阅读说明：本技术 一种共晶溶剂及其制备方法和应用、聚苯乙烯马来酸酐溶液及其制备方法和应用 (Eutectic solvent, preparation method and application thereof, polystyrene maleic anhydride solution, and preparation method and application thereof ) 是由 王顺平 冯练享 白清泉 于 2021-01-06 设计创作，主要内容包括：本发明提供了一种共晶溶剂及其制备方法和应用、聚苯乙烯马来酸酐溶液及其制备方法和应用,属于有机合成技术领域。本发明的共晶溶剂由包括以下重量份的原料制备得到：氯化胆碱100～200份、尿素0～120份、马来酸酐50～150份。本发明采用共晶溶剂制备聚苯乙烯马来酸酐,可避免使用有毒有害的有机溶剂,对环境友好,制备得到的聚苯乙烯马来酸酐溶液可直接用来制备皮革鞣剂,无需分离。(The invention provides a eutectic solvent, a preparation method and application thereof, a polystyrene maleic anhydride solution, a preparation method and application thereof, and belongs to the technical field of organic synthesis. The eutectic solvent is prepared from the following raw materials in parts by weight: 100-200 parts of choline chloride, 0-120 parts of urea and 50-150 parts of maleic anhydride. The method adopts the eutectic solvent to prepare the polystyrene maleic anhydride, can avoid using toxic and harmful organic solvents, is environment-friendly, and can directly prepare the leather tanning agent without separation.)

1. The eutectic solvent is characterized by being prepared from the following raw materials in parts by weight:

100-200 parts of choline chloride, 0-120 parts of urea and 50-150 parts of maleic anhydride.

2. A method of preparing the co-crystal solvent of claim 1, comprising the steps of: adding the preparation raw materials into a reactor, heating to 20-50 ℃, and stirring until the materials are completely melted into liquid to obtain the eutectic solvent.

3. Use of the eutectic solvent according to claim 1 or the eutectic solvent prepared by the preparation method according to claim 2 in the preparation of polystyrene maleic anhydride.

4. The preparation method of the polystyrene maleic anhydride solution is characterized by comprising the following steps:

dissolving an initiator in styrene to obtain a mixed solution;

heating the eutectic solvent to 70-120 ℃, and adding the mixed solution into the heated eutectic solvent for copolymerization reaction to obtain a polystyrene maleic anhydride solution;

the eutectic solvent is the eutectic solvent as defined in claim 1 or the eutectic solvent prepared by the preparation method as defined in claim 2.

5. The method of claim 4, wherein the initiator comprises one or more of benzoyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile; the mass ratio of the maleic anhydride to the initiator in the eutectic solvent is (50-100): 1.

6. The preparation method according to claim 4, wherein the mass ratio of the maleic anhydride to the styrene in the eutectic solvent is 98 (100-110).

7. The method according to claim 4, wherein the copolymerization is carried out for 1 to 4 hours.

8. The solution of polystyrene maleic anhydride prepared by the preparation method of any one of claims 4 to 7, which comprises polystyrene maleic anhydride and choline chloride.

9. Use of a polystyrene maleic anhydride solution according to claim 8 for the preparation of a leather tanning agent; the preparation method of the leather tanning agent comprises the following steps:

adding an alkalizer to the polystyrene maleic anhydride solution of claim 8 to carry out saponification to obtain a saponified product;

and adding water into the saponified product to obtain the leather tanning agent.

10. The use according to claim 9, wherein the saponification is carried out at a temperature of 40 to 60 ℃ for 1 to 5 hours;

the alkalizer comprises one or more of ammonia water, sodium hydroxide, potassium hydroxide, ammonia water, monoethanolamine, diethanolamine and triethanolamine; the mass ratio of the maleic anhydride to the alkalizer is 98 (15-100).

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a eutectic solvent, a preparation method and application thereof, a polystyrene maleic anhydride solution, a preparation method and application thereof.

Background

Styrene-Maleic Anhydride copolymers are important copolymers with excellent heat resistance, rigidity and dimensional stability. The anhydride functional group contained in the main chain can react with active groups such as hydroxyl, amino and the like to form a series of functional derivatives, so that the functional derivatives are widely applied to the fields of latex paint, water treatment agents, modifiers of adhesives, emulsifiers of pesticides, dispersing agents of pigments, textile assistants, leather tanning agents, printing ink, composite materials, curing agents of epoxy resins and the like.

According to the monomer structure, the maleic anhydride monomer structure is symmetrical and is difficult to self-polymerize, an electron-withdrawing group enables double bonds to have partial positive charges, styrene has benzene rings capable of enabling electrons to be conjugated, partial negative charges can be obtained through induction of the double bonds, and the two monomers with similar activities but opposite polarities are easy to alternately copolymerize. The synthesis method mainly comprises a homogeneous phase method and a heterogeneous phase method, wherein the homogeneous phase method mainly takes ketones such as acetone, butanone and the like as reaction media, reaction monomers, initiators and polymerization products are all dissolved in the media, and finally the polymerization products are separated by a precipitation segregation method; the heterogeneous method is a commonly used SMA synthesis method, because the monomer can be dissolved in toluene and the polymerization product cannot be dissolved in toluene, the heterogeneous method is called heterogeneous method, and the heterogeneous method has the advantages that the product is precipitated in the reaction process, the post-treatment process is simple and convenient, and the copolymer composition is easy to adjust. In either method, an organic solvent is required, which is not favorable for environmental protection.

When two monomers of styrene and maleic anhydride are polymerized in equal molar, an alternating SMA copolymer is formed, wherein the styrene with weak polarity and the maleic anhydride with strong polarity enable the styrene with weak polarity and the maleic anhydride with strong polarity to have obvious amphiphilic property, and the styrene with weak polarity and the maleic anhydride are compatible with hydrophobic materials and hydrophilic materials, so that the styrene and the maleic anhydride can be blended, hybridized and coated with a plurality of organic and inorganic functional materials to form a composite functional material. In either method, an organic solvent is required, which is not favorable for environmental protection. Polystyrene maleic anhydride used in the leather industry is a water-soluble product, and is generally used after solid polymer particles are swollen with alkali and then adjusted to a suitable content with water.

Disclosure of Invention

The invention aims to provide a eutectic solvent, a preparation method and application thereof, and a polystyrene maleic anhydride solution, a preparation method and application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a eutectic solvent, which is prepared from the following raw materials in parts by weight:

100-200 parts of choline chloride, 0-120 parts of urea and 50-150 parts of maleic anhydride.

The invention provides a preparation method of the eutectic solvent, which comprises the following steps: adding the preparation raw materials into a reactor, heating to 20-50 ℃, and stirring until the materials are completely melted into liquid to obtain the eutectic solvent.

The invention provides an application of the eutectic solvent in the scheme or the eutectic solvent prepared by the preparation method in the scheme in the preparation of polystyrene maleic anhydride.

The invention provides a preparation method of a polystyrene maleic anhydride solution, which comprises the following steps:

dissolving an initiator in styrene to obtain a mixed solution;

heating the eutectic solvent to 70-120 ℃, and adding the mixed solution into the heated eutectic solvent for copolymerization reaction to obtain a polystyrene maleic anhydride solution;

the eutectic solvent is the eutectic solvent described in the above scheme or the eutectic solvent prepared by the preparation method described in the above scheme.

Preferably, the initiator comprises one or more of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile; the mass ratio of the maleic anhydride to the initiator in the eutectic solvent is (50-100): 1.

Preferably, the mass ratio of the maleic anhydride to the styrene in the eutectic solvent is 98 (100-110).

Preferably, the time of the copolymerization reaction is 1 to 4 hours.

The invention provides a polystyrene maleic anhydride solution prepared by the preparation method, which comprises polystyrene maleic anhydride and choline chloride.

The invention provides an application of the solution of the polystyrene and the maleic anhydride in the scheme in preparing a leather tanning agent; the preparation method of the leather tanning agent comprises the following steps:

adding an alkalizer into the polystyrene maleic anhydride solution to carry out saponification reaction to obtain a saponified product;

and adding water into the saponified product to obtain the leather tanning agent.

Preferably, the saponification reaction is carried out at the temperature of 40-60 ℃ for 1-5 hours;

the alkalizer comprises one or more of ammonia water, sodium hydroxide, potassium hydroxide, ammonia water, monoethanolamine, diethanolamine and triethanolamine; the mass ratio of the maleic anhydride to the alkalizer is 98 (15-100).

The invention provides a eutectic solvent, which is prepared from the following raw materials in parts by weight: 100-200 parts of choline chloride, 0-120 parts of urea and 50-150 parts of maleic anhydride. The method adopts the eutectic solvent to prepare the polystyrene maleic anhydride, can avoid using toxic and harmful organic solvents, is environment-friendly, and can directly prepare the leather tanning agent without separation.

Detailed Description

The invention provides a eutectic solvent, which is prepared from the following raw materials in parts by weight:

100-200 parts of choline chloride, 0-120 parts of urea and 50-150 parts of maleic anhydride.

In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.

The eutectic solvent provided by the invention comprises 100-200 parts by weight of choline chloride, preferably 120-150 parts by weight, and more preferably 130-140 parts by weight.

Based on the weight part of choline chloride, the eutectic solvent provided by the invention comprises 0-120 parts of urea, preferably 0-80 parts of urea, and more preferably 0-60 parts of urea.

Based on the weight parts of choline chloride, the eutectic solvent provided by the invention comprises 50-150 parts of maleic anhydride, preferably 70-120 parts of maleic anhydride, and more preferably 90-100 parts of maleic anhydride.

The invention provides a preparation method of the eutectic solvent, which comprises the following steps: adding the preparation raw materials into a reactor, heating to 20-50 ℃, and stirring until the materials are completely melted into liquid to obtain the eutectic solvent.

The present invention does not require any particular speed of agitation, and can employ agitation speeds well known in the art.

The invention provides an application of the eutectic solvent in the scheme or the eutectic solvent prepared by the preparation method in the scheme in the preparation of polystyrene maleic anhydride. When preparing the polystyrene maleic anhydride, the eutectic solvent is used as a solvent, an organic solvent is not required to be additionally used, and the reactant maleic anhydride is provided.

The invention provides a preparation method of polystyrene maleic anhydride, which comprises the following steps:

dissolving an initiator in styrene to obtain a mixed solution;

heating the eutectic solvent to 70-120 ℃, and adding the mixed solution into the heated eutectic solvent for copolymerization reaction to obtain a polystyrene maleic anhydride solution; the eutectic solvent is the eutectic solvent in the scheme.

The invention adds initiator solution into styrene to obtain mixed solution. The present invention has no special requirement on the mixing process, and the mixing process can be uniformly mixed in any manner known in the art. In the present invention, the initiator preferably includes one or more of benzoyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile; when the initiator comprises a plurality of the substances, the proportion of each initiator is not particularly required, and any proportion can be adopted. The amounts of initiator and styrene are specified later.

According to the invention, a eutectic solvent is heated to 70-120 ℃, and the mixed solution is added into the heated eutectic solvent for copolymerization reaction, so as to obtain a polystyrene maleic anhydride solution.

In the invention, the mass ratio of the maleic anhydride to the initiator in the eutectic solvent is preferably (50-100): 1, more preferably (60-90): 1, and even more preferably (70-80): 1.

In the invention, the mass ratio of the maleic anhydride to the styrene in the eutectic solvent is preferably 98 (100-110), and more preferably 98: 104.

In the present invention, the manner of addition is preferably dropwise. The invention has no special requirement on the dropping mode, and the dropping can be carried out dropwise. The invention adopts a dripping mode to be beneficial to the full implementation of the copolymerization reaction.

In the present invention, the time of the copolymerization reaction is preferably 1 to 4 hours, and more preferably 2 to 3 hours. In the present invention, the time of the copolymerization reaction is measured from the completion of the dropwise addition of the mixed solution.

In the copolymerization reaction process, maleic anhydride and styrene in the eutectic solvent are subjected to copolymerization reaction to obtain a polystyrene maleic anhydride copolymer solution.

The invention adopts the eutectic solvent to prepare the polystyrene maleic anhydride, avoids using an organic solvent and is environment-friendly. The polystyrene maleic anhydride solution comprises polystyrene maleic anhydride, choline chloride and urea (if the urea is used in a eutectic solvent), and the leather tanning agent can be directly prepared without separation.

The invention provides a polystyrene maleic anhydride solution prepared by the preparation method in the scheme, which comprises polystyrene maleic anhydride and choline chloride. If the eutectic solvent used contains urea, the polystyrene maleic anhydride solution also contains urea.

The invention provides an application of the solution of the polystyrene and the maleic anhydride in the scheme in preparing a leather tanning agent; the preparation method of the leather tanning agent comprises the following steps:

adding an alkalizer into the polystyrene maleic anhydride solution to carry out saponification reaction to obtain a saponified product;

and adding water into the saponified product to obtain the leather tanning agent.

The invention adds alkalizer into the solution of polystyrene maleic anhydride to carry out saponification reaction, and then saponification product is obtained.

In the present invention, the alkalizer preferably includes one or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, monoethanolamine, diethanolamine and triethanolamine, and more preferably aqueous ammonia.

In the invention, the mass ratio of the maleic anhydride to the alkalizer is preferably 98 (15-100), more preferably 98 (40-80), and even more preferably 98 (50-60), based on the amount of the maleic anhydride, the amount of the polystyrene maleic anhydride.

In the invention, the temperature of the saponification reaction is preferably 40-60 ℃, and more preferably 45-55 ℃; the time of the saponification reaction is preferably 1 to 5 hours, and more preferably 2 to 4 hours. The invention makes the polystyrene maleic anhydride have hydrophilicity through saponification reaction.

In the saponification reaction process, the water solubility of a sample is preferably tested by adding water, and the next step is carried out after the water solubility is judged to be qualified; if the water solubility is not qualified, the saponification reaction time is prolonged until the water solubility is qualified.

After the saponified product is obtained, the invention directly adds water into the saponified product to obtain the leather tanning agent.

In the present invention, the water is preferably added in an amount of 30 to 40% by mass of the solid content by diluting the saponified styrene-maleic anhydride copolymer. In the present invention, the water is preferably distilled water.

The leather tanning agent is prepared by adopting the polystyrene maleic anhydride solution, and the polystyrene maleic anhydride solution contains choline chloride (and urea) which can be used as a leather-making moisturizing and water-retaining auxiliary agent, so that the leather is endowed with good filling performance and foam feeling.

The eutectic solvent, the preparation method and the application thereof, the polystyrene maleic anhydride solution, the preparation method and the application thereof provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.

Example 1

139 parts of choline chloride, 30 parts of urea and 98 parts of maleic anhydride are added into a reactor, heated to 40 ℃, and stirred until all materials are melted into liquid, so that the eutectic solvent is obtained.

Example 2

267 parts of eutectic solvent (containing 98 parts of maleic anhydride) in example 1 was added to a reaction kettle, the temperature was raised to 90 ℃, 1.5 parts of azobisisobutyronitrile was dissolved in 100 parts of styrene, and the solution was added dropwise to the reaction kettle over 3 hours, followed by copolymerization for 3 hours to obtain a polystyrene maleic anhydride solution.

And (3) cooling the polystyrene maleic anhydride solution to 40 ℃, adding 100 parts of ammonia water, stirring for 2 hours to carry out saponification reaction, sampling, adding water to test water solubility, adding 700 parts of distilled water into the reaction kettle after the solution is qualified, and stirring for 1 hour to obtain the leather tanning agent.

Example 3

135 parts of eutectic solvent (including 49 parts of maleic anhydride) in example 1 is added into a reaction kettle, the temperature is raised to 90 ℃, 0.8 part of benzoyl peroxide is dissolved into 55 parts of styrene, the solution is dripped into the reaction kettle for 2 hours, and then copolymerization reaction is carried out for 3 hours, thus obtaining the polystyrene maleic anhydride solution.

And (3) cooling the polystyrene maleic anhydride solution to 40 ℃, adding 25 parts of sodium hydroxide, stirring for 4 hours to carry out saponification reaction, sampling, adding water to test water solubility, adding 400 parts of distilled water into the reaction kettle after the solution is qualified, and stirring for 1 hour to obtain the leather tanning agent.

Example 4

139 parts of choline chloride and 98 parts of maleic anhydride are added into a reactor, heated to 40 ℃, and stirred until the materials are completely melted into liquid, so that the eutectic solvent is obtained.

Example 5

237 parts of eutectic solvent (containing 98 parts of maleic anhydride) in example 4 was added to a reaction kettle, the temperature was raised to 90 ℃, 1 part of azobisisobutyronitrile was dissolved in 100 parts of styrene, and the solution was added dropwise to the reaction kettle over 5 hours, followed by copolymerization for 2 hours to obtain a polystyrene maleic anhydride solution.

And (3) cooling the polystyrene maleic anhydride solution to 40 ℃, adding 60 parts of monoethanolamine, stirring for 2 hours to carry out saponification reaction, sampling, adding water to test water solubility, adding 750 parts of distilled water into the reaction kettle after the solution is qualified, and stirring for 1 hour to obtain the leather tanning agent.

Example 6

118 parts of the eutectic solvent (including 49 parts of maleic anhydride) in example 4 are added into a reaction kettle, the temperature is raised to 120 ℃, 0.9 part of benzoyl peroxide is dissolved into 55 parts of styrene, the solution is dropwise added into the reaction kettle for 2 hours, and then copolymerization reaction is carried out for 5 hours to obtain a polystyrene maleic anhydride solution.

And (3) cooling the polystyrene maleic anhydride solution to 40 ℃, adding 30 parts of potassium hydroxide, stirring for 3 hours to perform saponification reaction, sampling, adding water to test water solubility, adding 500 parts of distilled water into the reaction kettle after the solution is qualified, and stirring for 1 hour to obtain the leather tanning agent.

Performance testing

Taking three pieces of the same parts of the cowhide wet leather, softening, retanning with chromium, operating according to a conventional process, adding the leather tanning agent described in the embodiment 2 and the embodiment 5 in the retanning procedure after draining, adding the acrylic acid retanning agent LEATAN R12 (Qiheqiao chemical Co., Ltd.), each of which accounts for 10% of the weight of the leather, treating the leather in a rotating drum at 40 ℃ for 1.5 hours, draining, adding a fatting agent BUXOMAE-850 (Qiheqiao chemical Co., Ltd.) with the weight of the leather, rotating the leather at 50 ℃ for 1.5 hours, adding 1.2% of formic acid for fixing, finally washing the leather with water, carrying out vacuum drying, and testing the performance of the leather, wherein the results are shown in Table 1.

TABLE 1 leather Properties

Classes of leather tanning agents	Softness	Thickening ratio%	Tear resistance N
				Example 2	1.677	52.3	76.52
Example 5	1.626	50.7	75.17
				Acrylic acid retanning agent R12	1.343	29.7	71.20

In table 1, the softness is tested by using a leather softness tester DY-4023, the thickening rate is tested by using a leather thickness tester XK-3054, the calculation method is the ratio of the difference between the leather greased thickness and the blue wet leather thickness to the blue wet leather thickness, and the tearing resistance is tested by using an electronic tensile tester WDW-50M.

From the results of table 1, it can be seen that the styrene maleic anhydride polymer solution obtained by the present invention has better thickening rate and softness to leather than the conventional acrylic acid retanning agent.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.