CN119701809A

CN119701809A - Modified beta-CD microcapsule and preparation method and application thereof

Info

Publication number: CN119701809A
Application number: CN202411914997.1A
Authority: CN
Inventors: 黎梓涵; 周明吉; 马峰刚
Original assignee: Nanjing Chemical Fiber Co ltd; Nanjing Jinling Bio Based Fiber Co ltd
Current assignee: Nanjing Chemical Fiber Co ltd; Nanjing Jinling Bio Based Fiber Co ltd
Priority date: 2024-12-24
Filing date: 2024-12-24
Publication date: 2025-03-28

Abstract

The present invention discloses a modified β-CD microcapsule and a preparation method and application thereof, wherein β-cyclodextrin is modified using s-triazine. First, DMSO and β-cyclodextrin are added to a glass reaction vessel, a certain amount of trichloros-s-triazine is dissolved in acetone and then added to the glass reaction vessel, the reaction is carried out at 60°C for 8 hours, and the product is obtained after washing and drying. Secondly, the wall material powder is completely dissolved in deionized water at 70°C, and then the additive to be embedded is added dropwise to the solution. The stirred emulsion is placed in a homogenizer and placed at a pressure of 500 bar for 20 minutes. Finally, the emulsion is microencapsulated using a spray dryer to obtain the target product. The present invention aims to provide a carrier for adding functional additives to the stock solution, safely add the functional additives to the lyocell fiber, and greatly reduce or even eliminate the influence of the functional additives on the NMMO recovery system.

Description

Modified beta-CD microcapsule and preparation method and application thereof

Technical Field

The invention relates to the technical field of chemical product preparation, in particular to a modified beta-CD microcapsule, and a preparation method and application thereof.

Background

The lyocell fiber is prepared from natural cellulose as raw material by directly dissolving organic solvent NMMO and spinning. The supramolecular structure of lyocell fibres shows a pronounced fibril content, with crystallinity up to 53.26%, higher than that of conventional viscose fibres (crystallinity about 30%) and high wet modulus viscose fibres (crystallinity about 44%). The high degree of polymerization and high crystallinity of lyocell fibers imparts better physical and mechanical properties than other regenerated cellulose fibers, such as high dry and wet strength, high wet modulus, and small differences in dry and wet strength.

The lyocell fabric is woven by natural plant fibers and has an environment-friendly function which is not possessed by viscose fibers. Harmful gases such as sulfur dioxide, hydrogen sulfide and the like are released in the conventional viscose fiber remanufacturing process, and the viscose fiber is harmful to human bodies and pollutes the environment. The lyocell fabric has the characteristics of comfort, good hand feeling, easy dyeing and the like of cotton, has luxurious feeling of wool fabric and draping feeling of modal, and has bright surface and is very suitable for manufacturing high-grade clothes.

At present, due to the key cost problem of solvent recovery in the production process, functional auxiliary agents are difficult to directly add in the preparation process of the lyocell fiber stock solution, and a post-treatment process is mostly adopted for functional surface modification. The post-treatment process can avoid polluting an NMMO system, but can obviously influence the surface of the lyocell yarn, so that the surface of the fiber becomes rough and stiff, the physical property advantage of the lyocell is lost, the market competitiveness of the fiber is seriously reduced, the post-treatment process can only carry out surface modification, the performance of the auxiliary agent can be obviously reduced due to the influence of the washing times of fabrics, and the problem is avoided when the stock solution is added.

Therefore, how to provide a carrier for adding the functional auxiliary agent to the stock solution, and safely adding the functional auxiliary agent to the lyocell fiber, so that the influence of the functional auxiliary agent on an NMMO recovery system is greatly reduced or even eliminated becomes important.

Disclosure of Invention

The invention aims to provide a modified beta-CD microcapsule, a preparation method and application thereof, and aims to provide a carrier for adding functional auxiliary agents into stock solution, and safely adding the functional auxiliary agents into lyocell fibers.

In order to solve the technical problems, the invention provides a preparation method of a modified beta-CD microcapsule, which comprises the following steps:

Placing trichloro-s-triazine into acetone for full dissolution, adding the solution into a glass reaction container containing DMSO and beta-cyclodextrin, stirring the solution for 8 to 10 hours at a constant temperature of 60 to 105 ℃, carrying out suction filtration, washing the solution by using deionized water, and freeze-drying the solution to obtain microcapsule wall materials;

adding a solution of the microcapsule wall material completely dissolved in deionized water and a functional auxiliary agent solution dissolved in absolute ethyl alcohol into a homogenizer, and treating for 20 minutes at 500bar pressure to obtain a homogeneous emulsion;

And (3) microencapsulating the homogeneous emulsion by using a spray dryer to obtain the modified beta-CD microcapsule.

Preferably, the mass ratio of the DMSO to the beta-cyclodextrin is 6-8:15-20.

Preferably, the mass ratio of the acetone to the trichloro-s-triazine is 3-5:1-2.

Preferably, the microcapsule wall material is obtained after 6-8 hours of freeze drying.

Preferably, the microcapsule wall material is completely dissolved in deionized water at 70 ℃.

Preferably, the mass ratio of the microcapsule wall material to the functional auxiliary agent is 5:2.

Preferably, the homogeneous emulsion is added into a spray dryer, and the feed liquid microencapsulation treatment is carried out at an inlet air temperature of 180 ℃ with 80% air quantity, so as to obtain the modified beta-CD microcapsule.

In a second aspect, the invention provides a modified beta-CD microcapsule prepared by the method for preparing the modified beta-CD microcapsule.

In a third aspect, the modified beta-CD microcapsule is prepared by the preparation method and is applied to preparing lyocell fibers.

Compared with the prior art, the invention has the beneficial effects that the carrier is provided for adding the functional auxiliary agent into the stock solution, the functional auxiliary agent is safely added into the lyocell fiber, and the influence of the functional auxiliary agent on an NMMO recovery system is greatly reduced or even avoided. The beta-CD microcapsule is nontoxic and harmless, and the production process is environment-friendly and does not cause environmental pollution. The modified lyocell fiber can adapt to the warm-pressing environment of a lyocell fiber production system, and can avoid influencing the physical and chemical properties of the lyocell stock solution on the premise of ensuring that the core material is not damaged, and is directly used for stock solution addition.

Drawings

The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:

FIG. 1 is a flow chart of the steps of a method for preparing a modified beta-CD microcapsule according to the invention;

FIG. 2 is a graph comparing TG curves of modified and unmodified beta-CD walls.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

Into a 200mL three-necked flask, 19.5g of beta-cyclodextrin and 45g of DMSO were added, and after 3g of trichloro-s-triazine was dissolved in 8g of acetone, the mixture was put into the three-necked flask, and a reflux apparatus was set up, and the mixture was heated and stirred in a 105 ℃ oil bath for 8.5 hours under a nitrogen atmosphere. After cooling, the mixture was filtered under reduced pressure, and after filtration, the mixture was washed with 200mL of deionized water. After freeze-drying for 8 hours, 18.4g of microcapsule wall material was obtained as pale yellow powder.

Taking 15g of microcapsule wall material, completely dissolving in deionized water, dissolving 4g of lavender essential oil in 4ml of absolute ethyl alcohol, adding into a small homogenizer, and homogenizing for 20 minutes at 500bar pressure to obtain a homogeneous emulsion.

The homogeneous emulsion is added into a spray dryer, and the microcapsule treatment of the feed liquid is carried out at the inlet air temperature of 180 ℃ with 80% air quantity, thus obtaining 18.8g of finished microcapsule.

Example 2

Into a 2L glass reaction kettle, 193.2g of beta-cyclodextrin and 550g of DMSO are added, 30g of trichloro-s-triazine is dissolved in 85g of acetone, and then the mixture is put into a three-neck flask, a reflux device is built, and the mixture is heated and stirred for 8 hours in a 105 ℃ oil bath under the nitrogen atmosphere. After cooling, the mixture was filtered under reduced pressure, and after filtration, the mixture was washed with 2L of deionized water. After freeze-drying for 8 hours, 219.3g of a pale yellow powdery microcapsule wall material was obtained.

Taking 150g of microcapsule wall material, completely dissolving in deionized water, dissolving 40g of lavender essential oil in 40ml of absolute ethyl alcohol, adding into a homogenizer, and homogenizing for 20 minutes under 500bar pressure to obtain a homogeneous emulsion.

The homogeneous emulsion is added into a spray dryer, and the microcapsule treatment of the feed liquid is carried out at the inlet air temperature of 180 ℃ with 80% air quantity, thus obtaining 184.5g of finished microcapsule.

Comparative example 1

Thermogravimetric analysis (TG) was performed on the modified and unmodified β -CD walls using the method of example 1 to obtain a graph comparing the TG curves of the modified and unmodified β -CD walls (fig. 2).

It can be seen from fig. 2 that the modified beta-CD wall material has better thermal stability than the unmodified beta-CD wall material.

It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, but may be modified or substituted for some of the technical features thereof by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing modified β-CD microcapsules, characterized in that the steps of preparing the modified β-CD microcapsules include:

The trichloro-s-triazine was fully dissolved in acetone and then added to a glass reaction vessel containing DMSO and β-cyclodextrin, and then stirred at 60°C to 105°C for 8 to 10 hours, and then filtered, washed with deionized water, and freeze-dried to obtain a microcapsule wall material;

A solution in which the microcapsule wall material is completely dissolved in deionized water and a solution of the functional additive dissolved in anhydrous ethanol are added into a homogenizer and treated at a pressure of 500 bar for 20 minutes to obtain a homogenous emulsion;

The homogeneous emulsion was microencapsulated by a spray dryer to obtain modified β-CD microcapsules.

2 . The method for preparing modified β-CD microcapsules according to claim 1 , wherein the mass ratio of the DMSO to the β-cyclodextrin is 6-8:15-20.

3. The method for preparing modified β-CD microcapsules according to claim 1, characterized in that the mass ratio of the acetone to the trichloro-s-triazine is 3-5:1-2.

4. The method for preparing modified β-CD microcapsules according to claim 1, characterized in that the microcapsule wall material is obtained after freeze-drying for 6 to 8 hours.

5 . The method for preparing modified β-CD microcapsules according to claim 1 , wherein the microcapsule wall material is completely dissolved in deionized water at 70° C.

6 . The method for preparing modified β-CD microcapsules according to claim 1 , wherein the mass ratio of the microcapsule wall material to the functional auxiliary agent is 5:2.

7. The method for preparing modified β-CD microcapsules according to claim 1, characterized in that the homogeneous emulsion is added into a spray dryer and subjected to liquid microencapsulation treatment at an air volume of 80% and an inlet air temperature of 180°C to obtain the modified β-CD microcapsules.

8. A modified β-CD microcapsule, characterized in that it is prepared by the modified β-CD microcapsule preparation method according to any one of claims 1 to 7.

9. The modified β-CD microcapsule according to any one of claims 1 to 7, characterized in that it is used for preparing lyocell fibers.