CN111234448A - Anti-aging and mildew-proof polyformaldehyde material and preparation method thereof - Google Patents

Abstract

The invention discloses an anti-aging and mildew-proof polyformaldehyde material and a preparation method thereof, wherein the anti-aging and mildew-proof polyformaldehyde material is prepared from the following components in parts by weight: 100 parts of polyformaldehyde, 5-10 parts of petroleum resin, 0.5-1 part of zinc oxide, 0.5-1 part of benzotriazole, 1-2 parts of titanium dioxide, 1-2 parts of KH560 and 0.5-1 part of auxiliary agent. The addition of the petroleum resin can improve the processing performance of the composition, so that the processing is smooth, and the problems of poor plasticization and uneven dispersion in the processing process can be solved; according to the invention, the zinc oxide, the titanium dioxide and the benzotriazole are compounded, and the compound not only can penetrate through the cell wall of bacteria and be combined with the basic group on the nucleic acid of cells to kill the bacteria, but also can slowly decompose negatively charged electrons and positively charged holes to react with organic matters in the bacteria to kill the bacteria, so that the compound has a long-term sterilization effect; the compound also has good anti-aging effect, and the anti-aging effect is more excellent than that of the compound added with benzotriazole or titanium dioxide or zinc oxide.

Description

Anti-aging and mildew-proof polyformaldehyde material and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to an anti-aging and mildew-proof polyformaldehyde material and a preparation method thereof.

Background

The polyformaldehyde is a linear polymer without side chains, high in density and high in crystallinity, and has excellent comprehensive performance. Polyoxymethylene is a glossy, hard and dense material with a light yellow or white surface that can be used for a long period at temperatures ranging from-40 to 100 ℃. Its wear resistance and self-lubricating property are superior to most engineering plastics, and it also has good oil-resisting and peroxide-resisting properties. Is not acid-resistant, strong alkali-resistant and sunlight ultraviolet radiation-resistant. Polyoxymethylene has a tensile strength of 70MPa, low water absorption, dimensional stability, and gloss, which are all better than nylon, and is a highly crystalline resin, the toughest of thermoplastic resins. Has high heat resistance, bending strength, fatigue resistance, wear resistance and electrical property.

With the continuous development of the application, people put higher and more specific requirements on the polyformaldehyde, such as the requirement of having antibacterial and mildewproof properties. This is because the plastics are likely to produce mold due to migration of the internal additives or external contamination, which affects the use of the product. In addition, in order to improve the anti-aging performance of the polyformaldehyde, a toughening agent is generally added, and small molecular substances and monomers contained in the conventional toughening agent are a nutrient source of mould, so that the growth of the mould is promoted, and the consumption of an antibacterial agent in a mould-proof material is increased.

At present, the aim is generally achieved by adding antibacterial agents, wherein natural antibacterial agents have high safety but poor heat resistance and are easy to carbonize and decompose; the organic antibacterial agent has the defects of quick and high-efficiency sterilization, but poor long-acting property; the inorganic antibacterial agent has good long-term sterilization effect, but has slow antibacterial effect, and the silver and copper antibacterial agents have the problem of easy color change.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides an anti-aging and mildew-proof polyformaldehyde material and a preparation method thereof.

The purpose of the invention can be realized by the following technical scheme:

an anti-aging mildew-proof polyformaldehyde material is prepared from the following components in parts by weight:

in a further scheme, the melt mass flow rate of the polyformaldehyde at 230 ℃/2.16kg is 35-45g/10 min.

The titanium dioxide is rutile type, and the average particle size is 10 microns.

The auxiliary agent is prepared by compounding tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), tris (2, 4-di-tert-butylphenyl) phosphite and montan wax in a weight ratio of 1:1: 3.

The invention also aims to provide a preparation method of the anti-aging and mildew-proof polyformaldehyde material, which comprises the following steps:

(1) weighing 100 parts of polyformaldehyde, 5-10 parts of petroleum resin, 0.5-1 part of zinc oxide, 0.5-1 part of benzotriazole, 1-2 parts of titanium dioxide, 1-2 parts of KH560 and 0.5-1 part of auxiliary agent according to the weight ratio, and mixing in a high-speed mixer;

(2) adding the uniformly mixed materials into a double-screw extruder, and granulating to obtain an anti-aging and mildew-proof polyformaldehyde material; the temperature range of the double-screw extruder is 180-260 ℃.

The invention has the beneficial effects that:

1. the addition of the petroleum resin can improve the processing performance of the composition, so that the processing is smooth, and the problems of poor plasticization and uneven dispersion in the processing process can be solved.

2. According to the invention, the zinc oxide, the titanium dioxide and the benzotriazole are compounded, and the compound not only can penetrate through the cell wall of bacteria and be combined with the basic group on the nucleic acid of cells to kill the bacteria, but also can slowly decompose negatively charged electrons and positively charged holes to react with organic matters in the bacteria to kill the bacteria, so that the compound has a long-term sterilization effect.

3. The compound also has good anti-aging effect, and the anti-aging effect is more excellent than that of the compound added with benzotriazole or titanium dioxide or zinc oxide.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

The melt mass flow rate of the polyformaldehyde used in each embodiment of the invention is 40g/10min under the condition of 230 ℃/2.16 kg; the titanium dioxide was of the rutile type with an average particle size of 10 microns.

Example 1

Weighing 100 parts of polyformaldehyde, 0.5 part of zinc oxide, 5 parts of petroleum resin, 0.5 part of benzotriazole, 1 part of titanium dioxide, 1 part of KH560, 0.1 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 0.1 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.3 part of montan wax, and mixing for 5 minutes in a high-speed mixer;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

Example 2

Weighing 100 parts of polyformaldehyde, 8 parts of petroleum resin, 1 part of zinc oxide, 1 part of benzotriazole, 2 parts of titanium dioxide, 2 parts of KH560, 0.15 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 0.15 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.45 part of montan wax, and mixing for 5 minutes in a high-speed mixer;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

Example 3

Weighing 100 parts of polyformaldehyde, 0.5 part of zinc oxide, 10 parts of petroleum resin, 1 part of benzotriazole, 1.5 parts of titanium dioxide, 1.5 parts of KH560, 0.15 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 0.15 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.45 part of montan wax, and mixing in a high-speed mixer for 5 minutes;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

Example 4

Weighing 100 parts of polyformaldehyde, 5 parts of petroleum resin, 1 part of zinc oxide, 1 part of benzotriazole, 2 parts of titanium dioxide, 2 parts of KH560, 0.2 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.6 part of montan wax, and mixing for 5 minutes in a high-speed mixer;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

Comparative example 1

Weighing 100 parts of polyformaldehyde, 0.1 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), 0.1 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.3 part of montan wax, and mixing in a high-speed mixer for 5 minutes;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

Comparative example 2

Weighing 100 parts of polyformaldehyde, 1 part of titanium dioxide, 0.1 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), 0.1 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.3 part of montan wax, and mixing for 5 minutes in a high-speed mixer;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

Comparative example 3

Weighing 100 parts of polyformaldehyde, 0.5 part of zinc oxide, 0.1 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), 0.1 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.3 part of montan wax, and mixing in a high-speed mixer for 5 minutes;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

Comparative example 4

Weighing 100 parts of polyformaldehyde, 0.5 part of benzotriazole, 0.1 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), 0.1 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.3 part of montan wax, and mixing in a high-speed mixer for 5 minutes;

and extruding and granulating the uniformly mixed materials in a double-screw extruder.

Extruder temperature settings were: zone I180 deg.C, zone II 200 deg.C, zone III 220 deg.C, zone IV 240 deg.C, zone V260 deg.C, zone VI 260 deg.C, and head 260 deg.C.

After the pellets of the above examples and comparative examples were granulated, the pellets were air-dried at 100 ℃ for 3 hours and molded into test pieces by an injection molding machine. The specimens were left for 48 hours at a constant temperature of 23 ℃ under dry conditions and then tested for impact strength and pre-photoaging mildew resistance rating according to standards. And (4) after the residual sample strips are subjected to xenon lamp light aging for 1000 hours according to GB/T16422.1-2006, testing the mildew-proof grade after the light aging. The test results are shown in Table 1.

TABLE 1

The materials prepared in the examples and the comparative examples were subjected to xenon lamp aging tests under the following test conditions:

irradiance: 0.55W/(m)².nm)@420nm，

Continuous illumination: black mark temperature: (100 ± 2) ° c, relative humidity: (50. + -. 5)%,

a filter lens: the Window-B/SL is arranged in the Window,

exposure time: 3000 hours.

And (3) carrying out color difference comparison on the aged test and the comparative test, wherein the data are as follows:

TABLE 2

As can be seen from tables 1 and 2, the zinc oxide, the titanium dioxide and the benzotriazole are compounded, and the compound not only can penetrate through cell walls of bacteria and be combined with bases on nucleic acid of cells to kill the bacteria, but also can slowly decompose negatively charged electrons and positively charged holes to react with organic matters in the bacteria to kill the bacteria, so that the compound has a long-term sterilization effect.

In addition, the compound also has good anti-aging effect, and the anti-aging effect is more excellent than that of the single addition of benzotriazole, titanium dioxide or zinc oxide.

The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications can be made to the embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.

Claims (5)

1. An anti-aging mildew-proof polyformaldehyde material is characterized in that: the composition is prepared from the following components in parts by weight:

polyoxymethylene 100 parts

5-10 parts of petroleum resin

0.5 to 1 portion of zinc oxide

0.5-1 part of benzotriazole

1-2 parts of titanium dioxide

KH 5601-2 parts

0.5-1 part of assistant.

2. The anti-aging and mildew-proof polyformaldehyde material as claimed in claim 1, wherein: the melt mass flow rate of the polyformaldehyde at 230 ℃/2.16kg is 35-45g/10 min.

3. The anti-aging and mildew-proof polyformaldehyde material as claimed in claim 1, wherein: the titanium dioxide is rutile type, and the average particle size is 10 microns.

4. The anti-aging and mildew-proof polyformaldehyde material as claimed in claim 1, wherein the auxiliary agent is pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite and montan wax which are compounded in a weight ratio of 1:1: 3.

5. The method for preparing an anti-aging and anti-mildew polyoxymethylene material as claimed in any one of claims 1 to 4, wherein: the method comprises the following steps:

(1) weighing 100 parts of polyformaldehyde, 5-10 parts of petroleum resin, 0.5-1 part of zinc oxide, 0.5-1 part of benzotriazole, 1-2 parts of titanium dioxide, 1-2 parts of KH560 and 0.5-1 part of auxiliary agent according to the weight ratio, and mixing in a high-speed mixer;

(2) adding the uniformly mixed materials into a double-screw extruder, and granulating to obtain an anti-aging and mildew-proof polyformaldehyde material; the temperature range of the double-screw extruder is 180-260 ℃.