Bactericidal antiviral polypropylene melt-blown nonwoven material and method of making same

Abstract

The present application relates to a kind of bactericidal antiviral polypropylene melt-blown nonwoven material and its preparation method, belong to functional filter material field.First, the dilute amide functional monomer containing N-H and length controllable alkyl chain is selected, using the melt co-crystallization behavior of alkyl chain on monomer and polypropylene macromolecular chain, preparation co-crystallization polypropylene master batch;Then again through melt-blown spinning method, melt-blown nonwoven material is prepared, after sodium hypochlorite solution treatment makes N-H bond into N-Cl bond, i.e., obtain the bactericidal antiviral polypropylene melt-blown nonwoven fabric containing halamine structure.The bactericidal antiviral polypropylene melt-blown nonwoven material and its preparation method proposed in the present application have the advantages such as good dispersibility, high content of functional monomer;Antibacterial effect is good, and performance is durable;Structure is adjustable, and production process is stable and controllable.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of filter materials, in particular to a sterilization and anti-virus polypropylene melt-blown non-woven material and a preparation method thereof. BACKGROUND

[0002] Melt-blown non-woven materials composed of superfine fibers can efficiently block bacteria and viruses, and are key core materials for protective materials such as masks and protective clothing. However, existing melt-blown non-woven materials have single functions and poor anti-virus effects, resulting in short service life, large amount of use, and easy cross-infection of protective materials. Therefore, it is of great significance to develop melt-blown non-woven materials with sterilization and anti-virus functions.

[0003] At present, sterilization and anti-virus polypropylene non-woven materials on the market are mainly prepared by adding inorganic antibacterial agents to polypropylene master batches. For example, patent CN201210316357.1 reports an antibacterial polypropylene melt-blown non-woven filter material and a preparation method thereof. By adding nanometer tourmaline, nanometer titanium dioxide and nanometer zinc oxide to the melt-blown polypropylene, and improving the formula and preparation process, an antibacterial polypropylene melt-blown non-woven fabric is prepared. Patent CN202010446059 discloses a compound anti-virus and antibacterial multifunctional PP, PE and PET non-woven fabric and its preparation and application. Inorganic anti-virus and antibacterial metal / oxide and traditional Chinese medicine anti-virus and antibacterial components are loaded by specific methods using silica aerogel microspheres, and then mixed and extruded with fiber chips to obtain a master batch. Then the master batch is mixed with fiber chips to spin, and a compound anti-virus and antibacterial multifunctional PP, PE and PET non-woven fabric is obtained. However, inorganic powders are not easy to disperse in the melt blending process, which may affect the melt-blown spinning process and the performance of the non-woven fabric. In addition, organic antibacterial monomers can be grafted on the molecular chain of melt-blown polypropylene by chemical modification to prepare sterilization and anti-virus melt-blown non-woven materials. Among them, halamine antibacterial agents have the advantages of broad-spectrum antibacterial property, high antibacterial activity, fast sterilization rate, long-lasting antibacterial property, good regenerability and no toxic substances, and are widely studied and applied. For example, patent CN202011506583 provides a preparation method of a long-lasting antibacterial polypropylene non-woven fabric. By sequentially adsorbing and grafting dopamine, modified chitosan and halamine compound structures on the surface of the non-woven fabric, the polypropylene non-woven fabric has excellent and long-lasting antibacterial effect. Invention CN202010711332 provides an antibacterial polypropylene melt-blown material and a preparation method. A monomer containing a double bond and an antibacterial function is selected, the antibacterial monomer is grafted to the main chain of polypropylene by free radical graft copolymerization, and the molecular chain is formed by amine halogenation to form an antibacterial structure with halamine, thereby preparing an antibacterial polypropylene melt-blown material. However, since the polypropylene molecular chain does not contain active functional groups, the grafting rate of the antibacterial monomer is low, the production of the melt-blown non-woven fabric is unstable, and the antibacterial effect still needs to be improved. SUMMARY

[0004] The present application aims at the problems of poor dispersion effect of inorganic powder, low grafting rate of antibacterial monomer, unstable production, and still to be improved antibacterial effect in the process of preparing bactericidal and antiviral polypropylene nonwoven material by adding inorganic antibacterial agent in polypropylene master batch or grafting organic antibacterial monomer on chemically inert polypropylene molecular chain, and provides a new bactericidal and antiviral polypropylene melt-blown nonwoven material and a preparation method, which improves the dispersion, content, bactericidal and antiviral effect and production process stability of antibacterial monomer by adjusting the structure of functional monomer and optimizing the production process.

[0005] The object of the present application can be achieved by the following technical scheme:

[0006] A bactericidal and antiviral polypropylene melt-blown nonwoven material, which contains an enamide antibacterial functional monomer containing N-H and a length-controllable alkyl chain, and the crystallinity of the material is 35-40%.

[0007] In the technical scheme of the present application: the material is prepared by melt blending melt-blown grade polypropylene, the enamide antibacterial functional monomer containing N-H and a length-controllable alkyl chain, and a nucleating agent.

[0008] In the technical scheme of the present application: the melt-blown grade co-crystallized polypropylene master batch is melt-blown to prepare the co-crystallized polypropylene melt-blown nonwoven material; preferably, the melt-blown process temperature is 230-280 DEG C.

[0009] In the technical scheme of the present application: the co-crystallized polypropylene melt-blown nonwoven material is immersed in a sodium hypochlorite solution, then washed and dried to obtain the bactericidal and antiviral polypropylene melt-blown nonwoven material.

[0010] In the technical scheme of the present application: in the first step, the weight fractions of the melt-blown grade polypropylene, the enamide antibacterial functional monomer containing N-H and a length-controllable alkyl chain, and the nucleating agent are 80-120 parts, 1-30 parts, and 0.1-10 parts, respectively.

[0011] Preferably, in the first step, the weight fractions of the melt-blown grade polypropylene, the enamide antibacterial functional monomer containing N-H and a length-controllable alkyl chain, and the nucleating agent are 100 parts, 5-20 parts, and 0.2-1 part, respectively.

[0012] In the technical scheme of the present application: the structure of the enamide antibacterial functional monomer containing N-H and a length-controllable alkyl chain is as follows:

[0013]

[0014] Wherein: R1 is a long-chain alkyl group, the number of carbon atoms ranges from 10 to 25.

[0015] In the technical scheme of the present application: the enamide antibacterial functional monomer containing N-H and controllable length alkyl chain is 10-undecylenamide, hexenamide or 9-octadecenamide.

[0016] In the technical scheme of the present application: in the first step: the nucleating agent is an inorganic nucleating agent; preferably: the inorganic nucleating agent is one or a mixture of two of calcium carbonate, titanium dioxide and silicon dioxide; further preferably: the particle size of the inorganic nucleating agent is 100-800 nm; in the first step: the temperature of melt blending is 150-240 DEG C.

[0017] In the technical scheme of the present application: the mass concentration of sodium hypochlorite solution is 0.1%-5%, the pH of sodium hypochlorite solution is 1-9; the temperature of padding is 20-60 DEG C; the time of padding is 5-15 min.

[0018] A preparation method of the above-mentioned antibacterial and antiviral polypropylene melt-blown non-woven material, which comprises the following steps: melt blending melt-blown grade polypropylene, enamide antibacterial functional monomer containing N-H and controllable length alkyl chain and nucleating agent to obtain melt-blown grade co-crystallized polypropylene master batch; melt blowing the melt-blown grade co-crystallized polypropylene master batch to obtain co-crystallized polypropylene melt-blown non-woven material; padding the co-crystallized polypropylene melt-blown non-woven material in sodium hypochlorite solution, then washing and drying to obtain the antibacterial and antiviral polypropylene melt-blown non-woven material.

[0019] In the technical scheme of the present application: the antibacterial and antiviral polypropylene melt-blown non-woven material is applied to the preparation of masks and protective clothing.

[0020] The present application proposes to use co-crystallization method to prepare antibacterial and antiviral polypropylene melt-blown non-woven fabric containing halogenamine structure. First, select enamide functional monomer containing N-H and controllable length alkyl chain, use the melt co-crystallization behavior of alkyl chain on the monomer and polypropylene macromolecular chain to prepare co-crystallized polypropylene master batch; then prepare melt-blown non-woven material by melt blowing method, convert N-H bond to N-Cl bond after treatment with sodium hypochlorite to prepare antibacterial and antiviral polypropylene melt-blown non-woven fabric containing halogenamine structure. It has the advantages of good dispersibility, high content of functional monomer, good antibacterial effect, durable performance, adjustable structure, stable and controllable production process, etc.

[0021] The present application has the following advantages:

[0022] (1) The alkyl chain on the functional monomer and the polypropylene macromolecular chain are used for melt co-crystallization to realize effective combination of the functional monomer and the polypropylene. The alkyl chain structure of the functional monomer is similar to the structure of the polypropylene, so the monomer has better dispersibility and higher content, thereby improving the antibacterial and antiviral effect and durability.

[0023] (2) Through blending, the functional modification of melt-blown polypropylene is realized, which is different from free radical graft modification, is not limited by grafting rate, and reduces the occurrence of side reactions; the melting co-crystallization behavior of the polypropylene macromolecular chain can be regulated by regulating the length of the alkyl chain on the functional monomer, thereby improving the production stability of the co-crystallized melt-blown non-woven fabric. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 It is a schematic diagram of the polypropylene crystalline structure of the application. DETAILED DESCRIPTION

[0025] The application will be further described below in conjunction with examples, but the protection scope of the application is not limited thereto:

[0026] Melt-blown polypropylene: Hubei Tuoying New Material Co., Ltd.

[0027] Example 1

[0028] Preparation of a melt-blown co-crystallized polypropylene master batch containing N-H structure

[0029] The melt-blown polypropylene, 10-undecylenamide and nano-titanium dioxide nucleating agent (average particle size 200 nm) are blended according to a mass ratio of 100:10:0.5, and then melt-blended and granulated by using a twin-screw blending extruder, to prepare a melt-blown co-crystallized polypropylene master batch containing N-H structure, and the temperature of the twin-screw blending extruder is set to 150-220℃.

[0030] Preparation of a co-crystallized polypropylene melt-blown non-woven material

[0031] The melt-blown co-crystallized polypropylene master batch is used for melt-blown spinning, and the melt-blown spinning process temperature is 230-280℃, to prepare a co-crystallized polypropylene melt-blown non-woven material.

[0032] Preparation of a sterilization and antivirus polypropylene melt-blown non-woven material

[0033] The co-crystallized polypropylene melt-blown non-woven material is immersed in a sodium hypochlorite solution, the mass concentration of sodium hypochlorite is 1%, the pH value is 3, the immersion temperature is 20℃, and the immersion time is 10 minutes, then the material is cleaned with water and dried, to prepare a sterilization and antivirus polypropylene melt-blown non-woven material.

[0034] Examples 2-5

[0035] Examples 2-3 respectively provide a bactericidal and antiviral polypropylene melt-blown non-woven material and a method for preparing the same, compared with Example 1, the difference is that the mass percentage of the functional monomer of the N-H containing and length controllable alkyl chain is changed, thus leading to the change of the bacteriostatic rate, the antiviral activity rate and the crystallinity.

[0036] The bacteriostatic rate, the antiviral activity rate and the mechanical properties of the products obtained in Examples 1-3 are compared

[0037] Examples 10-undecylenamide Bacteriostatic rate / % Antiviral activity rate / % Crystallinity / % Example 1 10 parts 99％ 99.9％ 35％ Example 2 5 parts 62.7％ 68.2％ 37％ Example 3 15 parts 99％ 99.9％ 33％

[0038] Examples 4-5 respectively provide a bactericidal and antiviral polypropylene melt-blown non-woven material and a method for preparing the same, compared with Example 1, the difference is that the alkyl chain length of the functional monomer of the N-H containing and length controllable alkyl chain is changed, that is, the number of carbon atoms of the long chain alkyl, thus leading to the change of the melt processing stability, the dispersibility and the crystallinity.

[0039]

[0040]

[0041] Examples 6-7 respectively provide a bactericidal and antiviral polypropylene melt-blown non-woven material and a method for preparing the same, compared with Example 1, the difference is that the mass percentage of the nucleating agent is changed, thus leading to the change of the crystallinity and the breaking strength of the melt-blown non-woven fabric.

[0042]

Claims

1. A bactericidal and antiviral polypropylene meltblown nonwoven material, characterized in that: This nonwoven material uses meltblown polypropylene and antibacterial functional monomers containing NH and alkyl chains with controllable length as raw materials. Meltblown polypropylene, functional monomers, and nucleating agents are melt-blended to obtain meltblown co-crystalline polypropylene masterbatch. The meltblown co-crystalline polypropylene masterbatch is then meltblown spun to obtain co-crystalline polypropylene meltblown nonwoven material. The co-crystalline polypropylene meltblown nonwoven material is then impregnated in sodium hypochlorite solution, washed, and dried to obtain antibacterial and antiviral polypropylene meltblown nonwoven material. The structural formulas of enamide antibacterial functional monomers containing NH and alkyl chains of controllable length are as follows: ； Wherein: R1 is a long-chain alkyl group with a carbon atom count ranging from 10 to 25; The crystallinity of this nonwoven material is 35-40%.

2. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 1, characterized in that: The meltblown spinning process temperature is 230~280 ℃.

3. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 1 or 2, characterized in that: The weight percentages of meltblown polypropylene, olefinic antibacterial functional monomers containing NH and controllable alkyl chains, and nucleating agents are 80-120 parts, 1-30 parts, and 0.1-10 parts, respectively.

4. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 3, characterized in that: The weight percentages of meltblown polypropylene, NH-containing alkyl chain-containing antibacterial functional monomers and nucleating agents are 100 parts, 5-20 parts and 0.2-1 parts, respectively.

5. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 4, characterized in that: The antibacterial functional monomers of olefin amides containing NH and alkyl chains with controllable length are 10-undecenoamide, hexenamide, or 9-octadecenoamide.

6. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 1, characterized in that: In the first step: the nucleating agent is an inorganic nucleating agent.

7. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 6, characterized in that: Inorganic nucleating agents are one or a mixture of two of calcium carbonate, titanium dioxide, and silicon dioxide.

8. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 7, characterized in that: The particle size of the inorganic nucleating agent is 100~800nm; the melt blending temperature is 150~240℃.

9. The antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 1, characterized in that: The sodium hypochlorite solution has a mass concentration of 0.1% to 5% and a pH of 1 to 9; the immersion temperature is 20 to 60°C; and the immersion time is 5 to 15 minutes.

10. A method for preparing the antibacterial and antiviral polypropylene meltblown nonwoven material according to claim 1, characterized in that: Meltblown-grade co-crystalline polypropylene masterbatch can be prepared by melt-blending meltblown-grade polypropylene, amide-type antibacterial functional monomers containing NH and controllable alkyl chains, and nucleating agents; meltblown-grade co-crystalline polypropylene masterbatch is then meltblown spun to obtain co-crystalline polypropylene meltblown nonwoven material; the co-crystalline polypropylene meltblown nonwoven material is then impregnated in sodium hypochlorite solution, washed, and dried to obtain antibacterial and antiviral polypropylene meltblown nonwoven material.

11. The application of the antibacterial and antiviral polypropylene meltblown nonwoven material of claim 1 in the preparation of masks and protective clothing.

Images