allylsulfonate and the ammonium persulfate is 10% of the initial material weight;

and step S3, uniformly mixing the prepared intermediate 1 and the copolymer according to the weight ratio of 3: 1 to prepare the main agent.

The water-soluble particles are prepared by the following method:

step S11, adding carrageenan into a beaker filled with deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, performing suction filtration to prepare a carrageenan solution, dropwise adding a barium chloride solution with the concentration of 0.5mol/L into the carrageenan solution, controlling the dropwise adding time to be 5min, uniformly mixing after the dropwise adding is finished, performing suction filtration, washing a suction filtration product for three times by using absolute ethyl alcohol to prepare the carrageenan after primary treatment, and controlling the dosage ratio of the carrageenan, the deionized water and the barium chloride solution to be 5 g: 500 mL: 0.2 g;

step S12, adding the carrageenan after the primary treatment into deionized water, heating in a water bath at 60 ℃ and magnetically stirring until the carrageenan is dissolved, adding a 5% aqueous hydrogen peroxide solution, cooling to 50 ℃ after complete addition, preserving heat for 4 hours at the temperature, then dropwise adding a 10% aqueous sodium hydroxide solution to adjust the pH until the system is neutral, performing rotary evaporation, suction filtration and drying to obtain the carrageenan after the treatment, and controlling the dosage ratio of the carrageenan after the primary treatment, the deionized water and the aqueous hydrogen peroxide solution to be 5 g: 100 mL: 500 mL;

step S13, adding the processed carrageenan and aluminum tripolyphosphate into a three-neck flask, adding N, N-dimethylformamide, magnetically stirring at a rotating speed of 150r/min for 30min, heating to 45 ℃, adding phosphorus pentoxide, stirring at a constant speed at the temperature, reacting for 4h to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filter cake, carrying out vacuum drying at 50 ℃ for 10h to obtain water-soluble particles, and controlling the dosage ratio of the processed carrageenan, the aluminum tripolyphosphate, the N, N-dimethylformamide and the phosphorus pentoxide to be 2 g: 2.5 g: 100 mL: 1 g.

Comparative example 1

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

Comparative example 2

This comparative example compares to example 1 without the addition of water soluble particles.

Comparative example 3

This comparative example is a plasticizing softener in the market.

Adding plasticizing softening agents of examples 1-4 and comparative examples 1-3 into rubber powder in sequence, adding rubber activating agents in sequence, transferring the rubber powder into a devulcanizer, carrying out devulcanization regeneration at high temperature and high pressure, carrying out devulcanization pressure of 2.5MPa, and carrying out heat preservation for 30min to obtain reclaimed rubbers of examples 1-4 and comparative examples 1-3, and measuring tensile strength and elongation according to GB/T3686-1998;

as can be seen from the above table, the tensile strengths of examples 1-4 were 15.2-15.5MPa, the tensile strengths of comparative examples 1-3 were 14.6-15.0MPa, the elongations of examples 1-4 were 385% and those of comparative examples 1-3 were 350% and 310-.

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.