CN114427124B

CN114427124B - Antibacterial flame-retardant polypropylene fiber composition, preparation method thereof, fiber and non-woven fabric

Info

Publication number: CN114427124B
Application number: CN202011177412.4A
Authority: CN
Inventors: 郭鹏; 吕明福; 杨芝超; 初立秋; 徐耀辉; 张师军; 高达利; 宋文波; 尹华
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2020-10-29
Filing date: 2020-10-29
Publication date: 2024-02-13
Anticipated expiration: 2040-10-29
Also published as: CN114427124A

Abstract

The invention relates to an antibacterial flame-retardant polypropylene fiber composition, a preparation method thereof, fibers and non-woven fabrics, belonging to the technical field of polymer materials and plastic processing. The antibacterial flame-retardant polypropylene fiber composition comprises the following components in parts by weight: 100 parts of polypropylene base resin; 0.1-10 parts of elastomer and 0.05-4.0 parts of flame-retardant antibacterial agent, wherein the flame-retardant antibacterial agent is a polymer microsphere with guanidine salt grafted on the surface, and the polymer microsphere comprises a cross-linked structure of a structural unit A, a structural unit B and a structural unit C. The antibacterial flame-retardant polypropylene fiber is prepared from the antibacterial flame-retardant polypropylene fiber composition, and the antibacterial flame-retardant polypropylene non-woven fabric prepared from the fiber has the advantages of good filtering performance, small residual deformation, good touch feeling and good antibacterial flame-retardant performance.

Description

Antibacterial flame-retardant polypropylene fiber composition, preparation method thereof, fiber and non-woven fabric

Technical Field

The invention relates to the technical field of processing of high polymer materials and plastics, in particular to an antibacterial flame-retardant polypropylene fiber composition, a preparation method thereof, fibers and non-woven fabrics.

Background

Polypropylene resin is widely used for producing nonwoven fabrics due to its excellent mechanical formability, mechanical properties, high heat resistance, high cost performance and recyclability, and is applied to the fields of medical hygiene (medical masks, surgical gowns), labor protection and personal protection (dust masks, antifog haze masks, air purifier cartridges), personal hygiene articles (sanitary napkins, diaper, cotton wet tissues), and the like.

Among them, society in recent years has high demands on filterability of nonwoven products in the fields of environmental protection (e.g., PM2.5 haze particle protection) and personal health hygiene (air-spray transmissible infectious diseases such as H1N1, H5N6, SARS, covd-19). For example, a non-woven N95 mask is a particulate matter-proof mask certified by NIOSH (national institute of occupational safety and health). "N" means particles that are not suitable for oily properties; "95" means that the filtration efficiency reaches 95% under the detection conditions prescribed by the NIOSH standard. In order to enable the haze particles and bacterial virus filtration efficiency to reach 95%, the implementation means mainly comprise: the mesh density of the melt-blown layer is improved, a multi-layer composite non-woven fabric is used, the non-woven fabric subjected to electret treatment is used, and the adsorbent such as activated carbon, graphene and the like is added into a filter layer. Wherein, the fiber density of the non-woven fabric melt-blown layer is improved, the fiber diameter is reduced in the most convenient way, the production cost is improved lower, and the process is simple and convenient. The main way to achieve an increase in the mesh density of the nonwoven fabric is to reduce the denier of the nonwoven fabric, i.e. to use finer filaments.

The industrial production of finer tows is mainly achieved by using high melt index, narrow molecular weight distribution polypropylene as a starting material. The latter is achieved mainly by reducing the width of the molecular weight distribution of the polypropylene. The process for preparing polypropylene with narrow molecular weight distribution is generally obtained by peroxide degradation, but the use of peroxide, in addition to increasing production costs, also tends to cause taste in the final product, which affects the use of nonwoven products. Therefore, in order to improve the performance of polypropylene products and expand the application field, people are focusing on the development of new products of polypropylene with narrow molecular weight distribution so as to meet the demands of different fields on polypropylene resin. The polypropylene with narrow molecular weight distribution has wider Newtonian plateau area in the flowing process, the fluctuation of viscosity along with the change of shear rate is smaller, and the extrusion amount is easier to control stably. Raw fiber products of nonwoven fabrics, which generally require polymers having improved physical-mechanical properties such as flexural strength, impact resistance, and heat distortion resistance, require the use of polypropylene resins having a relatively narrow molecular weight distribution in combination with toughening and reinforcing polymers. In the aspect of spinning application, if the molecular weight distribution of the polypropylene is controlled to be narrow, the stability of the pressure of a spinning nozzle can be improved, and the fineness and uniformity of the ejected yarn can be ensured.

The molecular weight distribution of the polymer is directly affected by the properties of the catalyst employed in the polymerization reaction. For example, using metallocene catalysts, it is possible to produce narrow molecular weight distribution polypropylenes having molecular weight distributions of from 2.3 to 2.7. The oligomer content is obviously reduced, so that the peculiar smell generated in the resin processing process can be reduced, and the material performance is obviously improved. However, the metallocene catalyst has expensive loading cost, the activity of the loaded catalyst is low, the melt finger distribution uniformity of the product is required to be improved, and the catalyst is stableLimiting to a certain extent its range of application. Compared with a metallocene catalyst, the molecular weight distribution of polypropylene prepared by the Ziegler-Natta catalyst is wider, the MWD range is generally between 5 and 7, but the polypropylene has the advantages of low cost, high catalytic activity and the like, so that the preparation of the high-activity supported Ziegler-Natta catalyst and the obtaining of the polypropylene with the narrow molecular weight distribution and excellent material performance have wide application prospect. In recent years, research on the influence of Ziegler-Natta catalyst components, polymerization conditions, and the like on the molecular weight distribution of polypropylene has been started by various research institutions at home and abroad. Chinese patents CN103788259, CN103788260 and CN104250395 disclose a polypropylene with narrow molecular weight distribution and a preparation method thereof. It is characterized in that when the Ziegler-Natta catalyst preferably contains R ¹ ” _m” R ² ” _n” Si(OR ³ ”) _4-m”-n” The propylene polymer with narrow molecular weight distribution is directly prepared by using a reactor for polymerization under the condition that the indicated organosilicon compound is an external electron donor.

However, when a narrow molecular weight distribution polypropylene is used in the production of a melt blown layer, the high processing temperature used tends to degrade the polypropylene due to the need to maintain good melt flowability, which results in a decrease in the mechanical properties of the melt blown layer fibers, particularly in the tensile strength, which requires the addition of a toughening modifying resin to the base resin.

In order to further increase the filtration efficiency of the mask, it is necessary to reduce the fiber diameter and increase the electrostatic properties of the fibers, thereby adsorbing viruses and PM2.5 particles by the static electricity. It is necessary to incorporate a so-called electret in the resin. The electret refers to a dielectric material with a long-term charge storage function for releasing anions, and the stored charge can be single-polarity real charge (space charge) injected from outside or dipole charge formed by orderly orientation of dipoles in a polar dielectric, or two types of charges are simultaneously combined. The density and depth of the charge trapping energy traps in the melt-blown non-woven fabric are increased, negative ions are effectively released and charges are effectively stored, and the comprehensive filtering effect and thermal decay resistance of the melt-blown non-woven fabric are improved. The resistance of the non-woven fabric product is reduced and the filtering effect of the non-woven fabric product is improved under the condition of equal fiber fineness and gram weight.

When polypropylene is used in non-woven fabrics such as civil masks, the mouth and nose of a human body are contacted with the mask for many times, so that the mask can be used only once and is required to be discarded, and the product is wasted and the environment is polluted. The antibacterial agent is added into the non-woven fabric to inhibit bacteria, so that the service life of the household mask is prolonged. When the mask is sterilized by using ethanol for reuse, the mask is easy to burn, so that potential safety hazard is caused.

Therefore, there is a problem in that research and development of an antibacterial flame retardant polypropylene fiber composition, and fibers and nonwoven fabrics prepared therefrom are urgently needed.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides an antibacterial flame-retardant polypropylene fiber composition. In particular to an antibacterial flame-retardant polypropylene fiber composition, a preparation method thereof, fibers and non-woven fabrics. The antibacterial flame-retardant polypropylene fiber is prepared from the antibacterial flame-retardant polypropylene fiber composition, and the antibacterial flame-retardant polypropylene non-woven fabric prepared from the fiber has the advantages of good filtering performance, small residual deformation, good touch feeling and good antibacterial flame-retardant performance.

The invention aims at providing an antibacterial flame-retardant polypropylene fiber composition which comprises the following components in parts by weight:

100 parts of polypropylene base resin;

0.1 to 10 parts, preferably 1 to 5 parts, of an elastomer;

0.05 to 4.0 parts, preferably 0.2 to 3 parts, of flame retardant antibacterial agent.

Wherein,

the polypropylene base resin is a polypropylene base resin with narrow molecular weight distribution. In some embodiments of the present invention, the narrow molecular weight distribution polypropylene base resin has a molecular weight distribution M _w /M _n May be 3.7 to 5.7, preferably 4.0 to 4.5; polymer tailing index PI in molecular weight distribution width _HT May be greater than 2.3, preferably greater than 2.5; PI (proportional integral) _HT High indicating aggregationThe propylene has more remarkable macromolecular chain tail end, and the macromolecular chain tail end can be nucleated preferentially in crystallization, so that the crystallization temperature of polypropylene is increased, the crystallization speed is increased, the molding cycle is shortened, and the molding efficiency is improved. The isotacticity may be greater than 96%, preferably greater than 97%, more preferably greater than 98%; crystallization temperature T _C May be greater than 119 ℃, preferably greater than 121 ℃; the melt index MFR may be from 0.01 to 1000g/10min, preferably from 10 to 250g/10min, more preferably from 20 to 60g/10min.

In propylene polymerization, the molecular weight and melt flow rate of the polymer are usually adjusted by adding a chain transfer agent, which is usually hydrogen. The higher the hydrogen concentration, the lower the molecular weight of the resulting product and the higher the MFR. At the same time, chain transfer agents also have an effect on the molecular weight distribution of the polymer. It has been shown that for some high efficiency polypropylene catalysts, the molecular weight distribution width of the product is inversely proportional to the hydrogen added. Therefore, for the same narrow molecular weight distribution polypropylene, samples with low MFR are more difficult to prepare than samples with high MFR. The invention meets the requirements of narrow molecular weight distribution (for example, the molecular weight distribution index is 3.8-4.1) and lower MFR (for example, the MFR is 30-32 g/10 min) of polypropylene at the same time so as to adapt to the processing and use requirements of materials. The polypropylene base resin with narrow molecular weight distribution not only has narrow molecular weight distribution, but also has higher high molecular tailing index.

The polypropylene base resin with narrow molecular weight distribution does not use peroxide, and has low cost and no peculiar smell; the isotacticity is higher and adjustable, the melting point and the crystallization temperature are higher, and the mechanical strength is higher.

The elastomer can be at least one selected from ethylene propylene rubber (EPM), ethylene Propylene Diene Monomer (EPDM), ethylene/alpha-olefin random copolymer (POE), glycidyl methacrylate grafted POE, olefin Block Copolymer (OBC), polystyrene-polyethylene-polybutene-polystyrene (SEBS) and glycidyl methacrylate grafted SEBS;

Preferably, the elastomer can be at least one of ethylene propylene rubber (EPM), ethylene/alpha-olefin copolymer elasticity (POE) and Olefin Block Copolymer (OBC), glycidyl methacrylate grafted SEBS; more preferably, the POE is grafted with glycidyl methacrylate and the SEBS is grafted with glycidyl methacrylate.

The flame-retardant antibacterial agent can be a polymer microsphere with guanidine salt grafted on the surface, and the polymer microsphere can comprise a cross-linked structure of a structural unit A, a structural unit B and a structural unit C; wherein the structural unit a may be provided for maleic anhydride; the structural unit B may be provided for the monomer M; the structural unit C may be provided as a crosslinking agent;

wherein the monomers M may be provided by carbon four and/or carbon five;

the molar ratio of structural unit a to structural unit B may range from 0.5:1 to 1:0.5, preferably 0.75:1 to 1:0.75;

the polymer microsphere is dissolved in 5 times of acetone (50 ℃ C. And 30 min) to be less than or equal to 8wt% (such as 1wt%, 2wt%, 3wt%, 4wt%, 5.5wt%, 6.5wt%, 7.5wt%, 8wt% or any value between the above values);

the crosslinking degree of the flame-retardant and antibacterial polymer microsphere is more than or equal to 50 percent (such as 50 percent, 55 percent, 60 percent, 65 percent, 70 percent, 75 percent, 80 percent, 85 percent, 90 percent or any value between the above values), preferably more than or equal to 70 percent, and more preferably more than or equal to 90 percent.

The polymer microsphere is in a microsphere or spheroid shape; the average particle size is 200 to 2000nm (e.g., 2000nm, 250nm, 350nm, 450nm, 550nm, 650nm, 750nm, 850nm, 950nm, 1050nm, 1150nm, 1250nm, 1350nm, 1450nm, 1550nm, 1650nm, 1750nm, 1850nm, 2000nm, or any value therebetween). The guanidine salt flame-retardant antibacterial microsphere has a shell layer cross-linked structure, so that the guanidine salt flame-retardant antibacterial microsphere has better solvent resistance and thermal stability.

The crosslinking degree of the guanidine salt flame-retardant antibacterial microsphere represents the gel content, and is measured by a solvent extraction method. The average particle size is characterized by a number average particle size, as measured by means of a scanning electron microscope.

The crosslinking agent may be a vinyl-containing monomer capable of undergoing radical polymerization with various common difunctional or higher. Preferably, the crosslinking agent is divinylbenzene and/or propylene containing at least two acrylate groupsAnd the structural formula of the acrylic ester group is as follows: -O-C (O) -C (R') =ch ₂ R' is H or C1-C4 alkyl (such as methyl).

More preferably, the crosslinking agent may be selected from one or more of divinylbenzene, propylene glycol-based bis (meth) acrylate, ethylene glycol-based bis (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene glycol phthalate diacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, ethoxylated multifunctional acrylate, and the like;

The propylene glycol type di (methyl) acrylic ester can be selected from one or more of 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate and the like; the ethylene glycol di (meth) acrylate may be selected from one or more of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and the like.

The guanidine salt can be selected from one or more of small molecule guanidine salt and guanidine salt polymer, and the guanidine salt at least comprises one guanidine salt with flame retardance; the guanidine salt with flame retardance accounts for 30-100 wt% of the total weight of the guanidine salt; preferably 50 to 100 wt.%; more preferably 80 to 100wt%; specific examples are: 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 100%.

Wherein the small-molecule guanidine salt can be selected from one or more of guanidine phosphate, guanidine hydrochloride, guanidine nitrate, guanidine hydrobromic acid, guanidine oxalate, guanidine dihydrogen phosphate, guanidine hydrogen phosphate and amino guanidine salt; wherein the amino guanidine salt can be selected from one or more of aminoguanidine, diaminoguanidine and carbonate, nitrate, phosphate, oxalate, hydrochloride, hydrobromide, sulfonate of triaminoguanidine and other inorganic or organic salts; preferably guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, guanidine amino, diamino and guanidine nitrate, phosphate, hydrochloride, hydrobromide, sulfonate, etc.; further, one or more of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, nitrate, phosphate, hydrochloride, hydrobromide, sulfonate, etc. of aminoguanidine, diaminoguanidine and triaminoguanidine are preferable; still further, one or more of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, diguanidine hydrogen phosphate, guanidine hydrobromide, triaminoguanidine nitrate, aminoguanidine nitrate, triaminoguanidine phosphate, triaminoguanidine hydrochloride, triaminoguanidine hydrobromide, triaminoguanidine sulfonate, and the like are preferable.

The guanidine salt polymer can be selected from one or more of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine oxalate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyhexamethylene (bis) guanidine sulfonate, and other inorganic or organic salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine; preferably one or more of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, hexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine oxalate;

the guanidine salt with flame retardance can be selected from at least one of guanidine phosphate, guanidine hydrochloride, guanidine hydrobromic acid, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, and phosphate, hydrochloride, hydrobromide, nitrate, carbonate, oxalate, sulfonate of amino guanidine and polymer of guanidine salt; preferably at least one of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, amino guanidine phosphate, hydrochloride, hydrobromide, nitrate, sulfonate, polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate; wherein the amino guanidine is preferably at least one of amino guanidine, diamino guanidine and triaminoguanidine.

The polyhexamethylene (bis) guanidine hydrochloride mentioned above refers to polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and the like.

Flame retardant antimicrobial agents prepared and used in the present invention are described in association with application number 201911042238X, the entire contents of which are incorporated herein.

In some embodiments of the present invention,

the antibacterial flame-retardant polypropylene fiber composition can also comprise electrets; the electret can be used in an amount of 0.1-0.5 part by weight based on 100 parts by weight of the polypropylene base resin;

the electret can be at least one selected from aliphatic metal salts, piezoelectric ceramic powder or insulating polymer and other auxiliary agents capable of improving the electrostatic property of the melt-blown layer, and preferably at least one selected from zinc stearate, calcium stearate, sodium stearate, barium stearate, aluminum stearate, barium silicate, magnesium silicate, aluminum silicate, tourmaline, polytetrafluoroethylene and polyvinylidene fluoride. Barium silicate is preferred.

Wherein, preferably, the tourmaline has the general formula: XY ₃ Z ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ W ₄

X is mainly occupied by Na or Ca, possibly including K, or a part of vacancy vacancies;

y is mainly composed of Fe ²⁺ And (or) Mg ²⁺ ,Al ³⁺ ,Li ⁺ Or Fe (Fe) ³⁺ Is also generally covered by Mn ²⁺ And (or) Mn ³⁺ Occupying;

z is mainly composed of A1 ³⁺ ,Fe ³⁺ Or Cr ³⁺ May also include Mg ²⁺ And V ³⁺ The method comprises the steps of carrying out a first treatment on the surface of the Preferably A1 ³⁺ ,Fe ³⁺ Or Cr ³⁺ At least one of (a) and (b);

w is derived from OH ^- ,F ^- ,O ^2- Occupying.

In the present invention, Y is preferably Fe ²⁺ And (or) Mg ²⁺ Is a tourmaline.

In some embodiments of the present invention,

the antibacterial flame-retardant polypropylene fiber composition can also comprise at least one of aluminum hypophosphite flame retardant and melamine hydrobromide;

based on 100 parts by weight of the polypropylene base resin,

the weight of the aluminum hypophosphite flame retardant can be 0 to 2.0 parts, preferably 0.1 to 1.2 parts, more preferably 0 to 0.6 parts; the melamine hydrobromide may be present in an amount of 0 to 2.0 parts, preferably 0.1 to 1.2 parts, more preferably 0 to 0.8 parts;

wherein,

the aluminum phosphinate flame retardant can be selected from inorganic aluminum phosphinate and/or aluminum alkyl phosphinate; the aluminum alkyl phosphinate can be at least one selected from diethyl phosphinate aluminum, dipropyl phosphinate aluminum, phenyl phosphinate aluminum and the like; the aluminum phosphinate flame retardant is preferably selected from inorganic aluminum phosphinate and/or diethyl aluminum phosphinate.

In some embodiments of the present invention,

the antibacterial flame-retardant polypropylene fiber composition can also comprise a flame-retardant synergist;

The flame retardant synergist may be used in an amount of 0 to 1.0 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.05 to 0.6 part by weight, based on 100 parts by weight of the polypropylene base resin;

the flame retardant synergist can be at least one selected from 2, 3-dimethyl-2, 3-diphenyl butane (DMDPB, for short, cumyl) and p-isopropylbenzene polymer (cumyl).

In some embodiments of the present invention,

the antibacterial flame-retardant polypropylene fiber composition can comprise a slipping agent; the amount of the slipping agent may be 0.01 to 0.25 parts by weight, preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the polypropylene base resin;

the slipping agent can be at least one selected from stearamide, stearamide stearate, N, N' -ethylene bisstearamide, erucamide and oleamide. N, N' -ethylenebisstearamide is preferred.

In some embodiments of the present invention,

the antibacterial flame-retardant polypropylene fiber composition can comprise 0.10 to 0.4 weight part of nucleating agent; the nucleating agent may comprise a nucleating agent a and a nucleating agent B;

the amount of the nucleating agent A can be 0.05 to 0.2 weight parts based on 100 weight parts of the polypropylene base resin; the dosage of the nucleating agent B can be 0.05 to 0.2 weight part;

The nucleating agent A is an alpha nucleating agent and can be substituted aryl heterocyclic phosphate; preferably, the substituted aryl heterocyclic phosphate may be selected from at least one of sodium bis (p-tert-butylphenyl) phosphate, sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, aluminum 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, preferably aluminum 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate;

the nucleating agent B is beta nucleating agent and can be at least one of aryl dicarboxylic acid amide and N, N' -dicyclohexyl terephthalamide; among them, N' -dicyclohexyl terephthalamide is preferable.

In some embodiments of the present invention,

the antibacterial flame-retardant polypropylene fiber composition can also contain a mildew preventive; the mildew preventive may be used in an amount of 0 to 5.0 parts by weight, preferably 0.05 to 4.0 parts by weight, more preferably 0.1 to 3.6 parts by weight, based on 100 parts by weight of the polypropylene base resin;

the mildew preventive can be at least one of pyrithione, isothiazolinone, 10' -oxo-diphenol Oxazine (OBPA), 3-iodine-2-propynyl butyl carbamate (IPBC), 2, 4' -trichloro-2 ' -hydroxy diphenyl ether (triclosan), 2- (thiazole-4-yl) benzimidazole (thiabendazole) and the like with good mildew preventive effect;

Wherein the pyrithione is at least one selected from zinc pyrithione, copper pyrithione, dipyridyl thione, etc.;

the isothiazolinone may be selected from at least one of 2-methyl-1-isothiazolin-3-one (MIT), 5-chloro-2-methyl-1-isothiazolin-3-one (CMIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-n-octyl-3-isothiazolin-one (DCOIT), 1, 2-benzisothiazolin-3-one (BIT), 4-methyl-1, 2-benzisothiazolin-3-one (MBIT), 4-n-butyl-1, 2-benzisothiazolin-3-one (BBIT), and the like.

In the specific use, other functional auxiliary agents can be added, the thermoplastic resin is taken as 100 parts by weight, the dosage of the other functional auxiliary agents can be 0.1-100 parts by weight, and the specific dosage can be adjusted according to the needs. The other functional auxiliary agents can comprise at least one of antioxidants, light stabilizers, toughening agents, compatilizers, pigments, dispersants and the like.

The second purpose of the invention is to provide a preparation method of the antibacterial flame-retardant polypropylene fiber composition, which comprises the following steps:

and (3) melting and blending components comprising the polypropylene base resin, the flame-retardant antibacterial agent and the elastomer.

The method specifically comprises the following steps:

a. uniformly mixing components comprising polypropylene base resin, elastomer, aluminum phosphate flame retardant, melamine hydrobromide, antibacterial flame retardant, mildew inhibitor, electret and slipping agent; a high-speed mixer or a metering scale can be used for discharging;

b. and (c) extruding and granulating the mixed premix in the step (a), and drying to obtain the flame-retardant antibacterial polypropylene resin composition. In particular, instruments and equipment commonly used in the art, such as a twin screw extrusion granulator and the like, can be used.

A large number of experiments show that the guanidine salt flame-retardant antibacterial microsphere has good fluidity and low moisture absorption, and the guanidine salt does not adhere to walls in the preparation process of the flame-retardant antibacterial thermoplastic resin composition, is easy to discharge, is simple to produce and operate, and does not need excessive production condition control. The prepared flame-retardant antibacterial thermoplastic resin composition has good flame-retardant, antibacterial and mildew-proof effects and improved water resistance.

The preparation method of the flame-retardant antibacterial agent can comprise the following steps:

crosslinking and copolymerizing components comprising maleic anhydride, the monomer M and the crosslinking agent in the presence of an initiator to obtain polymer microspheres, and grafting the polymer microspheres with guanidine salt or guanidine salt solution to obtain the flame-retardant antibacterial agent;

Preferably, the method comprises the steps of,

the preparation method of the flame retardant antibacterial agent can comprise the following steps:

(1) In an organic solvent, in the presence of a first part of initiator, maleic anhydride and a first part of monomer M are contacted for reaction, and then a solution containing a cross-linking agent is introduced for continuous reaction; wherein the crosslinker-containing solution contains a crosslinker, optionally a second portion of monomer M, and optionally a second portion of initiator;

(2) And (3) adding guanidine salt or guanidine salt solution into the product obtained in the step (1) to continue the reaction, so that the guanidine salt is grafted on the surface of the product obtained in the step (1).

Wherein,

in the step (1) described above, the step of (c) is performed,

the ratio of the amount of maleic anhydride to the amount of the monomer M may be conventionally selected, but in a preferred embodiment of the present invention, the total amount of the first part of the monomer M and the second part of the monomer M in terms of terminal olefin may be 50 to 150mol, more preferably 75 to 100mol, with respect to 100mol of the maleic anhydride;

in the step (1), the monomer M may be fed in one step (i.e., the amount of the second portion of monomer M may be zero), or may be fed in two portions (i.e., the first portion of monomer M and the second portion of monomer M). According to a more preferred embodiment of the invention, the molar ratio between the second fraction of monomers M and the first fraction of monomers M is (0-100): 100 (e.g. 0, 1:100, 5:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value between the above values).

In the preparation method of the guanidine salt flame-retardant antibacterial microsphere, the dosage of the organic solvent can be selected conventionally as long as the medium is provided for the reaction in the step (1), and preferably, the dosage of the organic solvent can be 50-150L relative to 100mol of maleic anhydride.

In the step (1), the organic solvent may be a solvent common to various solution polymerization reactions, for example, the organic solvent includes an organic acid alkyl ester, that is, the organic solvent may be selected from an organic acid alkyl ester, or a mixture of an organic acid alkyl ester and an alkane, or a mixture of an organic acid alkyl ester and an aromatic hydrocarbon; wherein the alkyl esters of organic acids include, but are not limited to: at least one of methyl formate, ethyl formate, methyl propyl formate, methyl butyl formate, methyl isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propylene acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate; the alkanes include, but are not limited to: n-hexane and/or n-heptane. The aromatic hydrocarbons include, but are not limited to: at least one of benzene, toluene and xylene.

In the step (1) described above, the step of (c) is performed,

in the method for preparing the flame retardant antibacterial agent, the amount of the initiator is not particularly limited, and preferably, the total amount of the first part of initiator and the second part of initiator may be 0.05 to 10mol, preferably 0.5 to 5mol, and more preferably 0.8 to 1.5mol, with respect to 100mol of maleic anhydride. And/or the number of the groups of groups,

the amount of the crosslinking agent is not particularly limited, and preferably, the amount of the crosslinking agent may be 1 to 40mol, preferably 6 to 20mol, with respect to 100mol of maleic anhydride; and/or the number of the groups of groups,

in step (1), the initiator may be fed in one step (i.e., the amount of the second portion of initiator may be zero) or may be fed in two portions (i.e., the first portion of initiator and the second portion of initiator). According to a more preferred embodiment of the present invention, the molar ratio between the second part of initiator and the first part of initiator may be (0-100): 100 (e.g. 0, 1:100, 5:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value between the above values).

The initiator may be a reagent for initiating the polymerization reaction of maleic anhydride and olefin, which is common in the art, and may be a thermal decomposition type initiator. Preferably, the initiator may be selected from at least one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.

And/or the number of the groups of groups,

in the step (1), the maleic anhydride and the monomer M are contacted and reacted first, namely, the maleic anhydride and the monomer M are not reacted completely and only partially polymerized in the presence of an initiator. The conditions under which the maleic anhydride is contacted with the monomer M to react may be conventional conditions as long as the maleic anhydride is controlled to be only partially polymerized with the monomer M, and preferably, the conditions under which the maleic anhydride is contacted with the monomer M to react may include: the inert atmosphere is at a temperature of 50 to 90 ℃ (more preferably 60 to 70 ℃), a pressure (gauge pressure or relative pressure) of 0.3 to 1MPa (more preferably 0.4 to 0.5 MPa) and a time of 0.5 to 4 hours (more preferably 0.5 to 2 hours).

In the step (1), after maleic anhydride is contacted with the monomer M to carry out partial reaction, a solution containing a cross-linking agent is introduced to continue the reaction, so that the formation of a shell cross-linked structure is particularly facilitated. The conditions for continuing the reaction may be conventional conditions as long as the respective substrates are allowed to participate in the reaction as much as possible, and preferably, the conditions for continuing the reaction may include: the temperature is 50-90 ℃, the pressure is 0.3-1 MPa, and the time is 2-15 h. The temperature and pressure at which the reaction is continued may be the same as or different from the temperature and pressure at which the reaction is carried out by contacting the maleic anhydride with the monomer M as described above. According to a more preferred embodiment of the invention, the solution containing the crosslinking agent is introduced to continue the reaction in the following manner: the solution containing the cross-linking agent is added dropwise to the product obtained in step (1) at 50-90 ℃ (more preferably 60-70 ℃) for 1-3 hours, and the reaction is continued for 1-4 hours at a constant temperature.

In the method for producing the flame retardant antibacterial agent, the kind and content of the solvent in the solution containing the crosslinking agent are not particularly limited as long as the solute therein is sufficiently dissolved, and in general, the kind of the solvent in the solution containing the crosslinking agent may have the same choice as the organic solvent (i.e., include an alkyl ester of an organic acid as described above), and the content of the crosslinking agent in the solution containing the crosslinking agent may be 0.2 to 3mol/L.

In the step (2), the step of (c),

adding the guanidine salt or the guanidine salt aqueous solution into the product obtained in the step (1), and carrying out a reaction by rapid stirring; the amount of the guanidine salt may be conventionally selected, and preferably, the amount of the guanidine salt may be 5g to 5000g, preferably 20g to 3000g, more preferably 100g to 2000g, with respect to 1000g of maleic anhydride;

the guanidine salt aqueous solution may be used in an amount of 500 to 10000g, preferably 1000 to 8000g, more preferably 1000 to 6000g, with respect to 1000g of maleic anhydride. The concentration of the aqueous guanidine salt solution can be 0.5 to 50wt%, preferably 1 to 30wt%, more preferably 1 to 20wt%. And/or the number of the groups of groups,

in the step (2), the step of (c),

the grafting reaction may be carried out under conventional conditions, for example, the conditions of the grafting reaction may include: the temperature may be 0 to 100 ℃, preferably 2.5 to 90 ℃, more preferably 5 to 80 ℃, still more preferably 30 to 80 ℃; the reaction time may be 0.5 to 10 hours, preferably 0.5 to 8 hours, more preferably 0.5 to 6 hours; the stirring speed may be 50 to 1000rpm, preferably 50 to 500rpm, more preferably 100 to 500rpm.

In the step (2), the product (suspension) obtained in the step (1) may be subjected to a post-treatment (separation, washing and drying) and then subjected to a grafting reaction. The product obtained after drying is directly added into guanidine water solution for reaction. The washing may employ a conventional washing solvent, for example, at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether and methyl tertiary butyl ether. The concentration of the aqueous guanidine salt solution can be 0.5 to 50wt%, preferably 1 to 30wt%.

The final product obtained in the step (2) is subjected to further separation treatment to obtain the guanidine salt flame-retardant antibacterial microsphere product, for example, the separation treatment is carried out in the following manner: centrifugal separation, washing with water, washing with an organic solvent (that is, at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether and methyl tert-butyl ether may be used as the washing solvent as described above), centrifugal separation, and drying (e.g., vacuum drying) may be performed.

The inventor of the present invention found in the research that the guanidine salt flame-retardant antibacterial microsphere product of the present invention can be effectively prepared by directly grafting the suspension obtained in the step (1) with the aqueous guanidine salt solution without performing the step of removing the organic solvent. Thus, according to a preferred embodiment of the present invention, in step (2) of the present invention, the product obtained in step (1) may be directly reacted with an aqueous solution of a guanidine salt polymer (one pot method), thus obtaining a mixed system containing guanidine salt flame-retardant antibacterial microspheres, which is subjected to further separation treatment to obtain a guanidine salt flame-retardant antibacterial microsphere product, for example, by the following separation treatment: standing for layering, recycling the organic phase, centrifuging the heavy phase, washing with water, centrifuging, and drying (such as vacuum drying) to obtain guanidine salt flame-retardant antibacterial microsphere. The optimized method adopts a one-pot process, only one-time liquid-liquid separation, solid-liquid separation, washing and drying are needed for the product post-treatment, so that the time consumption of a single batch is effectively shortened, the process flow is simplified, unit equipment is reduced, and the energy consumption is effectively reduced; the process only needs one organic solvent as a reaction medium, the solvent can be recycled by layering and drying operations, no special water dividing device is needed, layering can be realized in the reactor, the solvent can be recycled without distillation and purification, energy saving and consumption reduction are realized, and the pollution of the used organic solvent to the environment can be effectively reduced.

The preparation method of the polypropylene base resin may include the steps of:

(1) Carrying out propylene prepolymerization reaction in the presence of a catalyst to obtain a propylene prepolymer;

(2) And (3) carrying out propylene polymerization in the presence of the propylene prepolymer obtained in the step (1).

Wherein,

in the step (1) described above, the step of (c) is performed,

the catalyst may be a Ziegler-Natta catalyst;

the reaction conditions of the prepolymerization reaction may include: in the gas phase or liquid phase, propylene is subjected to a prepolymerization reaction; the reaction temperature may be 0 to 25 ℃, preferably 10 to 20 ℃; the prepolymerization pressure can be 0.1 to 10.0MPa, preferably 1.5 to 3.5MPa; and/or the number of the groups of groups,

the prepolymerization times can be controlled to be 2 to 3000 g polymer/g catalyst, preferably 3 to 2000 g polymer/g catalyst. Wherein, the term "prepolymerization multiple" refers to the ratio of the weight of the prepolymer to the weight of the catalyst originally added.

In the step (2), the method specifically may include: and (3) carrying out propylene homo-polymerization or copolymerization reaction in a gas phase or a liquid phase in the presence of the propylene prepolymer obtained in the step (1) to obtain a propylene polymer.

The conditions for the propylene polymerization reaction may include:

the reaction temperature can be 80-150 ℃, preferably 80-100 ℃; and/or the number of the groups of groups,

The reaction pressure can be 1-6 MPa, preferably 2-5 MPa; and/or the number of the groups of groups,

the polymerization time can be 0.5 to 5 hours.

The polymerization reaction is preferably carried out in a gas-phase horizontal reaction kettle; the horizontal reaction kettle is provided with a horizontal stirring shaft, and adopts quenching liquid to remove heat; the stirring speed in the gas phase horizontal kettle can be 10-150 revolutions per minute, and the stirring blade can be one or more of T-shaped, rectangular, inclined slurry, door-shaped and wedge-shaped; the polymerization time or residence time is preferably controlled to be 1 to 3 hours; by means of molecular weight regulators H ₂ Controlling the melt flow rate of the polymer; the MFR of the resulting polymer can be controlled to be in the range of 0.01 to 1000g/10min, preferably 10 to 250g/10min, more preferably 20 to 60g/10min. The polypropylene product with high isotacticity is obtained by changing the polymerization temperature control in the step (2), and the narrow molecular weight distribution is realized.

According to some preferred embodiments of the present invention, the step (1) and the step (2) may be performed in one reactor for batch polymerization or may be performed in a different reactor for continuous polymerization. In a specific embodiment, step (1) is carried out continuously in a vertical stirred tank, while step (2) is carried out continuously in a horizontal stirred tank, i.e. the continuous polymerization is carried out in a different reactor.

The narrow molecular weight distribution polypropylene base resin prepared and used in the present invention is described in publication No. CN106632761A (201510418659.3, entitled "narrow molecular weight distribution polypropylene and method of preparing same"), the entire contents of which are incorporated herein by reference.

The invention further provides an antibacterial flame-retardant polypropylene fiber, which can be prepared according to the antibacterial flame-retardant polypropylene fiber composition or the antibacterial flame-retardant polypropylene fiber composition prepared according to the preparation method through a melt blowing method or a spunbonding method;

preferably, the average diameter of the antibacterial flame-retardant polypropylene fiber is 0.01-30 mu m;

more preferably, the antimicrobial flame retardant polypropylene fibers may be microfibers; in particular, the meltblown fibers may be microfibers or, more particularly, they may be fibers having an average diameter of about 15 to 30 μm; and/or the antibacterial flame retardant polypropylene fiber may have a denier of 0.05 to 8, preferably l.5 to 3.0. The non-woven fabric prepared by the tight arrangement of the denier ranges can meet the requirements of non-woven fabrics used for masks with the filtration rate of more than 90 percent required by NIOSH.

The fourth object of the present invention is to provide an antibacterial flame retardant polypropylene nonwoven fabric (nonwoven fabric) which can contain the antibacterial flame retardant polypropylene fiber;

The antibacterial polypropylene nonwoven of the present invention may be composed of continuous or discontinuous fibers (e.g., staple fibers). The fibers of the present invention are well suited for use in the manufacture of nonwoven fabrics.

The nonwoven fabric may have a weight of 0.015 to 0.25kg/m ² The weight per unit area is preferably 0.015 to 0.03kg/m ² Is heavy per unit area;

the nonwoven fabric has an average filament denier of 0.05 to 8, and a decrease in the average filament denier can produce a softer nonwoven fabric due to the use of polypropylene having a narrow molecular weight distribution. For example, when the filament denier reaches 0.05 to 1 denier, the nonwoven fabric has greater softness. As a relationship between denier and fiber diameter, reference is made to, but not limited to, denier = 1.73d, d being fiber diameter.

The fifth object of the present invention is to provide the use of said one antimicrobial flame retardant polypropylene fiber composition or said one antimicrobial flame retardant polypropylene fiber or said one antimicrobial flame retardant polypropylene nonwoven in any of the fiber product fields known in the art, preferably any of infant, feminine hygiene products, personal protection products, surgical gown fibers and carpet fibers; wherein, the personal protection product is preferably a mask, more preferably an N95 mask.

The term "base resin" as used herein refers to a neat resin, i.e., a resin that does not form a composition.

The term "nonwoven fabric" as used herein refers to a fabric formed without spinning a fabric, which is simply formed by orienting or randomly arranging woven staple or filaments to form a web structure, and then reinforcing the web structure by mechanical, thermal, or chemical means. The preparation method of the non-woven fabric mainly comprises the following steps: airlaid, meltblowing, spunbonding and carding.

The term "microfibers" as used herein refers to small diameter fibers having an average diameter of no greater than 100 microns.

The term "spunbond fibers" as used herein refers to small diameter fibers formed as follows: the molten thermoplastic material is extruded in the form of filaments from a plurality of fine, generally annular capillaries of a spinneret with the diameter of the extruded filaments then being rapidly attenuated by drawing.

"meltblown fibers" means fibers formed by drawing a stream of polymer melt extruded through a die orifice with a stream of high velocity hot air to form ultrafine fibers, known as meltblown fibers, which are collected on a web curtain or drum and bonded to themselves to form a meltblown web.

The term "optionally" as used herein means with or without the inclusion of, and also with or without the addition of.

The manner of mixing the compositions disclosed in the present invention includes mixing the components by a high speed mixer and subsequent melt mixing, or in a separate extruder (e.g., single screw technology, twin screw, multiple screw, buss kneader).

Compared with the prior art, the invention has the following beneficial effects:

(1) The non-woven fabric prepared by the fiber obtained by taking the polypropylene with narrow molecular weight distribution as the raw material can be widely applied to the fields of medical sanitation (medical mask and operating gown), labor protection and personal protection (dustproof mask), personal hygiene products (sanitary towel, diaper, cotton wet towel) and the like.

(2) The polypropylene non-woven fabric prepared by the invention has a non-crosslinked structure, can be recycled according to a common polypropylene modified material, does not cause secondary pollution, and meets the requirement of recycling economy.

(3) After the polypropylene with narrow molecular weight distribution is used, the torque of the spunbonding or melt-blowing extrusion mechanism is obviously reduced, the stability of the pressure of a spinning nozzle can be improved, and the fineness and uniformity of the ejected yarn are ensured.

(4) The product obtained by the narrow molecular weight distribution polypropylene prepared by the hydrogen telomerization method through a relative degradation method has lower content of volatile organic compounds (volatile organic compounds, VOC), and the product prepared into non-woven fabrics used for personal protection articles such as masks and the like is nontoxic, harmless and odorless.

(5) The invention provides a flame-retardant antibacterial polymer microsphere and a preparation method thereof, and the single-component guanidine salt microsphere with flame-retardant and antibacterial functions is prepared through structural design and formula regulation. Compared with the prior method of adding the flame retardant and the antibacterial agent respectively, the guanidine salt microsphere is easy to disperse in the thermoplastic resin substrate, and effectively improves the flame retardant and antibacterial efficiency.

(6) The invention provides a low-additive flame-retardant antibacterial thermoplastic resin composition and a preparation method thereof. The thermoplastic resin composition with flame retardance and antibacterial property is prepared by introducing the high-efficiency multifunctional single-component flame-retardant antibacterial microspheres through formula regulation. The flame retardant and antibacterial efficiency of the auxiliary agent are improved, the addition amount of the auxiliary agent is reduced, the dispersion performance is improved, and the prepared polypropylene composition has excellent comprehensive performance.

Detailed Description

The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

The invention will be described in further detail with reference to the following examples, which should be construed as: the present invention is by no means limited to these examples. The related data in the embodiment of the invention are obtained according to the following test method:

(1) Molecular weight distribution breadth index Mw/Mn, peak position molecular weight Mp, weight average molecular weight Mw and Z average molecular weight Mz: the gel permeation chromatograph with the model PL-GPC220 manufactured by UK Polymer Laboratories company is combined with an IR5 infrared detector, wherein the chromatographic column of the gel chromatograph is 3 serially connected Plgel 10 μm MIXED-B columns, the solvent and the mobile phase are 1,2, 4-trichlorobenzene (containing 0.3g/1000mL of antioxidant 2, 6-di-tert-butyl-p-cresol), the column temperature is 150 ℃, the flow rate is 1.0mL/min, and the universal calibration is carried out by adopting EasiCal PS-1 narrow distribution polystyrene standard sample manufactured by PL company.

(2) Polymer tailing index PI in molecular weight distribution width _HT : the peak molecular weight Mp, the weight average molecular weight Mw and the Z average molecular weight Mz measured by the above method (1) are calculated according to the following formula:

PI _HT ＝10 ⁵ ×(Mz/Mp)/Mw (1)

(3) Degree of isotacticity: measured according to the method described in national standard GB/T2412.

(4) Crystallization temperature T _C : the instrument was calibrated with metallic indium and zinc standards by using a DIAMOND DSC (PE company), the sample mass was about 5mg, the atmosphere was nitrogen, and the air flow was 20mL/min. Heating the to-be-detected granular material sample containing the antioxidant to 210 ℃ at a speed of 10 ℃ per minute, keeping the temperature for 5 minutes to eliminate the heat history, then cooling to 50 ℃ at a cooling speed of 10 ℃ per minute, recording a crystallization heat release curve, and recording the temperature corresponding to the peak value of the crystallization heat release curve as a crystallization temperature T _C 。

(5) Melt flow rate MFR: measured according to ISO1133, 230℃under a load of 2.16 kg.

(6) The titanium atom content of the titanium-containing solid catalyst component and the Ziegler-Natta catalyst were measured by using a 721 spectrophotometer available from the scientific development Co., ltd.

(7) Particle size and particle size distribution of the magnesium alkoxide and the catalyst were measured by a Malvern Mastersizer TM laser particle sizer, and n-hexane was used as a dispersant (span= (D90-D10)/D50).

(8) Determination of m value in magnesium alkoxide compound: 0.1 g of an alkoxy magnesium compound was taken, 10mL of an aqueous hydrochloric acid solution having a concentration of 1.2mol/L was added thereto, and the mixture was decomposed by shaking for 24 hours, and ethanol and 2-ethylhexanol therein were measured by a gas chromatograph (available from Allen analysis instruments Co., ltd., model GC-7960), and then the value of m was calculated according to the following formula:

wherein w1 is the mass of 2-ethylhexanol and w2 is the mass of ethanol.

(9) The content of internal electron donor in Ziegler-Natta catalysts was determined using Waters 600E liquid chromatography or gas chromatography.

(10) Heat distortion temperature HDT: measured according to ASTM D648. A load of 455kPa was placed at the center of a standard test piece of 127X 13X 3mm, and the temperature was raised at 2℃per minute to a temperature at which the deformation amount was 0.25 mm.

(11) Flexural modulus and flexural strength of polypropylene: measured according to ASTM D790-97, GB/T9341-2008 standard.

(12) Tensile strength of polypropylene: measured according to ASTM D638-00, GB/T1040.2-2006 standard.

(13) Izod notched impact strength (IZOD 23/-20 ℃ C.) of polypropylene: measured according to ASTM D256-00, GB/T1843-2008 standard.

(14) Flexural rigidity of nonwoven fabrics was tested by ASTM D5732-95:

A test specimen for flexural rigidity was obtained by cutting a 1 inch long by 6 inch long strip from the center of the cloth, with the long axis of the strip aligned parallel to the Machine Direction (MD) of the cloth. MD is defined as the direction of a web parallel to the collector motion or conveyor motion during web formation. For each sample, the basis weight (in grams per square meter) was determined by dividing the measured sample weight by the analytical balance (model BSA223S-CW, cerdolis, measured by area square meters). Flexural stiffness (G) of the cloth samples was measured according to ASTM D5732-95. C is calculated using the following formula 2.

G＝9.8m*C ³ 10 ^-3 (mN cm) (2)

Where G is the average flexural rigidity per unit width in milliNewton cm of the test piece (test piece), m is the basis weight of the sample measured in grams per square meter, and C is the flexural length in cm. For all measurements, the indicator was inclined 41.50 ° to the horizontal.

(15) Tensile Strength test of nonwoven fabrics ASTM D4595-11:

a2.5 cm wide by 15cm long strip was cut from the center of the web in the Machine Direction (MD) to obtain a sample for nonwoven fabric measurement. Basis weight in grams per square meter for each sample. The sample was then loaded into an Instron5967 equipped with a 100N sensor (calibrated and balanced) and a pneumatic wire contact clamp (plain end clamp face rubber coated) with an initial spacing of 2.5 inches in parallel with the crosshead displacement MD. This was done by first inserting the sample into the upper clamp and snapping the upper clamp to clamp 3cm from the narrow side of the sample. The elongation at break measurement was done using a contact extensometer. The sample was stretched at a speed of 0.5cm/s to break. Load and elongation (0.5% strain delta) were recorded per 0.25 mm displacement. The strain was calculated by dividing the clamp displacement by 5cm and multiplying by 100. The folded load (gf/gsm/2.5 cm width) was calculated by dividing the force measured in grams (gf) by the basis weight of the 2.5cm wide sample described above.

(16) Oxygen index test: the test was carried out according to the method described in national standard GB/T5454-1997.

(17) Glowing filament flammability index experimental standard number: GB/T5961.11-2006.

(18) Particulate matter filtration efficiency was tested according to the method described in GB 2626-2019.

Antibacterial detection standard and operation steps:

1. antibacterial test criteria: GB/T31402-2015 plastic surface antibacterial property test method for detecting bacteria: coli (Escherichia coli) ATCC 25922, staphylococcus aureus (Staphylococcus aureus) ATCC 6538.

2. An antibacterial test step, namely, testing by referring to an antibacterial plastic detection standard GB/T31402-2015, wherein the specific steps are as follows: and (3) sterilizing the sample to be tested by using 75% ethanol, airing, and diluting the strain into a bacterial suspension with proper concentration by using sterile water for standby. 0.2mL of the bacterial suspension was dropped onto the surface of the sample, and a polyethylene film (4.0 cm. Times.4.0 cm) of 0.1mm thickness was applied thereto to form a uniform liquid film between the sample and the film. The culture is carried out for 18 to 24 hours at 37 ℃ with a relative humidity of 90 percent. The bacterial liquid is washed down by sterile water, diluted into proper concentration gradient, and 0.1mL of the bacterial liquid is evenly coated on the prepared sterile agar medium. The cells were incubated at 37℃for 18 to 24 hours, and the results were observed. The negative control was replaced with a sterile dish and the other operations were the same.

3. The degree of crosslinking of the guanidine salt antibacterial microspheres is expressed in terms of gel content, as measured by a solvent extraction method. The specific method comprises the following steps: weighing a sample to be measured W ₁ Then placing the sample to be tested in acetone with 5 times of weight, extracting at 50 ℃ for 30min, and measuring and drying W2 after the extraction is finished, wherein the crosslinking degree is W ₂ /W ₁ X 100%. The content of the soluble matters is (1-W) ₂ /W ₁ )×100％。

Antibacterial pellets are prepared:

XQ101:

(1) The composition of the mixed butene gas is as follows: trans-2-butene, 40.83% by weight; cis-2-butene, 18.18% by weight; n-butane, 24.29 wt%; n-butene, 9.52 wt%; 2.78% by weight of isobutene; other, 4.4 wt%. 100g of maleic anhydride and 2g of azodiisobutyronitrile are dissolved in 800mL of isoamyl acetate to form solution I, metered mixed butene (the molar ratio of the maleic anhydride to the effective component (terminal olefin) in the mixed olefin is 1:1) is introduced, and the mixture is reacted for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;

(2) 25g of divinylbenzene is dissolved in 200mL of isoamyl acetate to obtain a solution II, the solution II is added into the reaction system by a plunger pump, the dropwise addition is carried out for 2 hours, and after the dropwise addition is finished, the reaction system is kept warm for reaction for 3 hours.

(3) After the reaction, the pressure was released, 200g (15 wt%) of each of guanidine dihydrogen phosphate and polyhexamethylene biguanide hydrochloride aqueous solution was added thereto, and the reaction was carried out at 80℃for 3 hours. And standing and layering the reacted system, centrifugally separating a heavy phase for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 4L of water into the solid, stirring and washing, centrifugally separating the solid for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the flame-retardant antimicrobial agent, namely the polymer microsphere 1# with the surface grafted with the guanidine salt. The average particle diameter of the obtained polymer microspheres is 1280nm. The resulting polymer microspheres were dissolved in 5 weight percent acetone at 50℃for 30min to give a dissolution of 5.5 weight percent.

XQ102

Flame retardant antibacterial agents were prepared as in example 1, except that the system after the reaction in step (2) was centrifuged at 5000rad/min for 30 minutes by a centrifuge to obtain crosslinked mixed butene/maleic anhydride polymer microspheres, which were purified by washing with n-hexane and dried in vacuo. Then, the dried crosslinked mixed butene/maleic anhydride polymer microspheres were added to 400g of a mixed aqueous solution of guanidine dihydrogen phosphate (20 wt%), polyhexamethylene biguanide hydrochloride (20 wt%), and reacted at 80℃for 3 hours. Centrifugally separating the reacted system for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 4L of water into the solid, stirring and washing, centrifugally separating the solid for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the flame-retardant antimicrobial agent, namely the polymer microsphere 2# with the surface grafted with the guanidine salt. The average particle diameter of the obtained polymer microspheres was 1310nm. The resulting polymer microspheres were dissolved in 5 times the weight of acetone at 50℃for 30min to give a dissolution of 5.6% by weight.

XQ103:

(1) 100g of maleic anhydride and 2g of azobisisobutyronitrile are dissolved in 800mL of isoamyl acetate to form a solution I, metered mixed butene (the molar ratio of the maleic anhydride to the effective components (terminal olefin) in the mixed olefin is 1:1) is introduced, and the mixture is reacted for 2 hours at 70 ℃ and 0.4MPa under the nitrogen atmosphere;

(2) 15g of divinylbenzene is dissolved in 200mL of isoamyl acetate to obtain a solution II, the solution II is added into the reaction system by a plunger pump, the dropwise addition is carried out for 2 hours, and after the dropwise addition is finished, the reaction system is kept warm for reaction for 3 hours.

(3) After the reaction, the pressure was released, 200g (20 wt%) of guanidine hydrobromide and 200g (20 wt%) of polyhexamethylene guanidine phosphate aqueous solution were added, respectively, and the reaction was carried out at 60℃for 7 hours. And standing and layering the reacted system, centrifugally separating a heavy phase for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 4L of water into the solid, stirring and washing, centrifugally separating the solid for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the flame-retardant antimicrobial agent, namely the polymer microsphere 3# with the surface grafted with the guanidine salt. The average particle diameter of the polymer microspheres obtained was 1210nm. The resulting polymer microspheres were dissolved in 5 times by weight of acetone at 50℃for 30min in a weight percentage of 6.5%.

XQ104:

(1) 100g of maleic anhydride and 1.5g of azobisisobutyronitrile are dissolved in 800mL of isoamyl acetate to form solution I, metered mixed butene (the molar ratio of the maleic anhydride to the effective component (terminal olefin) in the mixed olefin is 1:0.75) is introduced, and the mixture is reacted for 1 hour at 70 ℃ and 0.5MPa under nitrogen atmosphere;

(2) 0.5g of azobisisobutyronitrile and 18g of divinylbenzene are dissolved in 200mL of isoamyl acetate to obtain a solution II, the solution II is added into a reaction system by a plunger pump, the dropwise addition is carried out for 2 hours, and after the dropwise addition is finished, the reaction system is kept warm for reaction for 3 hours.

(3) After the reaction, the pressure was released, and 200g (20 wt%) of guanidine phosphate, 200g (20 wt%) of guanidine hydrobromide, and 200g (20 wt%) of polyhexamethylene guanidine phosphate aqueous solution were added, respectively, and the reaction was carried out at 60℃for 10 hours. And standing and layering the reacted system, centrifugally separating a heavy phase for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 4L of water into the solid, stirring and washing, centrifugally separating the solid for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the flame-retardant antimicrobial agent, namely the polymer microsphere 4# with the surface grafted with the guanidine salt. The average particle diameter of the obtained polymer microspheres was 1510nm. The resulting polymer microspheres were dissolved in 5 times the weight of acetone at 50℃for 30min at a weight percentage of 5.8%.

XQ105：

(1) The composition of the mixed carbon five gas is as follows: diene (isoprene, cyclopentadiene, 1, 4-pentadiene, piperylene), 47.83% by weight; mono-olefins (1-pentene, 2-pentene, cyclopentene, 2-methyl-1-butene, 2-methyl-2-butene), 13.18% by weight; alkane (n-pentane, isopentane, cyclopentane, 2-methylbutane), 21.29 wt.%; alkyne (butyne-2, 3-pentene-1 alkyne), 0.92% by weight; others 16.78 wt%. Dissolving 100g of maleic anhydride and 2g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed carbon five (the molar ratio of the maleic anhydride to the effective component (terminal olefin) in the mixed olefin is 1:0.5), and reacting for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;

(2) And 15g of the metered mixed carbon five (the molar ratio of maleic anhydride to the effective component (terminal olefin) in the part of mixed olefin is 1:0.5) and divinylbenzene are dissolved in 200mL of isoamyl acetate to form a solution II, the solution II is added into a reaction system by a plunger pump, dropwise adding is carried out for 2 hours, and after the dropwise adding is finished, the reaction system is kept warm for reaction for 3 hours.

(3) And (3) after the reaction, decompressing, standing and layering the system, centrifugally separating a heavy phase for 20 minutes at 5000rad/min by a centrifugal machine, adding 400mL of water into the solid, stirring and washing, centrifugally separating the solid for 20 minutes at 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the crosslinked mixed pentene/maleic anhydride polymer microsphere.

(4) 100g of crosslinked mixed pentene/maleic anhydride polymer microspheres were added to 400g of a mixed solution of aminoguanidine nitrate (15 wt%) and polyhexamethylene biguanide phosphate (15 wt%) and reacted at 50℃for 6 hours. Centrifugally separating the reacted system for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 4L of water into the solid, stirring and washing, centrifugally separating the solid for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the flame-retardant antimicrobial agent, namely the polymer microsphere 5# of the surface grafted guanidine salt polymer. The average particle size of the resulting polymer microspheres was 1458nm. The resulting polymer microspheres were dissolved in 5 times the weight of acetone at 50℃for 30min to give a dissolution of 5.6% by weight.

XQ106：

The flame retardant antimicrobial agent was prepared as in example 5, except that the amount of divinylbenzene in step (2) was changed to 10g, and finally polymer microspheres # 6 were obtained. The average particle diameter of the obtained polymer microsphere is 1200nm. The resulting polymer microspheres were dissolved in 5 times by weight of acetone at 50℃for 30min in a weight percentage of 7.0%.

XQ107：

The flame retardant antimicrobial agent was prepared as in example 1, except that the divinylbenzene in step (1) was changed to 36.0g of pentaerythritol tetraacrylate, finally obtaining polymeric microspheres 7#. The average particle size of the resulting polymer microspheres was 1320nm. The resulting polymer microspheres were dissolved in 5 times the weight of acetone at 50℃for 30min to give a dissolution of 5.2% by weight.

Preparation of polypropylene base resin HPP:

1. preparation of Polypropylene base resin HPP101

1) Raw materials

Preparation of the main catalyst: the 16L pressure-resistant reactor with stirrer was replaced with nitrogen gas, and 10L ethanol, 300mL 2-ethylhexanol, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder were added to the reactor and stirred and mixed uniformly, and the system was heated to 75℃while stirring to reflux the reaction until no more hydrogen gas was discharged. Stopping the reaction, washing with 3L ethanol, filtering and drying to obtain the dialkoxy magnesium carrier. The D50 was 30.2. Mu.m, SPAN was 0.81 and m was 0.015. 650g of the magnesium dialkoxide carrier, 3250mL of toluene and 65mL of di-n-butyl phthalate (DNBP) were taken and suspended. Adding 2600mL of toluene and 3900mL of titanium tetrachloride into a 16L pressure-resistant reaction kettle repeatedly replaced by high-purity nitrogen, heating to 80 ℃, adding the prepared suspension into the kettle, keeping the temperature for 1 hour, adding 65mL of di-n-butyl phthalate (DNBP), slowly heating to 110 ℃, keeping the temperature for 2 hours, and performing pressure filtration to obtain a solid. The resulting solid was added to a mixture of 5070mL of toluene and 3380mL of titanium tetrachloride, and then stirred at 110℃for 1 hour, thus being treated 3 times. And (3) filter pressing, washing the obtained solid with hexane for 4 times, wherein the dosage of each time is 600mL, filter pressing and drying to obtain the main catalyst solid component. The obtained catalyst solid component had a titanium atom content of 2.4% by weight and a di-n-butyl phthalate (DNBP) content of 9.5% by weight.

Triethylaluminum is used as a cocatalyst during polymerization; diethylaminotriethoxysilane (DAMTS) was used as an external electron donor; propylene and hydrogen are polymerization grade, and are used after water and oxygen are removed; hexane is used after dehydration.

2) Test device

The device adopts continuous kettle type prepolymerization and horizontal kettle gas phase series polymerization technology. The prepolymerization reactor is a vertical stirring kettle with jacket cooling, the volume is 5 liters, the stirring blade is turbine inclined slurry, and the stirring speed is 500 revolutions per minute; the horizontal gas phase reactor is a horizontal stirring kettle, the volume is 0.2 cubic meter, the stirring paddle is a T-shaped inclined blade, the inclination angle is 10 degrees, and the stirring speed is 100 revolutions per minute.

3) Test conditions

The first step of prepolymerization: the reaction pressure is 2.39MPa, the reaction temperature is 15 ℃, and the reaction time is 15 minutes; the feed amounts of the main catalyst, triethylaluminum, and Diethylaminotriethoxysilane (DAMTS) were 1.3g/hr, 0.067mol/hr, and 0.0058mol/hr, respectively; al/Si molar ratio of 8.59; the propylene feed amount was 15kg/hr.

Second step gas phase polymerization: the homopolymerization reaction temperature is 85 ℃, the reaction pressure is 2.35MPa, and the reaction time is 85 minutes; the propylene feed amount was 10kg/hr; the hydrogen/propylene molar ratio in the reaction gas phase was 0.013.

4) Analysis of Polymer Properties

The polymer obtained by the reaction was subjected to a 48-hour continuous test under the above conditions, the operation of the apparatus was stable, and the results are shown in Table 1.

2. Preparation of Polypropylene base resin HPP102

1) Raw material (same HPP 101);

2) Test device (same HPP 101);

3) Test conditions

The first step of prepolymerization: the reaction pressure is 2.39MPa, the reaction temperature is 15 ℃, and the reaction time is 15 minutes; the feed amounts of the main catalyst, triethylaluminum, and Diethylaminotriethoxysilane (DAMTS) were 0.75g/hr, 0.043mol/hr, and 0.0044mol/hr, respectively; al/Si molar ratio of 7.16; the propylene feed amount was 15kg/hr.

Second step gas phase polymerization: the homopolymerization reaction temperature is 95 ℃, the reaction pressure is 2.35MPa, and the reaction time is 85 minutes; the propylene feed amount was 10kg/hr; the hydrogen/propylene molar ratio in the reaction gas phase was 0.006.

4) Test results

3. Preparation of Polypropylene base resin HPP103

1) Raw material (same HPP 101);

2) Test device (same HPP 101);

3) Test conditions

Second step gas phase polymerization: the homopolymerization reaction temperature is 100 ℃, the reaction pressure is 2.35MPa, and the reaction time is 85 minutes; the propylene feed amount was 10kg/hr; the hydrogen/propylene molar ratio in the reaction gas phase was 0.006.

4) Test results

4. Preparation of Polypropylene base resin HPP104

1) Raw materials

Triethylaluminum is used as a cocatalyst during polymerization; dicyclopentyl dimethoxy silane (DCPDMS) is used as an external electron donor; propylene and hydrogen are polymerization grade, and are used after water and oxygen are removed; hexane is used after dehydration.

2) Test device (same HPP 101)

3) Test conditions

The first step of prepolymerization: the reaction pressure is 2.44MPa, the reaction temperature is 10 ℃, and the reaction time is 15 minutes; the feed amounts of the main catalyst, triethylaluminum and dicyclopentyldimethoxy silane (DCPDMS) are respectively 0.87g/hr, 0.047mol/hr and 0.0079mol/hr; al/Si molar ratio of 6.11; the propylene feed amount was 15kg/hr.

Second step gas phase polymerization: the homopolymerization reaction temperature is 85 ℃, the reaction pressure is 2.4MPa, and the reaction time is 90 minutes; the propylene feed amount was 10kg/hr; the hydrogen/propylene molar ratio in the reaction gas phase was 0.03.

4) Test results

5. Preparation of Polypropylene base resin HPP105

1) Raw materials (raw materials of comparative example 2 as in CN106632761 a);

2) Test device (same HPP 101);

3) Test conditions

The first step of prepolymerization: the reaction pressure is 2.34MPa, the reaction temperature is 10 ℃, and the reaction time is 15 minutes; the feed amounts of the main catalyst, triethylaluminum and dicyclopentyldimethoxy silane (DCPDMS) are respectively 0.6g/hr, 0.047mol/hr and 0.0079mol/hr; al/Si molar ratio of 6.11; the propylene feed amount was 15kg/hr.

Step (2) gas phase polymerization: the homopolymerization reaction temperature is 66 ℃, the reaction pressure is 2.3MPa, and the reaction time is 90 minutes; the propylene feed amount was 10kg/hr; the hydrogen/propylene molar ratio in the reaction gas phase was 0.05.

4) Test results

6. Preparation of Polypropylene base resin HPP106

1) Raw materials: other than unused electron donors, other than that used, are the same as HPP101;

2) Test device (same HPP 101);

3) Test conditions

The first step of prepolymerization: the reaction pressure is 2.5MPa, the reaction temperature is 15 ℃, and the reaction time is 15 minutes; the feeding amount of the main catalyst and the triethylaluminum is 0.4g/hr and 0.058mol/hr respectively; the propylene feed amount was 10kg/hr.

Second step gas phase polymerization: the homopolymerization reaction temperature is 91 ℃, the reaction pressure is 2.3MPa, and the reaction time is 60 minutes; the propylene feed amount was 10kg/hr; the hydrogen/propylene molar ratio in the reaction gas phase was 0.008.

The formulation and test results of the polypropylene compositions used in the examples are shown in Table 1.

In addition, a commercial high-flow narrow-molecular-weight polypropylene product with the trade name of H30S is prepared by peroxide degradation by a Zhenhai refining company. The polymers were subjected to analytical testing and the results are set forth in Table 1.

Example 1

1. Preparation of antibacterial flame-retardant polypropylene composition

The preparation method comprises the steps of (1) putting 101 100 parts by weight of polypropylene HPP, 4 parts by weight of an elastomer OBC (propylene block copolymer), 1.1 parts by weight of XQ101, 0.18 part by weight of aluminum hypophosphite, 0.36 part by weight of MHB, 0.1 part by weight of flame retardant synergist DMDPB, 0.2 part by weight of zinc pyrithione, 0.5 part by weight of magnesium tourmaline, 0.02 part by weight of erucamide, 0.2 part by weight of antioxidant 1010 (BASF company) and antioxidant 168 (BASF company) (1010:168 weight=1:1) into a low-speed mixer for fully and uniformly stirring, then carrying out melt blending on the mixed materials through a double-screw extruder, extruding and granulating at the extruder temperature of 190-220 ℃ and the rotating speed of 300r.p.m, and drying the extruded granules in a constant-temperature oven at 80 ℃ for 3hr to obtain flame retardant and antibacterial polypropylene composition particles.

2. Preparation of antibacterial polypropylene non-woven fabric

The test was carried out using a Reicofil 4 Spunbond Meltblown (Spunbond/Meltblow) apparatus from Leifenhao, germany. For this line, four extruders are run to a spinneret set (composite-fiber configuration). The operation of the production line may be single wire (S) and double wire (SS) as well as three wire (SSs) and four wire (SSSs). In addition, SMS, SMMS, SSMMS and SSMMSS may also be combined with the meltblown spunbond. These four extruders have different outputs and also pass through four spinning pumps with different outputs. For this test, the output of each spin pump was equal and the total output of extrusion was 0.75ghm, using the spunbond technique, to produce a fabric at a line speed of 150 meters per minute at 15gsm, the resulting fiber having 3dpf, the embossed calender roll and smooth roll being the same oil temperature. The temperature and pressure conditions of the calender rolls are shown in Table 3. Here, dpf means denier per filament (denier per fiber), ghm means grams of polymer per minute per hole, and gsm means grams per square meter.

Example 2

1. Preparation of antibacterial polypropylene fiber composition

The preparation method comprises the steps of placing 102 100 parts by weight of polypropylene HPP, 5 parts by weight of ethylene propylene diene monomer, 1.0 part by weight of XQ102, 0.2 part by weight of aluminum hypophosphite, 0.35 part by weight of MHB, 0.1 part by weight of flame retardant synergist DMDPB, 0.2 part by weight of zinc pyrithione, 0.5 part by weight of magnesium tourmaline, 0.02 part by weight of erucamide, 0.2 part by weight of antioxidant 1010 (BASF company) and antioxidant 168 (BASF company) (1010:168=1:1) into a low-speed mixer for fully and uniformly stirring, then melt-blending the mixture by a double-screw extruder, extruding and granulating at the extruder temperature of 190-220 ℃ and the rotating speed of 300r.p.m, and drying the extruded granules in a constant-temperature oven at 80 ℃ for 3hr to obtain flame retardant antibacterial polypropylene composition particles.

2. Preparation of antibacterial polypropylene non-woven fabric

The test was carried out using a Reicofil 4 Spunbond Meltblown (Spunbond/Meltblow) composite apparatus from Leifenhao, germany. For this line, four extruders are run to a spinneret set (composite-fiber configuration). The operation of the production line may be single wire (S) and double wire (SS) as well as three wire (SSs) and four wire (SSSs). In addition, SMS, SMMS, SSMMS and SSMMSS may also be combined with the meltblown spunbond. The four extruders have different outputs and also pass through four spinning pumps having different outputs. For this test, the output of each spin pump was equal and the extrusion was 0.8ghm total output, producing a cloth at 15gsm at a line speed of 165 meters/min, the resulting fiber having 3dpf, the embossed calender roll and smooth roll being the same oil temperature. The temperature and pressure conditions of the calender rolls are shown in Table 3. Here, dpf means denier per filament (denier per fiber), ghm means grams of polymer per minute per hole, and gsm means grams per square meter.

Example 3

1. Preparation of antibacterial polypropylene fiber composition

Polypropylene HPP103 100 weight parts, elastomer POE (ethylene-octene copolymer) 5 weight parts, XQ 103.0 weight parts, aluminum hypophosphite 0.25 weight parts, MHB0.2 weight parts, flame retardant synergist DMDPB 0.1 weight parts, zinc pyrithione 0.2 weight parts, barium silicate 0.5 weight parts, oil N, N' -ethylene bis-stearamide 0.02 weight parts, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) 0.2 weight parts are placed into a low-speed mixer to be fully and uniformly stirred, the mixture is then melted and blended through a twin-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, extrusion granulation is carried out, and the extruded granules are dried in a constant-temperature oven at 80 ℃ for 3hr, so as to obtain flame retardant and antibacterial polypropylene composition particles.

2. Preparation of antibacterial polypropylene non-woven fabric

The test was carried out using a Reicofil 4 Spunbond Meltblown (Spunbond/Meltblow) composite apparatus from Leifenhao, germany. For this line, four extruders are run to a spinneret set (composite-fiber configuration). The operation of the production line may be single wire (S) and double wire (SS) as well as three wire (SSs) and four wire (SSSs). In addition, SMS, SMMS, SSMMS and SSMMSS may also be combined with the meltblown spunbond. The four extruders have different outputs and also pass through four spinning pumps having different outputs. For this test, the output of each spin pump was equal and the extrusion was 0.65ghm total output, producing a cloth at 18gsm at a linear speed of 145 meters/min, the fiber having 2dpf, the embossed calender roll and smooth roll being the same oil temperature. The temperature and pressure conditions of the calender rolls are shown in Table 3. Here, dpf means denier per filament (denier per fiber), ghm means grams of polymer per minute per hole, and gsm means grams per square meter.

Example 4

1. Preparation of antibacterial polypropylene fiber composition

Polypropylene HPP104 100 weight parts, maleic anhydride grafted POE (ethylene-octene copolymer) 3 weight parts, XQ 104.2 weight parts, aluminum hypophosphite 0.2 weight parts, MHB0.25 weight parts, flame retardant synergist DMDPB 0.15 weight parts, zinc pyrithione 0.2 weight parts, barium silicate 0.5 weight parts, N, N' -ethylene bis-stearamide 0.02 weight parts, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) 0.2 weight parts are placed into a low-speed mixer to be fully and uniformly stirred, then the mixture is melt-blended by a twin-screw extruder at 190-220 ℃ at 300r.p.m, the extruded pellets are extruded and granulated, and the extruded pellets are dried in a constant-temperature oven at 80 ℃ for 3hr to obtain flame retardant antibacterial polypropylene composition particles.

2. Preparation of antibacterial polypropylene non-woven fabric

The test was carried out using a Reicofil 4 Spunbond Meltblown (Spunbond/Meltblow) composite apparatus from Leifenhao, germany. For this line, four extruders are run to a spinneret set (composite-fiber configuration). The operation of the production line may be single wire (S) and double wire (SS) as well as three wire (SSs) and four wire (SSSs). In addition, SMS, SMMS, SSMMS and SSMMSS may also be combined with the meltblown spunbond. The four extruders have different outputs and also pass through four spinning pumps having different outputs. For this test, the output of each spin pump was equal and the extrusion was 0.65ghm total output, producing a cloth at 18gsm at a linear speed of 145 meters/min, the fiber having 7dpf, the embossed calender roll and smooth roll being the same oil temperature. The temperature and pressure conditions of the calender rolls are shown in Table 3. Here, dpf means denier per filament (denier per fiber), ghm means grams of polymer per minute per hole, and gsm means grams per square meter.

Example 5

1. Preparation of antibacterial polypropylene fiber composition

Polypropylene HPP105 100 weight parts, maleic anhydride grafted POE (ethylene-octene copolymer) 3 weight parts, XQ 105.8 weight parts, aluminum hypophosphite 0.2 weight parts, MHB0.3 weight parts, flame retardant synergist DMDPB 0.1 weight parts, zinc pyrithione 0.2 weight parts, aluminum stearate 0.5 weight parts, N, N' -ethylene bis-stearamide 0.02 weight parts, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) 0.2 weight parts are placed into a low-speed mixer to be fully and uniformly stirred, then the mixture is melt-blended through a twin-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, extrusion granulation is carried out, and the extruded granules are dried in a constant-temperature oven at 80 ℃ for 3hr, so as to obtain flame retardant antibacterial polypropylene composition particles.

2. Preparation of antibacterial polypropylene non-woven fabric

Example 6

1. Preparation of antibacterial polypropylene fiber composition

3 parts by weight of polypropylene HPP106 100 parts by weight, 3 parts by weight of maleic anhydride grafted POE (ethylene-octene copolymer), 2.8 parts by weight of XQ106, 0.21 parts by weight of aluminum hypophosphite, 0.28 parts by weight of MHB, 0.1 parts by weight of flame retardant synergist DMDPB, 0.2 parts by weight of zinc pyrithione, 0.5 parts by weight of barium silicate, 0.02 parts by weight of N, N' -ethylene bis-stearamide, 0.2 parts by weight of antioxidant 1010 (BASF company) and antioxidant 168 (BASF company) (1010:168=1:1) are put into a low-speed mixer to be fully and uniformly stirred, then the mixture is melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed of 300r.p.m is 300, the extruded pellets are extruded and granulated, and the extruded pellets are dried in a constant-temperature oven at 80 ℃ for 3hr, so as to obtain flame retardant and antibacterial polypropylene composition particles.

2. Preparation of antibacterial polypropylene non-woven fabric

Example 7

1. Preparation of antibacterial polypropylene fiber composition

The preparation method comprises the steps of placing 101 100 parts by weight of polypropylene HPP, 3 parts by weight of SEBS, 107 parts by weight of XQ, 0.2 part by weight of aluminum hypophosphite, 0.25 part by weight of MHB, 0.15 part by weight of flame retardant synergist DMDPB, 0.15 part by weight of zinc pyrithione, 0.5 part by weight of magnesium tourmaline, 0.02 part by weight of N, N' -ethylene bis-stearamide, 0.2 part by weight of antioxidant 1010 (BASF company) and antioxidant 168 (BASF company) (1010:168=1:1) into a low-speed mixer for fully stirring uniformly, then melt-blending the mixed materials through a double-screw extruder, extruding and granulating at the extruder temperature of 190-220 ℃ and the rotating speed of 300r.p.m, and drying the extruded granules in a constant-temperature oven at 80 ℃ for 3hr to obtain flame retardant antibacterial polypropylene composition particles.

2. Preparation of antibacterial polypropylene non-woven fabric

Example 8

1. Preparation of antibacterial polypropylene fiber composition

Polypropylene HPP102 100 weight portions, glycidyl methacrylate grafted SEBS 2 weight portions, XQ101 weight portions, aluminum hypophosphite 0.2 weight portions, MHB0.25 weight portions, flame retardant synergist DMDPB 0.15 weight portions, zinc pyrithione 0.15 weight portions, magnesium tourmaline 0.5 weight portions, N, N ' -ethylene bis-stearamide 0.02 weight portions, 2' -methylene bis (4, 6-di-tert-butylphenyl) aluminum phosphate 0.05 weight portions, N, N ' -dicyclohexyl terephthalamide 0.05 weight portions, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) (1010:168=1:1) are placed into a low-speed mixer to be fully and evenly stirred, the mixture is melted and blended through a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, the extruded granules are granulated, and the extruded granules are dried in an oven at constant temperature of 80 ℃ for 3hr, so as to obtain flame retardant antibacterial polypropylene composition granules.

2. Preparation of antibacterial polypropylene non-woven fabric

Example 9

1. Preparation of antibacterial polypropylene fiber composition

Polypropylene HPP103 100 weight portions, glycidyl methacrylate grafted SEBS 2 weight portions, XQ102 weight portions, aluminum hypophosphite 0.2 weight portions, MHB0.25 weight portions, flame retardant synergist DMDPB 0.15 weight portions, zinc pyrithione 0.15 weight portions, magnesium tourmaline 0.5 weight portions, N, N ' -ethylene bis-stearamide 0.02 weight portions, 2' -methylene bis (4, 6-di-tert-butylphenyl) aluminum phosphate 0.2 weight portions, N, N ' -dicyclohexyl terephthalamide 0.2 weight portions, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) (1010:168=1:1) are placed into a low-speed mixer to be fully and evenly stirred, the mixture is melted and blended through a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, the extruded granules are granulated, and the extruded granules are dried in an oven at constant temperature of 80 ℃ for 3hr, so as to obtain flame retardant antibacterial polypropylene composition granules.

2. Preparation of antibacterial polypropylene non-woven fabric

Comparative example 1

1. Preparation of Polypropylene composition

2040 100 parts by weight of polypropylene, 0.02 part by weight of N, N' -ethylene bis-stearamide, 0.2 part by weight of antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) (1010:168=1:1) are put into a low-speed mixer to be fully and uniformly stirred, then the mixture is melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃ and the rotating speed is 300r.p.m, extrusion granulation is carried out, and the extruded granules are dried in a constant-temperature oven at 90 ℃ for 3 hours.

2. Preparation of Polypropylene nonwoven fabrics

The test was carried out using a Reicofil 4 Spunbond Meltblown (Spunbond/Meltblow) composite apparatus from Leifenhao, germany. For this line, four extruders are run to a spinneret set (composite-fiber configuration). The operation of the production line may be single wire (S) and double wire (SS) as well as three wire (SSs) and four wire (SSSs). In addition, SMS, SMMS, SSMMS and SSMMSS may also be combined with the meltblown spunbond. The four extruders have different outputs and also pass through four spinning pumps having different outputs. For this test, the output of each spin pump was equal and the extrusion was 0.75ghm total output, producing a cloth at 15gsm at a line speed of 150 meters/min, the fiber having 8dpf, the embossed calender roll and smooth roll being the same oil temperature. The temperature and pressure conditions of the calender rolls are shown in Table 3. Here, dpf means denier per filament (denier per fiber), ghm means grams of polymer per minute per hole, and gsm means grams per square meter.

Comparative example 2

1. Preparation of Polypropylene composition

Polypropylene HPP101 100 weight portions, N' -ethylene bis-stearamide 0.02 weight portions, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) (1010:168=1:1) are placed into a low-speed mixer to be fully and evenly stirred, then the mixture is melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, extrusion granulation is carried out, and the extruded granules are dried in a constant-temperature oven at 90 ℃ for 3 hours.

2. Preparation of Polypropylene nonwoven fabrics

Comparative example 3

1. Preparation of Polypropylene composition

Polypropylene HPP103 100 weight parts, XQ101 weight parts, aluminum hypophosphite 0.2 weight parts, MHB 0.35 weight parts, flame retardant synergist DMDPB0.1 weight parts, zinc pyrithione 0.2 weight parts, magnesium tourmaline 0.5 weight parts, N, N' -ethylene bis-stearamide 0.02 weight parts, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) (1010:168=1:1) are placed into a low-speed mixer to be fully and uniformly stirred, the mixture is melted and blended by a double-screw extruder, the extruder temperature is 190-220 ℃, the rotating speed is 300r.p.m, extrusion granulation is carried out, and the extruded granules are dried in a constant-temperature oven at 80 ℃ for 3hr, so that flame retardant and antibacterial polypropylene composition particles are obtained.

2. Preparation of Polypropylene nonwoven fabrics

Comparative example 4

1. Preparation of Polypropylene composition

Polypropylene HPP103 100 weight portions, glycidyl methacrylate grafted SEBS 2 weight portions, XQ 101.0 weight portions, aluminum hypophosphite 0.2 weight portions, MHB 0.35 weight portions, flame retardant synergist DMDPB0.1 weight portions, zinc pyrithione 0.2 weight portions, N, N' -ethylene bis-stearamide 0.02 weight portions, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) 0.2 weight portions are placed into a low-speed mixer to be fully and evenly stirred, the mixture is melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, the extruded granules are extruded and granulated, and the extruded granules are dried in a constant-temperature oven at 80 ℃ for 3 hours, so that flame retardant and antibacterial polypropylene composition particles are obtained.

2. Preparation of Polypropylene nonwoven fabrics

Comparative example 5

1. Preparation of Polypropylene composition

Polypropylene HPP103 100 weight portions, glycidyl methacrylate grafted SEBS 2 weight portions, zeolite silver-carrying antibacterial agent 1.0 weight portions, aluminum hypophosphite 0.2 weight portions, MHB 0.35 weight portions, flame retardant synergist DMDPB0.1 weight portions, zinc pyrithione 0.2 weight portions, magnesium tourmaline 0.5 weight portions, N, N' -ethylene bis-hard amide 0.02 weight portions, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) 0.2 weight portions are placed into a low-speed mixer to be fully and evenly stirred, then the mixture is melted and blended through a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, extrusion granulation is carried out, and the extruded granules are dried in a constant-temperature oven at 80 ℃ for 3hr, so as to obtain flame retardant antibacterial polypropylene composition particles.

2. Preparation of Polypropylene nonwoven fabrics

Comparative example 6

1. Preparation of Polypropylene composition

Polypropylene HPP103 100 weight portions, glycidyl methacrylate grafted SEBS 2 weight portions, zeolite silver-carrying antibacterial agent 1.0 weight portions, zinc pyrithione 0.2 weight portions, tourmaline 0.5 weight portions, N, N' -ethylene bis-stearamide 0.02 weight portions, antioxidant 1010 (BASF corporation) and antioxidant 168 (BASF corporation) 0.2 weight portions are placed into a low-speed mixer to be fully and evenly stirred, then the mixture is melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 300r.p.m, extrusion granulation is carried out, and the extruded granules are dried in a constant-temperature oven at 80 ℃ for 3 hours, so that flame-retardant antibacterial polypropylene composition particles are obtained.

2. Preparation of Polypropylene nonwoven fabrics

The mechanical, flame retardant and antibacterial properties of the nonwoven fabrics obtained in the above examples and comparative examples are shown in Table 2.

TABLE 1 Synthesis conditions and Properties of Polypropylene base resin

/>

From the data in table 1, it can be seen that:

(1) The polypropylene with narrow molecular weight distribution prepared by the invention has high isotacticity, and the reaction conditions can be adjusted according to the needs to obtain polypropylene with different isotacticity. The polypropylene has a low melting point, excellent rigidity and higher heat distortion temperature, and can be used for sealing materials.

(2) The polymer product HPP105 obtained by conventional polymerization at 66 ℃ has a relatively large molecular weight distribution index, i.e. a relatively broad molecular weight distribution, as characterized by the ratio of the weight average molecular weight to the number average molecular weight. The narrow molecular weight distribution polypropylene HPP101, HPP102 and HPP103 of the present invention has a narrow molecular weight distribution and higher mechanical strength than HPP 105.

(3) As can be seen from Table 1, the narrow molecular weight distribution polypropylene HPP101-HPP103 of the present invention has a molecular weight distribution width exceeding the level of the narrow molecular weight distribution by the degradation method and a high molecular tailing index PI as compared with H30S _HT And crystallization temperatures are significantly higher than those of the narrow distribution polypropylene by the degradation process. PI (proportional integral) _HT The higher indicates the presence of more significant macromolecular chain ends in the polypropylene, which can preferentially nucleate in crystallization. Therefore, the preparation method of the polypropylene with narrow molecular weight distribution has shorter molding cycle than the degradation method And the molding efficiency is higher, namely the direct polymerization method is more economical, environment-friendly and efficient.

(4) Table 2 shows that the nonwoven fabric provided by the invention has excellent mechanical properties and antibacterial properties, and has good inhibition performance on staphylococcus aureus and escherichia coli before and after water boiling. It can also be seen that the nonwoven fabrics prepared from the polypropylene base resins obtained in examples 1-3 and 7-9 have good mechanical properties, and in particular, the tensile strength in the MD and TD directions is higher than that of the nonwoven fabrics obtained from the polypropylene 2040 special for the general nonwoven fabrics, and the tensile strengths in the MD and TD directions are similar. As can be seen from comparative example 2, the addition of the elastomer significantly improves the mechanical properties; as is evident from comparative examples 1-2 and 5-6, neither the pellets nor the flame retardant reinforcing agent was added to achieve good flame retardant and antibacterial effects. As can be seen from comparative example 4, good NaCl filtration and DOP filtration effects could not be achieved without the addition of electrets. The non-woven fabrics prepared by using the formulas of examples 1-3 and 7-9 are used for masks, have good durability when used for filter elements of air purifiers, and have the effects of NaCl filtration and DOP filtration which are obviously lower than those of non-woven fabrics prepared by polypropylene used in comparative example 4. It can be seen from examples 8-9 that the addition of nucleating agents A and B has better effect for improving the mechanical properties of the nonwoven fabric and the NaCl filtration and DOP filtration efficiency. The invention relates to a mask obtained by melt-blowing cloth, which can reach KN95 grade. The filtering efficiency of the N95 type mask on particles with aerodynamic diameter of 0.3 mu m reaches more than 95 percent. Aerodynamic diameters of the aerobacterial and fungal spores vary mainly between 0.7-10 μm, also within the protective range of N95 type masks.

It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims

1. An antibacterial flame-retardant polypropylene fiber composition comprises the following components in parts by weight:

100 parts of polypropylene base resin;

0.1-10 parts of elastomer;

0.05 to 4.0 portions of flame-retardant antibacterial agent;

0.1 to 0.5 part of electret;

0.05 to 1.0 part of flame retardant synergist;

the polypropylene base resin is a polypropylene base resin with narrow molecular weight distribution; molecular weight distribution M of the narrow molecular weight distribution polypropylene base resin _w /M _n 3.7 to 5.7; the polymer tailing index PI in the molecular weight distribution width _HT Greater than 2.3;

the flame-retardant antibacterial agent is a polymer microsphere with guanidine salt grafted on the surface, and the polymer microsphere comprises a cross-linked structure of a structural unit A, a structural unit B and a structural unit C; wherein the structural unit A is provided for maleic anhydride; the structural unit B is provided for the monomer M; the structural unit C is provided for a crosslinking agent;

wherein the monomers M are provided by C four and/or C five;

the guanidine salt is selected from one or more of small-molecule guanidine salt and guanidine salt polymer, and at least comprises one guanidine salt with flame retardance;

the cross-linking agent is selected from vinyl-containing monomers with more than two functionalities and capable of undergoing free radical polymerization;

the polymer microsphere is in a microsphere or spheroid shape; the average particle size of the polymer microsphere is 200-2000 nm.

2. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the amount of the elastomer is 1 to 5 parts by weight based on 100 parts by weight of the polypropylene base resin.

3. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the amount of the flame-retardant antibacterial agent is 0.2 to 3 parts by weight based on 100 parts by weight of the polypropylene base resin.

4. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

molecular weight distribution M of the narrow molecular weight distribution polypropylene base resin _w /M _n 4.0 to 4.5; the polymer tailing index PI in the molecular weight distribution width _HT Greater than 2.5; the isotacticity is greater than 96%; crystallization temperature T _C Greater than 119 ℃; the melt index MFR is 0.01-1000 g/10min.

5. The antimicrobial flame retardant polypropylene fiber composition of claim 4 wherein:

the isotacticity of the polypropylene base resin with narrow molecular weight distribution is more than 97%; crystallization temperature T _C Greater than 121 ℃; the melt index MFR is 10 to 250g/10min.

6. The antimicrobial flame retardant polypropylene fiber composition of claim 5 wherein:

the isotacticity of the polypropylene base resin with narrow molecular weight distribution is more than 98%; the melt index MFR is 20 to 60g/10min.

7. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the elastomer is at least one selected from ethylene propylene rubber (EPM), ethylene Propylene Diene Monomer (EPDM), ethylene/alpha-olefin random copolymer (POE), glycidyl methacrylate grafted POE, olefin Block Copolymer (OBC), styrene-ethylene-butylene-styrene block polymer (SEBS) and glycidyl methacrylate grafted SEBS.

8. The antimicrobial flame retardant polypropylene fiber composition of claim 7 wherein:

the elastomer is at least one of ethylene propylene rubber (EPM), ethylene/alpha-olefin copolymer elasticity (POE), olefin Block Copolymer (OBC) and glycidyl methacrylate grafted SEBS.

9. The antimicrobial flame retardant polypropylene fiber composition of claim 7 wherein:

the elastomer is at least one of glycidyl methacrylate grafted POE and glycidyl methacrylate grafted SEBS.

10. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the guanidine salt with flame retardance accounts for 30-100 wt% of the total weight of the guanidine salt.

11. The antimicrobial flame retardant polypropylene fiber composition of claim 10 wherein:

the guanidine salt with flame retardance accounts for 50-100 wt% of the total weight of the guanidine salt.

12. The antimicrobial flame retardant polypropylene fiber composition of claim 11 wherein:

the guanidine salt with flame retardance accounts for 80-100 wt% of the total weight of the guanidine salt.

13. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

The molar ratio of the structural unit A to the structural unit B is in the range of 0.5:1 to 1:0.5;

and/or the number of the groups of groups,

the polymer microsphere has a dissolution rate of less than or equal to 8wt% in acetone with the weight being 5 times that of the polymer microsphere under the conditions of 50 ℃ and 30 min; and/or the number of the groups of groups,

the crosslinking degree of the polymer microsphere is more than or equal to 50 percent.

14. The antimicrobial flame retardant polypropylene fiber composition of claim 13 wherein:

the molar ratio of the structural unit A to the structural unit B is in the range of 0.75:1 to 1:0.75.

15. the antimicrobial flame retardant polypropylene fiber composition of claim 13 wherein:

the crosslinking degree of the polymer microsphere is more than or equal to 70 percent.

16. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the cross-linking agent is divinylbenzene and/or acrylic ester cross-linking agent containing at least two acrylic ester groups; the structural formula of the acrylic ester group is as follows: -O-C (O) -C (R') =ch ₂ R' is H or C1-C4 alkyl.

17. The antimicrobial flame retardant polypropylene fiber composition of claim 16 wherein:

the cross-linking agent is selected from one or more of divinylbenzene, propylene glycol di (methyl) acrylate, ethylene glycol di (methyl) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate and ethoxylated multifunctional acrylate.

18. The antimicrobial flame retardant polypropylene fiber composition of claim 17 wherein:

the propylene glycol type di (methyl) acrylic ester is selected from one or more of 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate and 1, 2-propylene glycol diacrylate; the ethylene glycol di (methyl) acrylate is selected from one or more of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate and tetraethylene glycol diacrylate.

19. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the small-molecule guanidine salt is one or more selected from guanidine phosphate, guanidine hydrochloride, guanidine nitrate, guanidine hydrobromide, guanidine oxalate, guanidine dihydrogen phosphate, guanidine hydrogen phosphate and amino guanidine salt; wherein the amino guanidine salt is selected from one or more of aminoguanidine, diaminoguanidine and carbonate, nitrate, phosphate, oxalate, hydrochloride, hydrobromide, sulfonate of triaminoguanidine, and other inorganic or organic salts;

The guanidine salt polymer is selected from one or more of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine oxalate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyhexamethylene (bis) guanidine sulfonate, and other inorganic or organic salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine.

20. The antimicrobial flame retardant polypropylene fiber composition of claim 19 wherein:

the small-molecule guanidine salt is selected from one or more of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, guanidine hydrobromide, and nitrate, phosphate, hydrochloride, hydrobromide and sulfonate of aminoguanidine, diaminoguanidine and triaminoguanidine.

21. The antimicrobial flame retardant polypropylene fiber composition of claim 20 wherein:

the small-molecule guanidine salt is selected from one or more of guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, guanidine hydrobromide, triaminoguanidine nitrate, aminoguanidine nitrate, triaminoguanidine phosphate, triaminoguanidine hydrochloride, triaminoguanidine hydrobromide and triaminoguanidine sulfonate.

22. The antimicrobial flame retardant polypropylene fiber composition of claim 19 wherein:

the guanidine salt polymer is one or more selected from polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine sulfonate and polyhexamethylene (bis) guanidine oxalate.

23. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the guanidine salt with flame retardance is selected from at least one of guanidine phosphate, guanidine hydrochloride, guanidine hydrobromic acid, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, and phosphate, hydrochloride, hydrobromide, nitrate, carbonate, oxalate, sulfonate of amino guanidine and polymer of guanidine salt.

24. The antimicrobial flame retardant polypropylene fiber composition of claim 23 wherein:

the guanidine salt with flame retardance is at least one selected from guanidine phosphate, guanidine hydrochloride, guanidine dihydrogen phosphate, guanidine hydrogen phosphate, amino guanidine phosphate, hydrochloride, hydrobromide, nitrate, sulfonate, polyhexamethylene (bis) guanidine hydrochloride and polyhexamethylene (bis) guanidine phosphate.

25. The antimicrobial flame retardant polypropylene fiber composition of claim 23 wherein:

The amino guanidine is at least one selected from amino guanidine, diamino guanidine and triaminoguanidine.

26. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the electret is at least one selected from aliphatic metal salt, piezoelectric ceramic powder or insulating polymer.

27. The antimicrobial flame retardant polypropylene fiber composition of claim 26 wherein:

the electret is at least one selected from zinc stearate, calcium stearate, sodium stearate, barium stearate, aluminum stearate, barium silicate, magnesium silicate, aluminum silicate, tourmaline, polytetrafluoroethylene and polyvinylidene fluoride.

28. The antimicrobial flame retardant polypropylene fiber composition of claim 27 wherein:

the tourmaline has a general formula: XY ₃ Z ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ W ₄ ；

X is selected from at least one of Na, ca and K;

y is selected from Fe ²⁺ 、Mg ²⁺ 、Al ³⁺ 、Li ⁺ 、Fe ³⁺ 、Mn ²⁺ 、Mn ³⁺ At least one of (a) and (b);

z is selected from A1 ³⁺ ,Fe ³⁺ Or Cr ³⁺ 、Mg ²⁺ And V ³⁺ At least one of (a) and (b);

w is selected from OH-, F-, O-, and ² -at least one of.

29. The antimicrobial flame retardant polypropylene fiber composition of claim 28 wherein:

in the general formula of the tourmaline,

x is selected from Na or Ca;

y is selected from Fe ²⁺ Or Mg (Mg) ²⁺ ；

Z is selected from Al ³⁺ ,Fe ³⁺ Or Cr ³⁺ At least one of them.

30. An antimicrobial flame retardant polypropylene fiber composition according to claim 1, characterized by comprising an aluminum phosphinate flame retardant, melamine hydrobromide;

based on 100 parts by weight of the polypropylene base resin,

0.1 to 2.0 parts of aluminum phosphinate flame retardant;

the melamine hydrobromide is 0.1-2.0 parts;

and/or the number of the groups of groups,

the aluminum phosphinate flame retardant is at least one selected from inorganic aluminum phosphinate, alkyl aluminum phosphinate and phenyl aluminum phosphinate; the aluminum alkyl phosphinate is at least one selected from aluminum diethyl phosphinate and aluminum dipropyl phosphinate.

31. The antimicrobial flame retardant polypropylene fiber composition of claim 30 wherein:

based on 100 parts by weight of the polypropylene base resin,

0.1 to 1.2 parts of aluminum hypophosphite flame retardant;

the melamine hydrobromide is 0.1-1.2 parts.

32. The antimicrobial flame retardant polypropylene fiber composition of claim 30 wherein:

the aluminum phosphinate flame retardant is selected from inorganic aluminum phosphinate and/or diethyl aluminum phosphinate.

33. The antimicrobial flame retardant polypropylene fiber composition of claim 1 wherein:

the flame retardant synergist is at least one selected from 2, 3-dimethyl-2, 3-diphenyl butane (DMDPB) and p-isopropylbenzene polymer (poly-cumyl).

34. The antimicrobial flame retardant polypropylene fiber composition according to claim 1, characterized by comprising a slip agent;

based on 100 parts by weight of the polypropylene base resin,

the dosage of the slipping agent is 0.01 to 0.25 part;

and/or the number of the groups of groups,

the slipping agent is at least one selected from stearamide, N, N' -ethylene bisstearamide, erucamide and oleamide.

35. The antimicrobial flame retardant polypropylene fiber composition of claim 34 wherein:

based on 100 parts by weight of the polypropylene base resin,

the amount of the slipping agent is 0.02-0.2 part.

36. The antimicrobial flame retardant polypropylene fiber composition according to claim 1, characterized by comprising a nucleating agent; the nucleating agent comprises a nucleating agent A and a nucleating agent B;

based on 100 parts by weight of the polypropylene base resin,

the dosage of the nucleating agent A is 0.05-0.2 part;

the dosage of the nucleating agent B is 0.05-0.2 part;

the nucleating agent A is an alpha nucleating agent and is substituted aryl heterocyclic phosphate or sodium bis (p-tert-butylphenyl) phosphate; the nucleating agent B is beta nucleating agent and is at least one of aryl dicarboxylic acid amide and N, N' -dicyclohexyl terephthalamide.

37. The antimicrobial flame retardant polypropylene fiber composition of claim 36 wherein:

the substituted aryl heterocyclic phosphate is at least one selected from sodium 2,2 '-methylenebis (4, 6-di-tert-butylphenyl) phosphate and aluminum 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate.

38. The antimicrobial flame retardant polypropylene fiber composition of claim 37 wherein:

the substituted aryl heterocyclic phosphate is selected from 2,2' -methylenebis (4, 6-di-tert-butylphenyl) aluminum phosphate.

39. The antimicrobial flame retardant polypropylene fiber composition of claim 36 wherein:

the nucleating agent B is N, N' -dicyclohexyl terephthalamide.

40. The antimicrobial flame retardant polypropylene fiber composition according to claim 1, characterized by comprising a mildew inhibitor; the weight of the polypropylene base resin is 100 parts, and the dosage of the mildew preventive is 0.05-5.0 parts; and/or the number of the groups of groups,

the mildew preventive is at least one selected from pyrithione, isothiazolinone, 10' -oxo-diphenol Oxazine (OBPA), 3-iodine-2-propynyl butyl carbamate (IPBC), 2, 4' -trichloro-2 ' -hydroxy diphenyl ether (triclosan) and 2- (thiazole-4-yl) benzimidazole (thiabendazole).

41. The antimicrobial flame retardant polypropylene fiber composition of claim 40 wherein:

the weight of the polypropylene base resin is 100 parts, and the dosage of the mildew preventive is 0.05-4.0 parts.

42. The antimicrobial flame retardant polypropylene fiber composition of claim 40 wherein:

the pyrithione is at least one selected from zinc pyrithione, copper pyrithione and dipyridyl thioketone; and/or the number of the groups of groups,

the isothiazolinone is selected from at least one of 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-n-octyl-3-isothiazolin-one (DCOIT), 1, 2-benzisothiazolin-3-one (BIT), 4-methyl-1, 2-benzisothiazolin-3-one (MBIT), n-butyl-1, 2-benzisothiazolin-3-one (BBIT).

43. The method of producing an antimicrobial flame retardant polypropylene fiber composition according to any one of claims 1 to 42, comprising the steps of:

44. The method of preparing an antimicrobial flame retardant polypropylene fiber composition of claim 43, wherein:

The preparation method of the flame-retardant antibacterial agent comprises the following steps:

and (3) in the presence of an initiator, crosslinking and copolymerizing components comprising maleic anhydride, the monomer M and the crosslinking agent to obtain polymer microspheres, and grafting the polymer microspheres with guanidine salt or guanidine salt solution to obtain the flame-retardant antibacterial agent.

45. The method of preparing an antimicrobial flame retardant polypropylene fiber composition according to claim 44, wherein:

46. The method for preparing the antibacterial flame-retardant polypropylene fiber composition according to claim 45, wherein:

in the step (1) described above, the step of (c) is performed,

the total amount of the first part of monomers M and the second part of monomers M calculated as terminal olefin is 50 to 150mol with respect to 100mol of the maleic anhydride;

In the step (1), the molar ratio between the second part of monomer M and the first part of monomer M is (0-100): 100;

and/or the number of the groups of groups,

the crosslinking agent is used in an amount of 1 to 40mol with respect to 100mol of maleic anhydride.

47. The method of preparing an antimicrobial flame retardant polypropylene fiber composition of claim 46, wherein:

in the step (1) described above, the step of (c) is performed,

the total amount of the first part of monomers M and the second part of monomers M calculated as terminal olefin is 75 to 100mol with respect to 100mol of the maleic anhydride;

and/or the number of the groups of groups,

the crosslinking agent is used in an amount of 6 to 20mol with respect to 100mol of maleic anhydride.

48. The method for preparing the antibacterial flame-retardant polypropylene fiber composition according to claim 45, wherein:

in the step (1) described above, the step of (c) is performed,

the total amount of the first part of initiator and the second part of initiator is 0.05 to 10mol relative to 100mol of maleic anhydride; and/or the number of the groups of groups,

the molar ratio between the second part of initiator and the first part of initiator can be (0-100): 100;

and/or the number of the groups of groups,

the initiator is at least one selected from dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.

49. The method of preparing an antimicrobial flame retardant polypropylene fiber composition of claim 48, wherein:

in the step (1) described above, the step of (c) is performed,

the total amount of the first part of initiator and the second part of initiator is 0.5 to 5mol with respect to 100mol of maleic anhydride.

50. The method for preparing the antibacterial flame-retardant polypropylene fiber composition according to claim 45, wherein:

the amount of the organic solvent used is 50 to 150L relative to 100mol of maleic anhydride.

51. The method for preparing the antibacterial flame-retardant polypropylene fiber composition according to claim 45, wherein:

the organic solvent is selected from alkyl organic acid esters, or a mixture of alkyl organic acid esters and alkanes, or a mixture of alkyl organic acid esters and aromatic hydrocarbons.

52. The method of preparing an antimicrobial flame retardant polypropylene fiber composition of claim 51 wherein:

the organic acid alkyl ester is selected from at least one of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate; the alkane is selected from n-hexane and/or n-heptane; the aromatic hydrocarbon is selected from at least one of benzene, toluene and xylene.

53. The method for preparing the antibacterial flame-retardant polypropylene fiber composition according to claim 45, wherein:

in the step (1) described above, the step of (c) is performed,

the conditions under which maleic anhydride reacts in contact with monomer M include: inert atmosphere, temperature of 50-90 ℃, pressure of 0.3-1 MPa and time of 0.5-4 h; and/or the number of the groups of groups,

the conditions for continuing the reaction include: the temperature is 50-90 ℃, the pressure is 0.3-1 MPa, and the time is 2-15 h.

54. The method for preparing the antibacterial flame-retardant polypropylene fiber composition according to claim 45, wherein:

in the step (2), the step of (c),

the guanidine salt is used in an amount of 5g to 5000g relative to 1000g of maleic anhydride;

the amount of the guanidine salt solution is 500-10000 g relative to 1000g of maleic anhydride;

and/or the number of the groups of groups,

in the step (2), the step of (c),

the grafting reaction conditions include: the temperature is 0-100 ℃; the reaction time is 0.5-10 h; the stirring speed is 50-1000 rpm;

and/or the number of the groups of groups,

the concentration of the guanidine salt aqueous solution is 0.5-50 wt%.

55. The method of preparing an antimicrobial flame retardant polypropylene fiber composition according to claim 54, wherein:

in the step (2), the step of (c),

the guanidine salt is used in an amount of 20g to 3000g relative to 1000g of maleic anhydride;

The dosage of the guanidine salt solution is 1000-8000 g relative to 1000g of maleic anhydride;

and/or the number of the groups of groups,

in the step (2), the step of (c),

the grafting reaction conditions include: the temperature is 2.5-90 ℃;

and/or the number of the groups of groups,

the concentration of the guanidine salt aqueous solution is 1-30wt%.

56. The method of preparing an antimicrobial flame retardant polypropylene fiber composition of claim 43, wherein:

the preparation method of the polypropylene base resin comprises the following steps:

57. The method for preparing an antimicrobial flame retardant polypropylene fiber composition according to claim 56, wherein:

in the step (1) described above, the step of (c) is performed,

the catalyst is a Ziegler-Natta catalyst;

the reaction conditions for the prepolymerization reaction include: the reaction temperature is 0-25 ℃, and the prepolymerization pressure is 0.1-10.0 MPa; and/or the number of the groups of groups,

controlling the prepolymerization multiple to be 2-3000 g polymer/g catalyst;

in the step (2), the step of (c),

the conditions for the propylene polymerization reaction include:

the reaction temperature is 80-150 ℃; and/or the number of the groups of groups,

the reaction pressure is 1-6 MPa; and/or the number of the groups of groups,

The polymerization reaction time is 0.5-5 h.

58. The method of making an antimicrobial flame retardant polypropylene fiber composition of claim 57 wherein:

in the step (1) described above, the step of (c) is performed,

controlling the prepolymerization multiple to be 3-2000 g polymer/g catalyst;

in the step (2), the step of (c),

the conditions for the propylene polymerization reaction include:

the reaction temperature is 80-100 ℃.

59. An antibacterial flame retardant polypropylene fiber, prepared by melt blowing an antibacterial flame retardant polypropylene fiber composition according to any one of claims 1 to 42 or prepared according to the method of any one of claims 43 to 58.

60. The antimicrobial flame retardant polypropylene fiber of claim 59, wherein:

the antibacterial flame-retardant polypropylene fiber is microfiber.

61. The antimicrobial flame retardant polypropylene fiber of claim 59, wherein:

the average diameter of the antibacterial flame-retardant polypropylene fiber is 0.01-30 mu m.

62. An antimicrobial flame retardant polypropylene nonwoven fabric comprising the antimicrobial flame retardant polypropylene fiber of any one of claims 59-61;

the nonwoven fabric has a weight of 0.015 to 0.25kg/m ² The unit area is heavy; and/or the number of the groups of groups,

the average filament denier of the non-woven fabric is 0.05-8.

63. The antimicrobial flame-retardant polypropylene nonwoven fabric of claim 62, wherein:

the nonwoven fabric has a weight of 0.015-0.03 kg/m ² Is heavy per unit area.

64. Use of an antimicrobial flame retardant polypropylene fiber composition according to any one of claims 1 to 42 or an antimicrobial flame retardant polypropylene fiber according to any one of claims 59 to 61 or an antimicrobial flame retardant polypropylene nonwoven fabric according to claim 62 or 63 in the field of fiber products.

65. The use according to claim 64, wherein:

the application is selected from any one of infant, feminine hygiene products, personal protection products, surgical gown fibers and carpet fibers.

66. The use according to claim 65, wherein:

the personal protection product is a mask.

67. The use according to claim 66, wherein:

the personal protection product is an N95 mask.