Preparation method and application of bulking agent emulsion for solid-phase synthesis

Abstract

The invention belongs to the technical field of bulking agent emulsion preparation, and particularly relates to a preparation method and application of a bulking agent emulsion for solid-phase synthesis, and the preparation method comprises the following steps: S1, pouring an emulsifying body and an emulsifying agent into an emulsifying tank, and stirring at 40-100 DEG C for 1-2 hours to enable the mixture to form a uniform melt; step S2, then controlling the stirring speed to be 100-600rpm, dropwise adding warm water with the temperature of 40-100 DEG C into the molten mixture, and completing dropwise adding within 0.5-1 hour; s3, after dripping is completed, heat preservation stirring continues to be conducted for 1-2 hours, then a mildew preventive is added into the mixture, and finally cooling and packaging are conducted. The technology is simple and convenient, energy consumption is low, and materials are easy to obtain; the product is good in water solubility and high in stability, and is not demulsified or layered when being mixed with strong acid; the product has an excellent loosening effect when being applied to solid powder synthesis, and can effectively prevent materials from caking and pilling, so that the materials can be fully and uniformly dispersed.

Description

Technical Field

[0001] The invention relates to the technical field of loosening agent emulsion preparation, in particular to a preparation method of a loosening agent emulsion for solid phase synthesis and application thereof. Background Art

[0002] Chemical synthesis is an important production method. Various compounds can be mass-produced through chemical synthesis to meet the society's demand for chemicals. Most chemical syntheses require the addition of various additives to achieve rapid and efficient production of products. Although the amount of additives usually accounts for only a small proportion, the lack of additives will lead to a significant increase in production costs or even the inability to obtain corresponding products.

[0003] Traditional liquid phase reactions require the use of a large amount of water as a solvent, which not only increases the cost of production and manufacturing, but also produces a large amount of industrial sewage and wastewater, causing irreversible damage to the environment. Solid phase reactions can solve the problem of using a large amount of water, but usually do not reach the level of reaction of liquid phase reactions, resulting in unqualified products. Various conventional surfactants, such as defoamers, leveling agents, dispersants, etc., are used in solid phase reaction research, but these additives are not ideal due to changes in application conditions and application scenarios, especially in inhibiting the easy agglomeration, difficulty in uniform dispersion, and agglomeration of solid phase reactions. They are almost of no help. Summary of the invention

[0004] The invention provides a method for preparing a loosening agent emulsion for solid phase synthesis, which solves the disadvantages in the prior art that solid powder is easy to agglomerate during chemical synthesis, cannot be dispersed and is uneven, which easily leads to the inability to carry out the reaction.

[0005] The present invention provides the following technical solutions:

[0006] On the one hand, the present application provides a method for preparing a loosening agent emulsion for solid phase synthesis, comprising the following steps:

[0007] Step S1, first pour the emulsified body and the emulsifier into an emulsification tank, and stir at 40-100° C. for 1-2 hours to make the mixture form a uniform melt;

[0008] Step S2, then controlling the stirring speed to 100-600 rpm, adding 40-100° C. warm water to the molten mixture dropwise for 0.5-1 hour;

[0009] Step S3: After the dripping is completed, the mixture is kept warm and stirred for 1-2 hours, and then a mildew inhibitor is added to the mixture, and finally cooled and packaged.

[0010] In a possible embodiment, the emulsified body is one or more of polydimethylsiloxane, polyether-modified silicone oil, and mineral oil, wherein the viscosity range of polydimethylsiloxane is 300-3000mPas, the viscosity range of polyether-modified silicone oil is 300-3000mPas, and the viscosity range of mineral oil is 100-2000mPas.

[0011] In a possible implementation, the emulsifier is at least one of PEG-4000, PEG-6000, PEG-8000, sorbitan monostearate, glycerol polyoxyethylene polyoxypropylene ether, butanol polyoxypropylene ether, and sodium dodecylbenzene sulfonate.

[0012] In a possible implementation, the tank body of the emulsification tank is made of stainless steel or glass, and the stirring paddle of the emulsification tank is an Intermig multi-stage emulsification paddle.

[0013] In a possible implementation manner, the mass ratio of the emulsified body to the emulsifier in the melt is 100:(10-65).

[0014] In a possible implementation manner, the warm water is obtained by heating ordinary tap water, deionized water, or distilled water.

[0015] In a possible implementation, the mildew inhibitor is at least one of chitosan, isothiazolinone, and phenol.

[0016] On the other hand, the present application provides an application of a loosening agent emulsion, wherein the loosening agent emulsion prepared by any of the above-mentioned methods for preparing a loosening agent emulsion for solid phase synthesis is applied to solid powder synthesis.

[0017] It is to be understood that the foregoing general description and the following detailed description are exemplary only and are not restrictive of the invention.

[0018] The present invention has simple process, low energy consumption and easy-to-obtain materials.

[0019] The product of the present invention has good water solubility and high stability, and does not break the emulsion or separate when mixed with strong acid.

[0020] In the present invention, the product has an excellent loosening effect when applied to solid powder synthesis, can effectively prevent the material from agglomerating and pilling, and can make the material fully and evenly dispersed. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Effect of self-made loosening agent emulsion on solid phase synthesis

[0022] Figure 2 Effect of commercial defoamers on solid phase synthesis

[0023] Figure 3 Effect of solid phase synthesis without loosening agent and defoamer DETAILED DESCRIPTION

[0024] In order to realize the preparation and application of the loosening agent for solid phase synthesis of the present invention, a detailed description is given below in conjunction with specific embodiments.

[0025] 1. Preparation of loosening agent emulsion:

[0026] Example 1

[0027] First, pour 1 kg of polydimethylsiloxane and 300 g of emulsifier into a 5 L glass emulsification tank and stir at 65 ° C for 2 hours to make the mixture form a uniform melt;

[0028] The viscosity of polydimethylsiloxane is 1000 mPas, and the emulsifier is composed of 100 g each of PEG-4000, sorbitan monostearate, and glycerol polyoxyethylene polyoxypropylene ether;

[0029] Adjust the stirring speed of the emulsification tank to 300 rpm, add 3 kg of deionized warm water at 65°C to the melt, and add it all in 1 hour. Continue stirring for 1.5 hours after the addition is completed, then add 20 g of isothiazolinone to the mixture, then cool it and put it into a barrel.

[0030] Example 2

[0031] First, pour 1 kg of polyether-modified silicone oil and 450 g of emulsifier into a 5 L glass emulsification tank and stir at 65 ° C for 2 hours to make the mixture form a uniform melt;

[0032] The viscosity of the polyether-modified silicone oil is 1000 mPas, and the emulsifier is composed of 150 g each of PEG-4000, sorbitan monostearate, and sodium dodecylbenzene sulfonate;

[0033] Adjust the stirring speed of the emulsification tank to 350 rpm, add 2.5 kg of deionized warm water at 65°C to the melt, and add it all in 1 hour. Continue stirring for 1.5 hours after the addition is completed, then add 20 g of isothiazolinone to the mixture, then cool it and put it into a barrel.

[0034] Example 3

[0035] First, pour 1 kg of mineral oil and 450 g of emulsifier into a 5 L glass emulsification tank and stir at 80 ° C for 1 hour to make the mixture form a uniform melt;

[0036] The viscosity of the mineral oil is 1500 mPas, and the emulsifier is composed of 150 g each of PEG-6000, sorbitan monostearate, and butanol polyoxypropylene ether;

[0037] Adjust the stirring speed of the emulsification tank to 500 rpm, add 2.8 kg of tap water at 80°C to the melt, and add it all in 1 hour. Continue stirring for 1.5 hours after the addition is completed, then add 20 g of chitosan to the mixture, cool it, and put it into a barrel.

[0038] Example 4

[0039] First, pour 500g of polydimethylsiloxane, 500g of polyether-modified silicone oil and 150g of emulsifier into a 5L glass emulsification tank, and stir at 80°C for 1 hour to make the mixture form a uniform melt;

[0040] The viscosity of polydimethylsiloxane and polyether-modified silicone oil is 400 mPas, and the emulsifier is composed of 50 g each of PEG-8000, glycerol polyoxyethylene polyoxypropylene ether, and sodium dodecylbenzene sulfonate;

[0041] Adjust the stirring speed of the emulsification tank to 450 rpm, add 2.8 kg of warm tap water at 80°C to the melt, and complete the dripping in 1 hour. Continue stirring for 1 hour after the dripping is completed, then add 15 g of phenol to the mixture, then cool and bucket.

[0042] Example 5

[0043] First, pour 600g of polydimethylsiloxane, 400g of mineral oil and 240g of emulsifier into a 5L glass emulsification tank, and stir at 70°C for 1 hour to make the mixture form a uniform melt;

[0044] The viscosity of polydimethylsiloxane is 2000mPas, the viscosity of mineral oil is 500mPas, and the emulsifier is composed of 80g each of sorbitan monostearate, glycerol polyoxyethylene polyoxypropylene ether, and butanol polyoxypropylene ether;

[0045] Adjust the stirring speed of the emulsification tank to 550 rpm, add 2.8 kg of distilled warm water at 70°C to the melt, and complete the addition in 0.5 hour. Continue stirring for 1 hour after the addition is completed, then add 15 g of isothiazolinone to the mixture, then cool and bucket.

[0046] In order to further illustrate the reliability of the method provided by the present invention, the preparation process and the stirring paddle are changed contrary to the present invention as a comparative verification.

[0047] Comparative Example 1

[0048] First, pour 1 kg of polydimethylsiloxane, 300 g of emulsifier, and 3 kg of deionized water into a 5L glass emulsification tank, control the system temperature to 65°C, stir for 4.5 hours, then add 20 g of isothiazolinone to the mixture, then cool and barrel.

[0049] The viscosity of polydimethylsiloxane is 1000 mPas, and the emulsifier is composed of 100 g each of PEG-4000, sorbitan monostearate, and glycerol polyoxyethylene polyoxypropylene ether.

[0050] Comparative Example 2

[0051] First, pour 1 kg of polydimethylsiloxane and 300 g of emulsifier into a 5 L glass emulsification tank and stir at 65 ° C for 2 hours to make the mixture form a uniform melt;

[0052] The viscosity of polydimethylsiloxane is 1000 mPas, and the emulsifier is composed of 100 g each of PEG-4000, sorbitan monostearate, and glycerol polyoxyethylene polyoxypropylene ether;

[0053] Stir with an ordinary double-blade polytetrafluoroethylene stirring rod at a speed of 500 rpm, add 3 kg of deionized warm water at 65°C to the melt, and add it all in 1 hour. Continue stirring for 1.5 hours after the addition is completed, then add 20 g of isothiazolinone to the mixture, then cool and bucket.

[0054] The stability tracking results of the above examples and comparative examples are shown in Table 1. In the stability test with phosphoric acid, phosphoric acid and the sample are prepared at a mass ratio of 1:1.

[0055] Table 1 Stability tracking table of the products of the embodiments and comparative examples

[0056] sample Water Solubility Storage stability Phosphate stability Particle size Example 1 Miscible in any ratio >12 months No stratification in 30 days 600-800nm Example 2 Miscible in any ratio >12 months No stratification in 30 days 630-750nm Example 3 Miscible in any ratio >12 months No stratification in 30 days 550-650nm Example 4 Miscible in any ratio >12 months No stratification in 30 days 400-700nm Example 5 Miscible in any ratio >12 months No stratification in 30 days 580-870nm Comparative Example 1 Oily, immiscible with water After 1 hour, the layers will be separated Layer immediately --- Comparative Example 2 Oily, partially miscible Leave for 3 days to stratify Leave for 1 day to stratify 30-60μm

[0057] It can be found from Table 1 that the loosening agent emulsion for solid phase synthesis prepared by the technical solution provided by the present invention has good water solubility, stability and stability with phosphoric acid, and the main distribution range of its particle size is less than 1 μm.

[0058] On the other hand, the comparative examples showed poor water solubility and stability, and the particle size was much larger than that of Examples 1-5. Among them, comparative example 1 was not emulsified at all, and it was still oil-water two-phase; although comparative example 2 had a certain water solubility, it was extremely unstable and would quickly stratify after being left standing. The two comparative examples illustrate that changing some of the conditions of the present invention may result in failure. 2. Application of loosening agent emulsion:

[0059] Example 1

[0060] Add 20kg of ferrous sulfate heptahydrate and 5.3kg of glycine into a 40-liter mixing tank, start stirring, stir at 800rpm for 2 minutes, then add 2.6kg of auxiliary agent, continue stirring for 30 minutes, stop the reaction, and obtain ferrous glycine product. The reaction process is shown in the attached Figure 1 shown.

[0061] The auxiliary agent is prepared according to the mass ratio of "water: phosphoric acid: loosening agent emulsion = 1.0:0.1:0.2". The loosening agent emulsion is prepared according to the method provided by the present invention.

[0062] Comparative Example 1

[0063] Add 20kg of ferrous sulfate heptahydrate and 5.3kg of glycine into a 40-liter mixing tank, start stirring, stir at 800rpm for 2 minutes, then add 2.6kg of auxiliary agent, continue stirring for 30 minutes, stop the reaction, and obtain ferrous glycine product. The reaction process is shown in the attached Figure 2 shown.

[0064] The auxiliary agent is prepared according to the mass ratio of "water: phosphoric acid: defoamer = 1.0: 0.1: 0.2". The defoamer is commercially available and prepared according to the method provided by invention patents CN102350097B and CN103801119A.

[0065] Comparative Example 2

[0066] Add 20kg of ferrous sulfate heptahydrate and 5.3kg of glycine into a 40-liter mixing tank, start stirring, stir at 800rpm for 2 minutes, then add 2.6kg of auxiliary agent, continue stirring for 30 minutes, stop the reaction, and obtain ferrous glycine product. The reaction process is shown in the attached Figure 3 shown.

[0067] Among them, the additive is prepared according to the mass ratio of "water: phosphoric acid = 1.2:0.1".

[0068] Combined with the accompanying drawings, the above Example 1 and Comparative Example 1 and Comparative Example 2 are analyzed, and it can be found that Figure 1 The product is evenly dispersed without agglomeration or large balls. Figure 2 The presence of obvious large balls indicates uneven dispersion and agglomeration. Figure 3 Then it will agglomerate and clump violently.

[0069] This further illustrates that the loosening agent emulsion for solid phase synthesis prepared by the method provided by the present invention has excellent effect and is suitable for industrial promotion.

[0070] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention; the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A method for preparing a loosening agent emulsion for solid phase synthesis, characterized in that: The steps include: Step S1, first pour the emulsified body and the emulsifier into an emulsification tank, and stir at 40-100° C. for 1-2 hours to make the mixture form a uniform melt; Step S2, then controlling the stirring speed to 100-600 rpm, adding 40-100° C. warm water to the molten mixture dropwise for 0.5-1 hour; Step S3: After the dripping is completed, the mixture is kept warm and stirred for 1-2 hours, and then a mildew inhibitor is added to the mixture, and finally cooled and packaged.

2. The method for preparing a loosening agent emulsion for solid phase synthesis according to claim 1, characterized in that: The emulsifying body is one or more of polydimethylsiloxane, polyether-modified silicone oil, and mineral oil, wherein the viscosity of polydimethylsiloxane is in the range of 300-3000mPas, the viscosity of polyether-modified silicone oil is in the range of 300-3000mPas, and the viscosity of mineral oil is in the range of 100-2000mPas.

3. The method for preparing a loosening agent emulsion for solid phase synthesis according to claim 2, characterized in that: The emulsifier is at least one of PEG-4000, PEG-6000, PEG-8000, sorbitan monostearate, glycerol polyoxyethylene polyoxypropylene ether, butanol polyoxypropylene ether, and sodium dodecylbenzene sulfonate.

4. The method for preparing a loosening agent emulsion for solid phase synthesis according to claim 3, characterized in that: The tank body of the emulsification tank is made of stainless steel or glass, and the stirring paddle of the emulsification tank is an Intermig multi-stage paddle.

5. The method for preparing a loosening agent emulsion for solid phase synthesis according to claim 4, characterized in that: The mass ratio of the emulsified body to the emulsifier in the melt is 100:(10-65).

6. The method for preparing a loosening agent emulsion for solid phase synthesis according to claim 5, characterized in that: The warm water is obtained by heating one of ordinary tap water, deionized water and distilled water.

7. The method for preparing a loosening agent emulsion for solid phase synthesis according to claim 6, characterized in that: The mildew inhibitor is at least one of chitosan, isothiazolinone and phenol.

8. An application of a loosening agent emulsion, wherein the loosening agent emulsion prepared by the method for preparing a loosening agent emulsion for solid phase synthesis according to any one of claims 1 to 7 is applied to solid powder synthesis.

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