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, a non-water-soluble phase and a compatibilizer, the water-soluble phase comprises a water-soluble matrix and a functional component; the compatibilizer comprises a maleic anhydride grafted compound and / or an acrylic acid copolymer. The pore diameter of the sustained-release material is accurately regulated and controlled by selecting the proper compatibilizer, so that the dissolution rate of functional components in the sustained-release material is controlled, and the problems that the total release amount of functional substances is low and the functional substances cannot be slowly released are solved.

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 purpose of the present invention is to provide a sustained-release functional material and a preparation method thereof. The sustained-release functional material realizes precise regulation of the pore size of the sustained-release material by selecting a suitable volume extender, thereby controlling the dissolution rate of the functional components in the sustained-release material, 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, which includes a water-soluble phase, a non-water-soluble phase and a compatibilizer; the water-soluble phase includes a water-soluble matrix and a functional component; the compatibilizer includes a maleic anhydride grafted compound and / or an acrylic copolymer.

[0007] In the present invention, the functional components are encapsulated in a water-soluble matrix and then form a uniform co-continuous structure with the non-water-soluble phase with the aid of a compatibilizer.

[0008] It can be seen that the present invention not only solves the problem of low release rate of functional molecules, but also can achieve a sustained release effect. Among them, the compatibilizer has a great influence on the size and continuity of the co-continuous structure. Since the compatibility of the water-soluble phase and the non-water-soluble phase is poor, the phase region formed in the blending process is large. After adding the compatibilizer, the two phases are modified by the volume expansion, which can promote the uniform mixing of the two phases to form a co-continuous structure with better continuity. The release channel that can change with the degree of water solubility is formed due to the presence of the water-soluble polymer matrix. The functional molecules can be released synchronously in water with the dissolution of the water-soluble polymer matrix, and the functional molecules are also fully released as the water-soluble polymer matrix is ​​completely dissolved. After testing, when the compatibilizer selects maleic anhydride grafted compounds and / or acrylic copolymers, the particle size of the water-soluble phase particles in the co-continuous structure can reach 100nm~10μm, so that a relatively low sustained release rate can be obtained, and the release rate of the functional components reaches: 0.0001~0.003g / L.

[0009] On this basis, the distribution of the water-soluble polymer matrix in the co-continuous structure (including size, volume proportion, etc.) can be adjusted by adjusting the type and dosage of the compatibilizer, the non-water-soluble phase, the type of the water-soluble polymer 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.

[0010] Preferably, the amount of the extender added to the sustained-release functional material is 1 to 10 wt %, more preferably 3 to 8 wt %.

[0011] Preferably, the non-aqueous phase includes at least one of the following: POE, EVA, PBAT, PCL, PLA, PBS, PE, PP, PS, ABS.

[0012] Preferably, the water-soluble polymer matrix includes at least one of the following: PEG, PEO, PVA, PAM.

[0013] Preferably, the compatibilizer includes at least one of the following: PP-g-MAH, PE-g-MAH, EVA-g-MAH, POE-g-MAH.

[0014] Preferably, the functional component includes at least one of a bactericide, a water softener, a scale inhibitor, and a color fixative.

[0015] 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;

[0016] 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;

[0017] The scale inhibitor includes at least one of the following: sodium citrate, disodium ethylenediaminetetraacetate;

[0018] The color fixing agent includes at least one of the following: polyquaternary ammonium salt, polyhexamethylene guanidine, and polyhexamethylene biguanide.

[0019] Preferably, in the water-soluble phase, the mass percentage of the water-soluble matrix is ​​95% to 60%.

[0020] Preferably, the mass ratio of the non-aqueous phase to the aqueous phase is 70:30 to 30:70.

[0021] Preferably, the sustained-release functional material has a release rate of the functional component in water of 0.0001 to 0.003 g / L.

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

[0023] Preferably, the sustained-release functional material has a co-continuous structure.

[0024] The second aspect of the present invention provides a method for preparing the sustained-release functional material according to the first aspect, comprising: blending the water-soluble masterbatch, the non-water-soluble phase and the compatibilizer to obtain the sustained-release functional material.

[0025] Specifically, any of the following may be used:

[0026] The non-water-soluble phase, the water-soluble polymer matrix, the compatibilizer and the functional component are extruded and blended or mixed to obtain a sustained-release functional material;

[0027] Alternatively, the water-soluble polymer matrix and the functional components are first extruded and blended or kneaded to obtain a water-soluble masterbatch; and then the water-soluble masterbatch, the non-aqueous phase and the compatibilizer are extruded and blended or kneaded to obtain a sustained-release functional material.

[0028] In summary, compared with the prior art, the present invention achieves the following technical effects:

[0029] Compatibilizers such as maleic anhydride grafted compounds and / or acrylic copolymers are added to the water-soluble phase and the non-water-soluble phase to promote the uniform blending of the two phases, which can form a sustained-release material with a co-continuous structure with good continuity. The material has a pore size in a specific size range and can achieve almost complete release of functional components. By optimizing the type and amount of the compatibilizer, the type of the non-water-soluble matrix, and the type and proportion 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

[0030] 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:

[0031] Figure 1 The figure is a schematic diagram of the microstructure of a sustained-release material of the present invention. DETAILED DESCRIPTION

[0032] 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.

[0033] The chemical substances involved in the present invention are defined as follows.

[0034] POE: Polyolefin elastomer.

[0035] EVA: Ethylene-vinyl acetate copolymer.

[0036] PBAT: poly(butylene terephthalate-adipate).

[0037] PCL: poly-ε-caprolactone.

[0038] PLA: Polylactic acid.

[0039] PBS: polybutylene succinate.

[0040] PE: Polyethylene.

[0041] PP: Polypropylene.

[0042] PS: Polystyrene.

[0043] ABS: Acrylonitrile butadiene styrene plastic.

[0044] PVA: polyvinyl alcohol.

[0045] PEG: polyethylene glycol.

[0046] PEO: Polyethylene oxide.

[0047] PAM: polyacrylamide.

[0048] PP-g-MAH: Maleic anhydride grafted polypropylene.

[0049] PE-g-MAH: maleic anhydride grafted polyethylene.

[0050] EVA-g-MAH: Maleic anhydride grafted ethylene-vinyl acetate copolymer.

[0051] POE-g-MAH: Maleic anhydride grafted polyolefin elastomer.

[0052] 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.

[0053] In order to solve the above technical problems, the present invention provides a sustained-release functional material, comprising a water-soluble phase, a non-water-soluble phase and a compatibilizer; the water-soluble phase comprises a water-soluble matrix and functional components; the compatibilizer comprises a maleic anhydride grafted compound and / or an acrylic copolymer.

[0054] In the present invention, the functional components are encapsulated in a water-soluble polymer matrix, and then form a uniform co-continuous structure with the non-water-soluble phase with the assistance of a compatibilizer. 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 polymer matrix, but also the functional molecules can be released synchronously into water as the water-soluble polymer matrix is ​​dissolved, and as the water-soluble polymer matrix is ​​completely dissolved, the functional molecules are also completely released.

[0055] It can be seen that the present invention not only solves the problem of low release rate of functional molecules, but also can achieve a sustained release effect. Among them, the compatibilizer has a great influence on the size and continuity of the co-continuous structure. Since the compatibility between the water-soluble phase and the non-water-soluble phase is poor, the phase region formed during the blending process is large. After adding the compatibilizer, it plays a role of volume modification on the two, which can promote the uniform mixing of the two to form a co-continuous structure with better continuity. According to tests, when the compatibilizer selects maleic anhydride grafted compounds and / or acrylic copolymers, the particle size of the water-soluble phase particles in the co-continuous structure can reach 100nm~10μm, so that a relatively low sustained release rate can be obtained, and the release rate of the functional components reaches: 0.0001~0.003g / L.

[0056] The co-continuous structure of the present invention is 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. The water-soluble phase can be evenly dispersed in the non-aqueous phase, and the water-soluble phase of the present invention covers the functional components. Therefore, when the sustained-release functional material with such a structure contacts water, the water-soluble phase will continuously dissolve in water, thereby continuously releasing the functional components.

[0057] 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.

[0058] The functional components coated by the above sustained-release functional materials can be any, including but not limited to agents for cleaning or caring for clothes, and can also be agents for purifying water, etc. In the present invention, the combination of non-water-soluble phase and water-soluble phase components is arbitrary, including but not limited to those listed in Table 1 below.

[0059] Table 1

[0060]

[0061]

[0062] In addition, the size and continuity of the co-continuous structure can be adjusted by adjusting the type, amount, molecular weight, etc. of the compatibilizer.

[0063] In some embodiments, the non-aqueous phase includes at least one of the following: POE, EVA, PBAT, PCL, PLA, PBS, PE, PP, PS, ABS.

[0064] In some embodiments, the water-soluble polymer matrix includes at least one of the following: PEG, PEO, PVA, PAM.

[0065] In some embodiments, the compatibilizer includes at least one of the following: PP-g-MAH, PE-g-MAH, EVA-g-MAH, POE-g-MAH.

[0066] In some embodiments, the amount of the extender added to the sustained-release functional material is 1-10wt%, including but not limited to 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 10wt%, wherein the range of 3-8wt% is preferred. Here, "wt%" refers to weight percentage.

[0067] On this basis, the distribution (including size, volume percentage, etc.) of the water-soluble polymer matrix in the co-continuous structure can be adjusted by adjusting the type of the non-aqueous phase, the water-soluble polymer 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.

[0068] In some embodiments, the non-aqueous phase comprises at least one of the following: PE, PP.

[0069] In some embodiments, the water-soluble polymer matrix includes at least one of the following: PEG, PEO.

[0070] In some embodiments, the functional component includes at least one of a bactericide, a water softener, a scale inhibitor, and a color fixative.

[0071] 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.

[0072] 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.

[0073] In some embodiments, the antiscalant includes at least one of the following: sodium citrate, disodium ethylenediaminetetraacetate.

[0074] In some embodiments, the fixing agent includes at least one of the following: polyquaternary ammonium salt, polyhexamethylene guanidine, polyhexamethylene biguanide.

[0075] In some embodiments, in the water-soluble phase, the mass percentage of the water-soluble matrix is ​​95% to 60%.

[0076] In some embodiments, the mass ratio of the non-aqueous phase to the aqueous phase is 70:30 to 30:70.

[0077] In some embodiments, the sustained-release functional material has a release rate of the functional component in water of 0.0001 to 0.003 g / L.

[0078] In some embodiments, the particle size of the water-soluble phase particles in the co-continuous structure is 100 nm to 10 μm.

[0079] 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.

[0080] Among them, the one-step method is mainly:

[0081] The non-water-soluble phase, the water-soluble polymer matrix, the compatibilizer and the functional component are extruded and blended or mixed to obtain a sustained-release functional material;

[0082] The two-step method mainly comprises: firstly, extruding and blending the water-soluble polymer matrix and the functional components or mixing them together to obtain a water-soluble masterbatch; and then extruding and blending the water-soluble masterbatch, the non-aqueous phase and the compatibilizer or mixing them together to obtain a sustained-release functional material.

[0083] The present invention also provides the following embodiments.

[0084] Example 1

[0085] Sustained-release functional materials with bactericidal effect

[0086] Take PEO, polyhexamethyleneguanidine PHMG, low-density polyethylene (PE), and a compatibilizer (maleic anhydride grafted polyethylene) and prepare according to the following steps.

[0087] (1) PEO (molecular weight 300,000) was dried at 50°C for 6 hours;

[0088] (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;

[0089] 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;

[0090] (3) using a twin-screw extruder, the water-soluble masterbatch obtained in step (2), low-density polyethylene (Maoming Petrochemical low-density polyethylene 2426H, number average molecular weight 90,000), and a compatibilizer are secondly blended in a mass ratio of 55 / 40 / 5, and 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;

[0091] The mixture obtained by the second blending is air-cooled to below 50° C., and then granulated to obtain a sustained-release antibacterial material.

[0092] Example 2

[0093] The difference from Example 1 is that the functional components are different, polyhexamethylene guanidine PHMG is replaced by calcium sulfite, and the other conditions are the same as Example 1.

[0094] Examples 3 to 4

[0095] The difference from Example 1 is that the non-water-soluble matrix is ​​different, and the low-density polyethylene is replaced by PP (homopolymer polypropylene T30S) and POE (POE6102), respectively, and the other conditions are the same as Example 1.

[0096] Examples 5 to 6

[0097] The difference from Example 1 is that the water-soluble polymer matrix is ​​different, PEO is replaced by PEG (PEG-200) and PVA (PVA-1799), and the other conditions are the same as Example 1.

[0098] Examples 7 to 8

[0099] The difference from Example 1 is that the types of compatibilizers are different, which are replaced by maleic anhydride grafted polypropylene and ethylene-acrylic acid copolymer respectively, and the other conditions are the same as Example 1.

[0100] Examples 9 to 12

[0101] The difference from Example 1 is that the amounts of the compatibilizers are different, namely 0.5wt%, 5wt%, 10wt% and 12wt% respectively; the other conditions are the same as Example 1.

[0102] Comparative Example 1

[0103] The difference from Example 1 is that the type of compatibilizer is different, which is ethylene-methacrylic acid copolymer.

[0104] Comparative Example 2

[0105] The difference from Example 1 is that the raw material does not have a compatibilizer, and the weight ratio of the water-soluble masterbatch to the low-density polyethylene remains unchanged, and the other conditions are the same as Example 1.

[0106] 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.

[0107] 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.

[0108] Table 2

[0109]

[0110] Note: In the compatibilizer column in the table, A, B, C, and D represent maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer, respectively.

[0111] The above data show that the type, dosage and molecular weight of the compatibilizer, as well as the type of non-water-soluble phase and the type of water-soluble polymer matrix have a significant impact on the sustained-release effect.

[0112] 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 comprises a water-soluble phase, a non-water-soluble phase and a compatibilizer; the water-soluble phase comprises a water-soluble matrix and functional components; the compatibilizer comprises a maleic anhydride grafted compound and / or an acrylic copolymer.

2. The sustained-release functional material according to claim 1, characterized in that: The amount of the extender added to the sustained-release functional material is 1 to 10 wt %, preferably 3 to 8 wt %.

3. The sustained-release functional material according to claim 1 or 2, 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.

4. The sustained-release functional material according to claim 1, characterized in that: The water-soluble matrix includes at least one of the following: PEG, PEO, PVA, PAM.

5. The sustained-release functional material according to claim 1, characterized in that: The compatibilizer includes at least one of the following: PP-g-MAH, PE-g-MAH, EVA-g-MAH, POE-g-MAH.

6. The sustained-release functional material according to claim 1, characterized in that: The functional component includes at least one of a bactericide, a water softener, a scale inhibitor, and a color fixative; The fungicide preferably 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; The water softener preferably includes 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 preferably includes at least one of the following: sodium citrate, disodium ethylenediaminetetraacetate; The color fixing agent preferably includes at least one of the following: polyquaternary ammonium salt, polyhexamethylene guanidine, polyhexamethylene biguanide.

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 ​​95% to 60%.

8. The sustained-release functional material according to claim 1 or 7, characterized in that: The mass ratio of the non-aqueous phase to the aqueous phase is 70:30 to 30:

70.

9. The sustained-release functional material according to claim 1, characterized in that: The sustained-release functional material has a release rate of the functional component in water of 0.0001 to 0.003 g / L; The particle size of the water-soluble phase particles in the co-continuous structure is preferably 100 nm to 10 μm; Preferably, the sustained-release functional material has 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 water-soluble masterbatch, the non-water-soluble phase and the compatibilizer are blended to obtain a sustained-release functional material.

Images