CN115057968A

CN115057968A - Antibacterial polypropylene resin and preparation method thereof

Info

Publication number: CN115057968A
Application number: CN202210741576.8A
Authority: CN
Inventors: 马勇; 李海强; 韩亚晓; 潘晓龙; 张弘宇
Original assignee: Chambroad Chemical Industry Research Institute Co Ltd
Current assignee: Chambroad Chemical Industry Research Institute Co Ltd
Priority date: 2022-06-28
Filing date: 2022-06-28
Publication date: 2022-09-16
Anticipated expiration: 2042-06-28
Also published as: CN115057968B

Abstract

The invention provides an antibacterial polypropylene resin, which is prepared from the following raw materials: 100 parts of polypropylene, 0.1-5 parts of modified triclosan, 0.1-2 parts of antioxidant and 0.001-0.2 part of initiator diluent. The application also provides a preparation method of the antibacterial polypropylene resin. According to the invention, the modified triclosan and the polypropylene are connected together in a chemical bond mode by using a melt grafting mode, so that the macromolecular chain of the polypropylene is provided with substances with antibacterial groups, and the antibacterial polypropylene resin has excellent antibacterial performance under the condition of adding a small amount of the modified triclosan through further formula adjustment, and the degradation and yellowing of the polypropylene main chain are reduced.

Description

Antibacterial polypropylene resin and preparation method thereof

Technical Field

The invention relates to the technical field of polypropylene resin, in particular to antibacterial polypropylene resin and a preparation method thereof.

Background

Polypropylene (PP) serving as general thermoplastic plastic with the largest productivity in the world has the advantages of no toxicity, no odor, small density, good heat resistance, easiness in processing and forming, good electrical insulation, chemical resistance, good mechanical strength and wear resistance, and therefore, the PP can be widely applied to the fields of daily necessities, toys, machinery, buildings, textiles, packaging, electronic and electric appliances, automobile interior and exterior trimming parts and the like. With the development of economic society, the awareness of health and environmental protection of people is further improved. In a proper environment, the polypropylene plastic can breed a large amount of microbes such as bacteria and fungi on the surface of a product, and seriously harms the health and safety of human beings. Because polypropylene does not have an antibacterial function, the development of an antibacterial polypropylene resin has extremely important significance and value.

Currently, antibacterial agents mainly include organic antibacterial agents, inorganic antibacterial agents and natural antibacterial agents. The preparation method of the antibacterial polypropylene resin mainly comprises two main types of physical blending modification and chemical modification. The physical blending modification is used as a main preparation method of the antibacterial polypropylene, the antibacterial agent component is directly added into the polypropylene for blending and extrusion, although the inorganic antibacterial agent has good heat resistance, the inorganic antibacterial agent has higher price, is easy to agglomerate and difficult to disperse, is seriously precipitated on the surface of a product, and has poor antibacterial long-acting property; the natural antibacterial agent has the advantages of low raw material source, poor weather resistance and easy degradation of the quality of polypropylene products; the organic antibacterial agent is easy to volatilize, has poor heat resistance and is easy to decompose, so that the product is yellowed, and the long-acting antibacterial performance is not achieved. The antibacterial polypropylene resin prepared in the prior art has poor quality and serious yellowing, and seriously influences the application range of downstream products.

The Chinese patent with the application number of CN2004100419011 adopts the doped silver as the antibacterial agent, although the antibacterial performance can be improved, the problems of high silver cost and easy color change of products exist, and the application of the downstream market is limited. The Chinese patent with publication No. CN109293838B grafts polypropylene with maleic anhydride to obtain an intermediate, and the intermediate is then reacted with a brominated organic antibacterial agent through nucleophilic reaction to prepare the novel grafted antibacterial polypropylene, which solves the problems of poor antibacterial long-term effect, uneven dispersion and easy precipitation of the antibacterial agent of PP products, but because the main chain of the polypropylene is degraded in the grafting reaction process, yellowing is generated, and the use of downstream products is affected. In view of the above problems in the prior art, there is a need to improve the long-acting antibacterial performance of organic antibacterial agents in polypropylene, reduce the yellowing index, and improve the product quality.

Disclosure of Invention

The invention aims to provide the polypropylene resin with low yellowing and high-efficiency antibacterial property.

In view of the above, the present application provides an antibacterial polypropylene resin, which is prepared from the following raw materials in parts by weight:

preferably, the antioxidant is selected from the group consisting of 1: (0.25-4) a hindered phenol antioxidant and a phosphite antioxidant; the content of the hindered phenol antioxidant is 0.05-1 part, and the content of the phosphite antioxidant is 0.05-1 part.

Preferably, the polypropylene is selected from one or two of homo-polypropylene and co-polypropylene, and the melt mass flow rate of the polypropylene is 0.2-50 g/10 min.

Preferably, the modified triclosan is prepared by carrying out esterification reaction on triclosan and acryloyl chloride compounds, wherein the modified triclosan contains olefin double bonds, and the particle size of the modified triclosan is not less than 10 meshes.

Preferably, the initiator is selected from one or more of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, di-t-butyl peroxide (DTBP), di-t-amyl peroxide, dicumyl peroxide and benzoyl peroxide; the initiator is selected from one or more of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, di-tert-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide and benzoyl peroxide.

The application also provides a preparation method of the antibacterial polypropylene resin, which comprises the following steps:

mixing an initiator and a solvent to obtain initiator diluent;

mixing the modified triclosan, the polypropylene and the antioxidant to obtain a premix;

and mixing the initiator diluent and the premix, and then carrying out a melt reaction to obtain the antibacterial polypropylene resin.

Preferably, the solvent is white oil, and the mass ratio of the initiator to the white oil is 1: (8-40).

Preferably, the initiator diluent is added to an injection pump and the premix is mixed in a high speed mixer; the mixing time of the high-speed mixer of the initiator diluent is 1-10 min, the rotating speed is 10-200 r/min, and the temperature is 15-50 ℃.

Preferably, the mixing of the initiator diluent and the premix is specifically:

and injecting the initiator diluent into a reaction section of a double-screw extruder, and adding the premix into the double-screw extruder.

Preferably, the length-diameter ratio of the double-screw extruder is 40: 1-60: 1, the rotating speed is 50-600 r/min, and the processing temperature is 150-300 ℃.

The application provides an antibacterial polypropylene resin which is prepared from polypropylene, modified triclosan, an antibacterial agent and an initiator; wherein the modified triclosan is connected with the polypropylene in a chemical bond mode, so that a polypropylene macromolecular chain is provided with an antibacterial group; furthermore, the polypropylene melt grafting effect is effectively regulated and controlled by regulating and controlling the components of the polypropylene resin, and the degradation and yellowing of the polypropylene main chain are reduced.

Drawings

FIG. 1 is a schematic diagram of the melt grafting preparation principle of the antibacterial polypropylene resin;

FIG. 2 is an infrared spectrum of the antibacterial polypropylene resin.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

Aiming at the requirements of polypropylene resin on antibacterial property and anti-yellowing property in the prior art, the application provides the antibacterial polypropylene resin, and the polypropylene resin has excellent low-yellowing property and high-efficiency antibacterial property by adding polypropylene, modified triclosan, an antibacterial agent and an initiator and adjusting the content of the antibacterial agent and the initiator. Specifically, the embodiment of the invention discloses an antibacterial polypropylene resin which is prepared from the following raw materials in parts by weight:

in the antibacterial polypropylene resin provided by the application, the polypropylene is selected from one or more of homo-polypropylene and co-polypropylene, and when the homo-polypropylene and the co-polypropylene are simultaneously selected, the addition ratio of the homo-polypropylene and the co-polypropylene is 1-99% independently; the melt mass flow rate (230 ℃, 2.16kg) of the polypropylene is 0.2-50 g/10 min.

The modified Triclosan (TCS) is used as an antibacterial agent, is prepared from triclosan and acryloyl chloride compounds through esterification reaction, is white solid powder, contains olefin double bonds capable of generating chemical bonding with acrylic acid molecular chains, and has the particle size of more than or equal to 10 meshes. The reaction mechanism of the modified triclosan and the polypropylene is shown in figure 1, so that the obtained polypropylene resin has a good antibacterial effect, and is environment-friendly and nontoxic. The content of the modified triclosan is 0.1-5 parts by weight, more specifically 0.25-4.5 parts by weight, and more specifically 0.5-3.0 parts by weight.

In the present application, the antioxidant includes one or both of a primary antioxidant and a secondary antioxidant; specifically, the primary antioxidant is selected from one or more of aromatic amine antioxidants and hindered phenol antioxidants, and the secondary antioxidant is selected from one or more of thiodipropionate and phosphite esters; specifically, the primary antioxidant is selected from hindered phenol antioxidants, and the secondary antioxidant is selected from phosphite antioxidants; more specifically, the hindered phenolic antioxidant is selected from one or more of 1098 (chemical name of N, N' -1, 6-hexylene-bis- [3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide ]), 1010 (chemical name of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]) and 1076 (chemical name of octadecyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate); the phosphite antioxidant is one or two of 618 (chemical name is dioctadecyl pentaerythritol diphosphite) and 168 (chemical name is tri (2, 4-di-tert-butylphenyl) phosphite); in a specific embodiment, the antioxidant is selected from antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1: (0.25-4), wherein the content of the antioxidant 1010 is 0.05-1 part by weight, and the content of the antioxidant 168 is 0.05-1 part by weight; in a specific embodiment, the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1: 2-1: 4.

The initiator is well known to those skilled in the art and is selected from one or more of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide and benzoyl peroxide, and is selected from di-t-butyl peroxide, having a density of 0.796g/cm ³ . The content of the initiator is 0.001-0.2 parts by weight, specifically 0.01-0.15 parts by weight, more specifically 0.02-0.10 parts by weight.

mixing an initiator and a solvent to obtain initiator diluent;

The preparation method of the polypropylene resin specifically comprises the following steps:

(a) adding an initiator into white oil for dilution, uniformly mixing to obtain initiator diluent, and adding the initiator diluent into an initiator injection pump;

(b) screening out modified triclosan solid powder by using a stainless steel screen, adding the modified triclosan solid powder, polypropylene and an antioxidant into a high-speed mixer with a jacket, and uniformly mixing to obtain a premix;

(c) and injecting initiator diluent in an injection pump into a reaction section of the double-screw extruder, adding the premix into the double-screw extruder, and carrying out melt reaction, extrusion, cooling, bracing and granulating to obtain the antibacterial polypropylene resin.

In the step (a), the mass ratio of the initiator to the white oil is 1: 8-1: 40, specifically, the mass ratio of the initiator to the white oil is 1: 9-1: 39, in a specific embodiment, the mass ratio of the initiator to the white oil is 1: 9.

in the step (b), the mixing time of the high-speed mixer is 1-10 min, the rotating speed is 10-150 r/min, and the mixing temperature is 15-50 ℃; more specifically, the mixing time is 3-9 min, the rotating speed is 30-100 r/min, and the temperature is 20-40 ℃.

In the step (c), the injection rate of the initiator diluent is 0.1-20 ml/min;

in said step (c), the twin-screw extruder has a length to diameter ratio of 40: 1-60: 1, the processing temperature is 150-300 ℃, and the rotating speed is 50-600 r/min; specifically, the length-diameter ratio is (44-56): 1. the processing temperature is 170-240 ℃, and the rotating speed is 100-500 r/min.

In the invention, modified triclosan and polypropylene are connected together in a chemical bond mode by using a melt grafting mode, so that a polypropylene macromolecular chain is provided with a substance with an antibacterial group; by optimizing the formula and the process conditions, the melt grafting effect of the polypropylene can be effectively regulated and controlled, and the degradation and yellowing of the polypropylene main chain are reduced; and the whole preparation process is simple in process, low in cost, good in controllability and easy to realize industrialization.

For further understanding of the present invention, the antibacterial polypropylene resin and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.

Comparative example 1

(1) Uniformly mixing 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

(2) and (2) feeding the premix into a double-screw extruder through a feed opening for carrying out melt reaction, extrusion, cooling, bracing and granulating to obtain the polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min.

Comparative example 2

(1) According to DTBP: white oil is 1: 9(m/m) adding 0.02 part of initiator DTBP into white oil for dilution, uniformly mixing to obtain initiator DTBP diluent, and adding the initiator DTBP diluent into an initiator injection pump;

(2) uniformly mixing 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 revolutions per minute;

(4) 3g of polypropylene resin is weighed and dissolved in 90ml of dimethylbenzene, the mixture is cooled to room temperature after being completely dissolved, 90ml of methanol (AR) is added to separate out polypropylene, and the mixture is filtered and vacuum-dried (90 ℃ C., 5h) to obtain polymer powder. The samples were subjected to infrared spectroscopy.

Comparative example 3

(2) screening 10 parts of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extrusion, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Comparative example 4

(1) According to DTBP: white oil is 1: 9(m/m) adding 0.0005 part of initiator DTBP into white oil for dilution, uniformly mixing to obtain initiator DTBP diluent, and adding the initiator DTBP diluent into an initiator injection pump;

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

(3) injecting 0.005 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Comparative example 5

(1) According to DTBP: white oil is 1: 9(m/m) adding 0.5 part of initiator DTBP into white oil for dilution, uniformly mixing to obtain initiator DTBP diluent, and adding the initiator DTBP diluent into an initiator injection pump;

(3) injecting diluent of 5 parts of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Comparative example 6

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 0.5min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Comparative example 7

(2) 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes is screened out by a stainless steel screen, and is uniformly mixed with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, the mixing time of the high-speed mixer is 20min, the rotating speed is 30 revolutions per minute, the mixing temperature is 20 ℃, and the modified triclosan antibacterial agent is melted in the mixer due to long mixing time, so that the material is hardened, cannot enter a double-screw extruder through a feed opening, and subsequent experiments are not carried out.

Comparative example 8

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 5 r/min, and the mixing temperature is 20 ℃;

Comparative example 9

(2) 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes is screened out by a stainless steel screen, and is uniformly mixed with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, the mixing time of the high-speed mixer is 3min, the rotating speed is 200 r/min, the mixing temperature is 20 ℃, and due to the fact that the mixing rotating speed is high, the modified triclosan antibacterial agent is melted in the mixer due to heat of friction, materials are hardened, cannot enter a double-screw extruder through a feed opening, and follow-up experiments are not carried out.

Comparative example 10

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 5 ℃;

Comparative example 11

(2) 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes is screened out by a stainless steel screen, and is uniformly mixed with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, the mixing time of the high-speed mixer is 3min, the rotating speed is 30 revolutions per minute, the mixing temperature is 80 ℃, and due to the fact that the mixing temperature is too high, the modified triclosan antibacterial agent melts in the mixer, so that the materials are hardened, cannot enter a double-screw extruder through a feed opening, and subsequent experiments are not carried out.

Comparative example 12

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 24: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Comparative example 13

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 72: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Comparative example 14

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 140 ℃, the rotating speed is 100 r/min, and the extrusion experiment can not be carried out because the processing temperature is lower than the melting point of polypropylene and the current is overloaded and stopped.

Comparative example 15

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 320 ℃, and the rotating speed is 100 r/min;

Comparative example 16

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extrusion, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 30 r/min;

Comparative example 17

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 800 r/min;

Example 1

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

(4) 3g of polypropylene resin is weighed and dissolved in 90ml of dimethylbenzene, the mixture is cooled to room temperature after being completely dissolved, 90ml of methanol (AR) is added to separate out polypropylene, and the mixture is filtered and vacuum-dried (90 ℃ C., 5h) to obtain polymer powder. And extracting the dried polymer by using acetone (at 100-110 ℃) to remove possible antibacterial agent molecular homopolymers, drying the extraction residues to obtain purified grafted polypropylene powder, and carrying out infrared spectrum test on a sample.

Example 2

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extrusion, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Example 3

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.4 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 4

(1) According to DTBP: white oil is 1: 9(m/m) adding 0.01 part of initiator DTBP into white oil for dilution, uniformly mixing to obtain initiator DTBP diluent, and adding the initiator DTBP diluent into an initiator injection pump;

(3) injecting 0.1 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling, bracing and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Example 5

(1) According to DTBP: white oil is 1: 9(m/m) adding 0.03 part of initiator DTBP into white oil for dilution, uniformly mixing to obtain initiator DTBP diluent, and adding the initiator DTBP diluent into an initiator injection pump;

(3) injecting 0.3 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

(4) 3g of polypropylene resin is weighed and dissolved in 90ml of dimethylbenzene, the mixture is cooled to room temperature after being completely dissolved, 90ml of methanol (AR) is added to separate out polypropylene, and the mixture is filtered and vacuum-dried (90 ℃ C., 5h) to obtain polymer powder. And extracting the dried polymer by using acetone (at 100-110 ℃) to remove possible antibacterial agent molecular homopolymers, drying the extraction residues to obtain purified grafted polypropylene powder, and performing infrared spectrum test on a sample.

Example 6

(1) According to DTBP: white oil is 1: 9(m/m) adding 0.05 part of initiator DTBP into white oil for dilution, uniformly mixing to obtain initiator DTBP diluent, and adding the initiator DTBP diluent into an initiator injection pump;

(3) injecting 0.5 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling, bracing and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Example 7

(1) According to DTBP: white oil is 1: 9(m/m) adding 0.1 part of initiator DTBP into white oil for dilution, uniformly mixing to obtain initiator DTBP diluent, and adding the initiator DTBP diluent into an initiator injection pump;

(3) injecting 1 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Example 8

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 6min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 9

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 9min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 10

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 50 r/min, and the mixing temperature is 20 ℃;

Example 11

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 100 r/min, and the mixing temperature is 20 ℃;

Example 12

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 30 ℃;

Example 13

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 40 ℃;

Example 14

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling, bracing and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 40:1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Example 15

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extrusion, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 60:1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Example 16

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 170 ℃, and the rotating speed is 100 r/min;

Example 17

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 240 ℃, and the rotating speed is 100 r/min;

Example 18

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 200 r/min;

Example 19

(3) injecting 0.2 part of diluent of initiator DTBP in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 400 r/min;

Example 20

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 50 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 21

(2) screening 0.5 part of modified triclosan solid powder with the particle size D of 80 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 22

(2) screening 0.25 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the modified triclosan solid powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 23

(2) screening 1 part of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel sieve, and uniformly mixing the powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 24

(2) screening 2 parts of modified triclosan solid powder with the particle size D of 30 meshes by using a stainless steel screen, and uniformly mixing the powder with 100 parts of polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168 in a high-speed mixer with a jacket to obtain a premix, wherein the mixing time of the high-speed mixer is 3min, the rotating speed is 30 r/min, and the mixing temperature is 20 ℃;

Example 25

(1) According to the following formula 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane: white oil is 1: 9(m/m) adding 0.02 part of initiator 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane into white oil for dilution, uniformly mixing to obtain initiator 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane diluent, and adding the initiator into an initiator injection pump;

(3) injecting 0.2 part of diluent of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane as an initiator in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling, drawing strips and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

Example 26

(1) According to the weight ratio of benzoyl peroxide: white oil is 1: 9(m/m) adding 0.02 part of initiator benzoyl peroxide into white oil for dilution, uniformly mixing to obtain initiator benzoyl peroxide diluent, and adding the initiator benzoyl peroxide diluent into an initiator injection pump;

(3) injecting 0.2 part of diluent of initiator benzoyl peroxide in an injection pump into a reaction section of a double-screw extruder, feeding the premix into the double-screw extruder through a feed opening for melting reaction, extruding, cooling and bracing, and granulating to obtain the antibacterial polypropylene resin, wherein the length-diameter ratio of the double-screw extruder is 52: 1, the processing temperature is 190 ℃, and the rotating speed is 100 r/min;

The conditions for testing the heat resistance of the antibacterial polypropylene resin prepared in the above embodiment are as follows: in N ₂ Under the protection of airflow, the temperature of the sample is increased from 25 ℃ to 800 ℃ at the temperature increase rate of 10 ℃/min, and the condition of weight loss decomposition of the sample is observed;

the yellowness index of the antibacterial polypropylene resins prepared in the above comparative examples and examples was tested according to the method of GB/T39822-2021.

The results of the mechanical properties of the antibacterial polypropylene resins prepared in the above comparative examples and examples are shown in tables 1 and 2 below;

TABLE 1 mechanical Properties data Table for polypropylene resins prepared in comparative examples

Note: comparative examples 7, 9, 11 and 14 did not produce polypropylene resins.

TABLE 2 Table of mechanical Properties of Polypropylene resin prepared in example

The antibacterial performance and the anti-mold performance of the antibacterial polypropylene resin prepared in the above embodiment are tested and evaluated according to the special requirements of the antibacterial material with antibacterial, degerming and purifying functions of GB 21551.2-2010 household and similar-purpose appliances, and the results are shown in the following table 3.

TABLE 3 data Table of antibacterial and antifungal Properties of the Polypropylene resin prepared in the example

TABLE 4T of Polypropylene resin prepared in example _-5％ And T _d，max Watch (A)

As can be seen from Table 1, in comparative example 2, the modified triclosan is not added, the initiator completely acts on the polypropylene molecular chain to break and degrade, the mechanical strength is reduced, and the yellow index value is higher. Comparative example 14 the processing temperature did not reach the melt extrusion temperature requirement and no antibacterial polypropylene resin product could be obtained; in addition, after the process parameters and the formula are changed, except that the yellow index of the comparative example 11 is smaller, the yellow indexes of the products of the other comparative examples are higher, the appearance texture is poor, the mechanical property is poor, and the significance of actual production is avoided, so that the antibacterial performance detection is not carried out; however, in the comparative example 10, the mixing temperature needs to be reduced by the cold medium, the processing condition is strict, the production cost is high, and the significance of actual production is not realized, so that the antibacterial performance detection is not carried out.

Compared with the comparative example, the mechanical strength of the antibacterial polypropylene resin is not obviously reduced after the antibacterial agent is added in the example of the table 2; with the increase of the addition amount of the modified triclosan antibacterial agent, the yellow index is in a rising trend and is between 5 and 8; the yellow index rises with the increase of the addition amount of DTBP of the initiator diluent; the addition amount and the action mechanism of the antioxidant 1010 have certain influence on the yellow index.

The test results in table 3 show that: the results of the antibacterial tests of the examples show: after a proper amount of DTBP initiator diluent is added, the antibacterial polypropylene resin has a good antibacterial effect only by adding a small amount of modified triclosan, and also has a good mildew-proof effect.

It can be seen from the infrared spectrum 2 that at 1730cm ^-1 The characteristic peak (C ═ O) of carbonyl of the modified triclosan appears, so that the chemical bond combination of the modified triclosan and the polypropylene molecular chain is realized by using a melt grafting method.

T in Table 4 _-5％ And T _d，max The data show that the antibacterial polypropylene resin prepared by the method also has good heat resistance. In addition, under the condition of ensuring that the antibacterial polypropylene resin has better mechanical property, the yellow index can be effectively reduced and the yellowing can be reduced by adjusting the formula and the process parameters.

The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. The antibacterial polypropylene resin is prepared from the following raw materials in parts by weight:

2. the antimicrobial polypropylene resin according to claim 1, wherein the antioxidant is selected from the group consisting of 1: (0.25-4) a hindered phenol antioxidant and a phosphite antioxidant; the content of the hindered phenol antioxidant is 0.05-1 part, and the content of the phosphite antioxidant is 0.05-1 part.

3. The antimicrobial polypropylene resin according to claim 1 or 2, wherein the polypropylene is one or two selected from homo-polypropylene and co-polypropylene, and the melt mass flow rate of the polypropylene is 0.2 to 50g/10 min.

4. The antibacterial polypropylene resin according to claim 1 or 2, wherein the modified triclosan is prepared by esterification of triclosan and acryloyl chloride compounds, the modified triclosan contains olefinic double bonds, and the particle size of the modified triclosan is not less than 10 meshes.

5. The antimicrobial polypropylene resin of claim 1 or 2, wherein the initiator is selected from one or more of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, di-t-butyl peroxide (DTBP), di-t-amyl peroxide, dicumyl peroxide and benzoyl peroxide; the initiator is selected from one or more of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, di-tert-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide and benzoyl peroxide.

6. The method for preparing the antibacterial polypropylene resin according to claim 1, comprising the steps of:

mixing an initiator and a solvent to obtain initiator diluent;

7. The preparation method according to claim 6, wherein the solvent is white oil, and the mass ratio of the initiator to the white oil is 1: (8-40).

8. The method of claim 6, wherein the initiator diluent is added to a syringe pump, and the premix is mixed in a high-speed mixer; the mixing time of the high-speed mixer of the initiator diluent is 1-10 min, the rotating speed is 10-200 r/min, and the temperature is 15-50 ℃.

9. The method according to claim 6, wherein the mixing of the initiator diluent and the premix is in particular:

10. The preparation method of claim 9, wherein the double-screw extruder has a length-diameter ratio of 40:1 to 60:1, a rotation speed of 50 to 600 rpm, and a processing temperature of 150 to 300 ℃.