Slow-release functional material and preparation method thereof

Abstract

The invention relates to a slow-release functional material and a preparation method thereof. The slow-release functional material comprises a water-soluble phase and a non-water-soluble phase, the water-soluble phase comprises a water-soluble matrix and a functional component; wherein the mass ratio of the non-water-soluble phase to the water-soluble phase is (40: 60)-(60: 40); when the slow-release functional material is in water, the release rate of the water-soluble phase in the water is 0.0001-0.0032 g / L. The problem that the total release amount of functional molecules is low is solved, and the slow release effect can be achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and in particular to a sustained-release functional material and a preparation method thereof. Background Art

[0002] In the field of cleaning, the current way to achieve multiple functions such as deodorization, scale prevention, and sterilization is usually to add functional substances to the working environment, such as aromatherapy for deodorization, salts for scale prevention, silver phosphate for sterilization, guanidines for long-term antibacterial effect, and healthy natural sterilization. In order to facilitate use and maintain the long-term effectiveness of the functional effects, the above functional substances usually need to be loaded in a carrier, such as silver phosphate needs to be loaded in glass, natural antibacterial agents and guanidines need to be loaded in a plastic matrix, and activated carbon that can load scale-inhibiting salts can be loaded. However, in essence, the above functional substances are mostly inorganic substances or small molecules, which are basically randomly dispersed in the matrix, and it is difficult to form a stable release path. Therefore, in theory, only the functional substances dispersed on the surface can be released and play a functional role, but the functional substances inside the matrix are difficult to dissolve in water and release, and the role of the functional substances cannot be fully exerted.

[0003] To this end, the present invention is proposed. Summary of the invention

[0004] The object of the present invention is to provide a sustained-release functional material and a preparation method thereof, wherein the sustained-release functional material realizes precise regulation of the pore size of the sustained-release material by controlling the mass ratio of the two phases within a certain range, thereby controlling the dissolution rate of the functional components in the sustained-release material, thereby solving the problem of low total release of functional substances and inability to sustain release.

[0005] In order to achieve the above objectives, the present invention provides the following technical solutions:

[0006] The first aspect of the present invention provides a sustained-release functional material.

[0007] It includes a water-soluble phase and a water-insoluble phase; the water-soluble phase includes a water-soluble matrix and functional components;

[0008] Wherein, the mass ratio of the non-aqueous phase to the aqueous phase is 40:60 to 60:40;

[0009] When the sustained-release functional material is in water, the release rate of the water-soluble phase in water is 0.0001 to 0.0032 g / L.

[0010] In the present invention, the functional components are encapsulated in a water-soluble matrix and then form a sustained-release material with a non-water-soluble phase. In this way, not only a release channel that can change with the degree of water solubility is formed due to the presence of the water-soluble matrix, but also the functional molecules can be released synchronously into water as the water-soluble matrix is ​​dissolved, and as the water-soluble matrix is ​​completely dissolved, the functional molecules are also completely released.

[0011] It can be seen that the present invention not only solves the problem that the functional molecules cannot be fully released, but also can achieve a sustained release effect. According to tests, when the mass ratio of the non-aqueous phase to the aqueous phase is in the range of 40:60 to 60:40, the particle size of the aqueous phase particles in the co-continuous structure can reach 100nm to 10μm, thereby obtaining a relatively low sustained release rate, and the release rate of the functional component reaches: 0.0001 to 0.0032g / L. Such a product is suitable for low-dosage functional component types.

[0012] On this basis, the distribution (including size, volume proportion, etc.) of the water-soluble matrix in the co-continuous structure can be adjusted by adjusting the non-aqueous phase, the type of the water-soluble matrix, the proportion of each component, etc., thereby adjusting the release channel characteristics of the functional components to regulate the sustained release life, etc., as listed below.

[0013] Preferably, the non-aqueous phase includes at least one of the following: POE, EVA, PBAT, PCL, PLA, PBS, PE, PP, PS, ABS.

[0014] Preferably, the non-aqueous phase comprises at least one of the following: PBAT, PCL, PLA, PBS, PP, PE.

[0015] Preferably, the water-soluble matrix includes at least one of PEO, PVA, PEG and polyacrylamide.

[0016] Preferably, the functional component includes at least one of a bactericide, a water softener, a scale inhibitor, and a color fixative.

[0017] Preferably, the fungicide includes at least one of the following: monoguanidine fungicides, biguanide fungicides, amino acid fungicides, quaternary ammonium salt fungicides, metal fungicides, metal oxide fungicides, polyphenol fungicides, pyridine fungicides, and plant extract fungicides;

[0018] The water softener comprises at least one of the following: phosphates, silicates, imide sulfonates, amino acid derivatives, hydroxy acids and their derivatives, polyacrylic acid and their derivatives;

[0019] The scale inhibitor includes at least one of the following: sodium citrate, disodium ethylenediaminetetraacetate;

[0020] The color fixing agent includes at least one of the following: polyhexamethylene guanidine, polyhexamethylene biguanide, and polyquaternary ammonium salt.

[0021] Preferably, the non-aqueous phase and the aqueous phase are mixed to form a co-continuous structure.

[0022] Preferably, the particle size of the water-soluble phase particles in the co-continuous structure is 100 nm to 10 μm.

[0023] The second aspect of the present invention provides a method for preparing the sustained-release functional material according to the first aspect, comprising:

[0024] The non-water-soluble phase, the water-soluble matrix and the functional component are blended to obtain a sustained-release functional material;

[0025] Alternatively, the water-soluble masterbatch and the non-water-soluble phase are blended to obtain a sustained-release functional material.

[0026] The preparation method described above can be adjusted depending on the equipment type, cost, type of functional ingredients, etc.

[0027] In summary, compared with the prior art, the present invention achieves the following technical effects:

[0028] A specific type of non-water-soluble phase and a specific type of water-soluble matrix are selected and blended in a ratio of 40:60 to 60:40 to obtain a sustained-release material. The material has a co-continuous structure, has the advantages of sustained release and complete release, and is suitable for functional components with lower release amounts. The release rate of the sustained-release material in water can be controlled at 0.0001 to 0.0032 g / L. The sustained-release material has a pore size in a specific size range. By further optimizing the type of non-water-soluble matrix, the type and ratio of the water-soluble material, the pore size of the sustained-release material can be accurately controlled for the combination of the two phases, thereby controlling the dissolution rate of the effective substance in the sustained-release material, improving the stability of the sustained-release material, and ensuring that the sustained-release material has a predetermined service life and a good user experience. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present application. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0030] Figure 1 The figure is a schematic diagram of the microstructure of a sustained-release material of the present invention. DETAILED DESCRIPTION

[0031] The embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. In the examples, if specific conditions are not specified, they are carried out according to normal conditions or the conditions recommended by the manufacturer. The original drugs, reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased commercially or can be prepared according to the prior art.

[0032] The chemical substances involved in the present invention are defined as follows.

[0033] POE: Polyolefin elastomer.

[0034] EVA: Ethylene-vinyl acetate copolymer.

[0035] PBAT: poly(butylene terephthalate-adipate).

[0036] PCL: poly-ε-caprolactone.

[0037] PLA: Polylactic acid.

[0038] PBS: polybutylene succinate.

[0039] PE: Polyethylene.

[0040] PP: Polypropylene.

[0041] PS: Polystyrene.

[0042] ABS: Acrylonitrile butadiene styrene plastic.

[0043] PVA: polyvinyl alcohol.

[0044] PEG: polyethylene glycol.

[0045] PEO: Polyethylene oxide.

[0046] In existing water-based cleaning or care products, the carriers for loading functional ingredients have no sustained-release effect, and the total release amount of the functional ingredients is low.

[0047] In order to solve the above technical problems, the present invention provides a sustained-release functional material, which includes a water-soluble phase and a water-insoluble phase; the water-soluble phase includes a water-soluble matrix and a functional component;

[0048] Wherein, the mass ratio of the non-aqueous phase to the aqueous phase is 40:60 to 60:40;

[0049] When the sustained-release functional material is in water, the release rate of the water-soluble phase in water is 0.0001 to 0.0032 g / L.

[0050] In the above sustained-release functional materials, the functional components are encapsulated in a water-soluble matrix, and then form a co-continuous structure or other uniformly mixed structure with the non-water-soluble phase. In this way, not only a release channel that can change with the dissolution amount is formed due to the presence of the water-soluble matrix, but also the functional molecules can be released synchronously into the water as the water-soluble matrix is ​​dissolved, and as the water-soluble matrix is ​​completely dissolved, the functional molecules are also completely released.

[0051] It can be seen that the present invention not only solves the problem of low total release of functional molecules, but also can achieve a sustained release effect. According to tests, when the mass ratio of the non-aqueous phase to the aqueous phase is in the range of 40:60 to 60:40, the particle size of the aqueous phase particles in the co-continuous structure can reach 100nm to 10μm, thereby obtaining a relatively low sustained release rate, and the release rate of the functional component reaches 0.0001 to 0.0032g / L. Such a product is suitable for low-dosage functional component types.

[0052] The sustained-release functional material of the present invention may exist in the form of a co-continuous structure, which refers to a three-dimensional network structure constructed by mixing a water-soluble phase and a non-water-soluble phase. Figure 1 In the microstructure shown, the gray area is the matrix formed by the non-aqueous phase, and the white area is the water-soluble phase, and the water-soluble phase can be evenly dispersed in the non-aqueous phase. Taking the present invention as an example, since the water-soluble phase of the present invention also coats the functional components, when the sustained-release functional material with such a structure contacts water, the water-soluble phase will continuously dissolve in the water, thereby continuously releasing the functional components.

[0053] The water-soluble phase particles described in the present invention refer to particles dispersed by a non-aqueous phase, that is, water-soluble phase particles dispersed in a non-aqueous phase.

[0054] The functional components coated by the above sustained-release functional materials can be arbitrary, including but not limited to agents for cleaning or caring for clothes, and can also be agents for purifying water, etc.

[0055] In addition, controlling the mass ratio of the non-aqueous phase and the aqueous phase can adjust the dispersion size of each phase region, such as the particle size of the aqueous phase dispersed particles, thereby adjusting the sustained release characteristics. In the present invention, in order to achieve a release concentration of 0.0001 to 0.0032 g / L, the mass ratio of the non-aqueous phase and the aqueous phase is preferably in the range of 40:60 to 60:40, and can be 40:60, 42:58, 45:55, 47:53, 50:50, 55:45, 60:40, etc.

[0056] In the present invention, the combination of the non-water-soluble phase and the water-soluble phase components is arbitrary, including but not limited to those listed in Table 1 below.

[0057] Table 1

[0058] Non-aqueous phase Water soluble matrix PBAT PVA PCL PEG PLA PEO PBS Polyacrylamide PE PVA PP PEG ABS PEO PS Polyacrylamide

[0059] On this basis, the distribution of the water-soluble matrix in the co-continuous structure (including size, volume percentage, etc.) can be adjusted by adjusting the non-aqueous phase, the type of the water-soluble matrix, the polymer molecular weight, the ratio of each component, etc., thereby adjusting the release channel characteristics of the functional components to regulate the sustained release life, etc., as listed below.

[0060] In some embodiments, the non-aqueous phase includes at least one of the following: POE, EVA, PBAT, PCL, PLA, PBS, PE, PP, PS, ABS.

[0061] In some embodiments, the non-aqueous phase includes at least one of the following: PBAT, PCL, PLA, PBS, PE, PP, PS, ABS.

[0062] In some embodiments, the non-aqueous phase includes at least one of the following: PBAT, PCL, PLA, PBS.

[0063] In some embodiments, the water-soluble matrix includes at least one of PEO, PVA, PEG, and polyacrylamide.

[0064] In some embodiments, the water-soluble matrix includes at least PEO.

[0065] In some embodiments, the molecular weight of PEO is 300,000.

[0066] In some embodiments, the functional component includes at least one of a bactericide, a water softener, a scale inhibitor, and a color fixative.

[0067] In some embodiments, the fungicide includes at least one of the following: monoguanidine fungicides, biguanide fungicides, amino acid fungicides, quaternary ammonium salt fungicides, metal fungicides, metal oxide fungicides, polyphenol fungicides, pyridine fungicides, and plant extract fungicides.

[0068] In some embodiments, the water softener includes at least one of the following: phosphates, silicates, imide sulfonates, amino acid derivatives, hydroxy acids and their derivatives, polyacrylic acid and their derivatives.

[0069] In some embodiments, the antiscalant includes at least one of the following: sodium citrate, disodium ethylenediaminetetraacetate.

[0070] In some embodiments, the fixing agent includes at least one of the following: polyhexamethylene guanidine, polyhexamethylene biguanide, and polyquaternary ammonium salt.

[0071] In some embodiments, the particle size of the water-soluble phase particles is 100 nm to 10 μm.

[0072] The sustained-release functional material provided by the present invention can be blended by a one-step method or a two-step method, and the selection can be made according to the equipment type, cost, type of functional components, etc.

[0073] Among them, the one-step method mainly comprises: extruding and blending the non-water-soluble phase, the water-soluble matrix and the functional component or mixing and blending them to obtain a sustained-release functional material;

[0074] The two-step method mainly comprises: firstly, extruding and blending the water-soluble matrix and the functional components or mixing them together to obtain a water-soluble masterbatch; and then extruding and blending the water-soluble masterbatch and the non-water-soluble phase or mixing them together to obtain a sustained-release functional material.

[0075] The present invention also provides the following embodiments.

[0076] Example 1

[0077] Sustained-release functional materials with bactericidal effect

[0078] Take PEO, polyhexamethyleneguanidine PHMG, and low-density polyethylene and prepare them according to the following steps.

[0079] (1) PEO (molecular weight 300,000) was dried at 50°C for 6 hours;

[0080] (2) using a twin-screw extruder, PEO and polyhexamethylene guanidine PHMG are first blended in a mass ratio of 2:1, the operating temperature of the twin-screw extruder is: the temperature of zone 1 is 80°C, the temperature of zone 2 is 120°C, the temperature of zone 3 is 140°C, the temperature of zone 4 is 140°C, the temperature of zone 5 is 140°C, the temperature of zone 6 is 140°C, and the die temperature is 120°C; the screw speed is 50 rpm, and the material residence time is 3 min;

[0081] The mixture obtained by the first blending is air-cooled to below 50° C., and then granulated to obtain a water-soluble masterbatch with a particle size of 2-5 mm;

[0082] (3) using a twin-screw extruder, the water-soluble masterbatch obtained in step (2) and low-density polyethylene (Maoming Petrochemical low-density polyethylene 2426H, number average molecular weight 90,000) are blended for the second time at a mass ratio of 55:45, the operating temperature of the twin-screw extruder is: the temperature of zone 1 is 80°C, the temperature of zone 2 is 140°C, the temperature of zone 3 is 170°C, the temperature of zone 4 is 170°C, the temperature of zone 5 is 170°C, the temperature of zone 6 is 170°C, and the die temperature is 160°C; the screw speed is 50 rpm, and the material residence time is 3 min;

[0083] The mixture obtained by the second blending is air-cooled to below 50° C., and then granulated to obtain a sustained-release antibacterial material.

[0084] Example 2

[0085] The difference from Example 1 is that the blending ratio of water-soluble masterbatch and low-density polyethylene is replaced with 50:50, and the other conditions are the same as Example 1.

[0086] The difference between Example 3 and Example 1 is that the blending ratio of water-soluble masterbatch and low-density polyethylene is replaced with 60:40, and the other conditions are the same as Example 1.

[0087] Example 4

[0088] The difference from Example 1 is that the non-water-soluble matrix is ​​different, that is, homopolymerized polypropylene T30S, and the other conditions are the same as Example 1.

[0089] Example 5

[0090] The difference from Example 1 is that the non-water-soluble matrix is ​​different, that is, homopolymer polypropylene T30S, the blending ratio of water-soluble masterbatch and polypropylene is replaced with 60:40, and the other conditions are the same as Example 1.

[0091] Example 6

[0092] The difference from Example 1 is that the non-water-soluble matrix is ​​different, that is, homopolymer polypropylene T30S, the blending ratio of water-soluble masterbatch and polypropylene is replaced with 65:35, and the other conditions are the same as Example 1.

[0093] Comparative Example 1-2

[0094] The difference from Example 1 is that the mass ratio of water-soluble masterbatch to low-density polyethylene is different, namely 30:70 and 70:30 respectively, and the other conditions are the same as Example 1.

[0095] The sustained-release properties of the materials of the above embodiments and control examples in water were tested, and the results are shown in Table 2.

[0096] The test method for the release rate is as follows: prepare the sustained-release carrier material into a sample of 10mm×10mm×4mm with a mass of m1, and rinse it with tap water at a flow rate of 2.5L / min. After the sample mass becomes constant, take it out and dry it, and weigh it with a mass of m2. The volume of water used for rinsing is v, and the dissolution rate = (m1-m2) / v.

[0097] Table 2

[0098] sample Water soluble phase release rate g / L Particle size of water-soluble phase particles / μm Example 1 0.0024 1.8～4.3 Example 2 0.0013 1.3～4.1 Example 3 0.0032 2.1～4.6 Example 4 0.0003 1.2～2.7 Example 5 0.0014 1.5～3.8 Example 6 0.0025 1.7～4.6 Comparative Example 1 0.00004 0.7～2.7 Comparative Example 2 0.09 Matrix phase

[0099] The above data show that the type of non-aqueous phase, the type of water-soluble matrix and the ratio of the two have a significant impact on the sustained-release effect.

[0100] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be based on the protection scope of the claims.

Claims

1. A sustained-release functional material, characterized in that: It includes a water-soluble phase and a water-insoluble phase; the water-soluble phase includes a water-soluble matrix and functional components; Wherein, the mass ratio of the non-aqueous phase to the aqueous phase is 40:60 to 60:40; When the sustained-release functional material is in water, the release rate of the water-soluble phase in water is 0.0001 to 0.0032 g / L.

2. The sustained-release functional material according to claim 1, characterized in that: The non-aqueous phase includes at least one of the following: POE, EVA, PBAT, PCL, PLA, PBS, PE, PP, PS, and ABS.

3. The sustained-release functional material according to claim 2, characterized in that: The non-aqueous phase includes at least one of the following: PBAT, PCL, PLA, PBS, PP, and PE.

4. The sustained-release functional material according to any one of claims 1 to 3, characterized in that: The water-soluble matrix includes at least one of PEO, PVA, PEG and polyacrylamide.

5. The sustained-release functional material according to claim 1, characterized in that: The functional components include at least one of a bactericide, a water softener, a scale inhibitor, and a color fixative.

6. The sustained-release functional material according to claim 5, characterized in that: The fungicide includes at least one of the following: monoguanidine fungicide, biguanide fungicide, amino acid fungicide, quaternary ammonium salt fungicide, metal fungicide, metal oxide fungicide, polyphenol fungicide, pyridine fungicide, plant extract fungicide; The water softener comprises at least one of the following: phosphates, silicates, imide sulfonates, amino acid derivatives, hydroxy acids and their derivatives, polyacrylic acid and their derivatives; The scale inhibitor includes at least one of the following: sodium citrate, disodium ethylenediaminetetraacetate; The color fixing agent includes at least one of the following: polyhexamethylene guanidine, polyhexamethylene biguanide, and polyquaternary ammonium salt.

7. The sustained-release functional material according to claim 1, characterized in that: In the water-soluble phase, the mass percentage of the water-soluble matrix is ​​60% to 95%.

8. The sustained-release functional material according to claim 1, characterized in that: The particle size of the water-soluble phase particles is 100 nm to 10 μm.

9. The sustained-release functional material according to any one of claims 1 to 8, characterized in that: The water-insoluble phase and the water-soluble phase are mixed to form a co-continuous structure.

10. The method for preparing the sustained-release functional material according to any one of claims 1 to 9, characterized in that: include: The non-water-soluble phase, the water-soluble matrix and the functional component are blended to obtain a sustained-release functional material; Alternatively, the water-soluble matrix is ​​first blended with the functional component to obtain a water-soluble masterbatch, and the water-soluble masterbatch is then blended with a non-water-soluble phase to obtain a sustained-release functional material.

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