CN113930004B - Transparency modifier for gas-phase anti-rust film - Google Patents
Transparency modifier for gas-phase anti-rust film Download PDFInfo
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- CN113930004B CN113930004B CN202111545555.0A CN202111545555A CN113930004B CN 113930004 B CN113930004 B CN 113930004B CN 202111545555 A CN202111545555 A CN 202111545555A CN 113930004 B CN113930004 B CN 113930004B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
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- Extrusion Moulding Of Plastics Or The Like (AREA)
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Abstract
The invention provides a transparency modifier for a gas-phase anti-rust film, belonging to the technical field of anti-rust film preparation. The transparency modifier of the gas-phase antirust film consists of FLAMESTANOR 116, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, peroxide crosslinked polyethylene and copolymerization modifier. Under the combined action of FLAMESTAB NOR 116 and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, the antirust additive in the gas phase antirust film keeps stable in structure in the film blowing process and later use, and does not generate colored substances; under the combined action of peroxide crosslinked polyethylene and copolymerization modifier, the polyethylene resin keeps the crystallinity and regularity in the film blowing process, so that the higher transparency of the polyethylene resin is kept, and the transparency of the gas-phase antirust film is improved.
Description
Technical Field
The invention relates to the technical field of preparation of an anti-rust film, and particularly relates to a transparency modifier for a gas-phase anti-rust film.
Background
The gas phase rust-proof film is a metal rust-proof plastic film which is gradually developed in recent years, a gas phase corrosion inhibitor contained in the film can be automatically volatilized to the surface of metal, and the gas phase corrosion inhibitor forms a protective layer on the surface of the metal to play a role in inhibiting the corrosion of the metal. The gas-phase antirust film has the characteristics of long antirust period, simplicity and convenience in operation, wide use scene, low cost and the like, is a metal protection packaging material which is developed quickly in recent years, and has very important significance for the metal processing industry.
At present, the gas-phase antirust film is processed by taking polyethylene resin as a base material and adding chemical substances with volatile performance into the base material, and most of the chemical substances are not good in compatibility with the polyethylene resin and are generally added in a blending mode in a solid powder mode, so that certain influence is inevitably generated on the transparency of the gas-phase antirust film.
In fact, the transparency of most of gas-phase antirust films at home and abroad is poorer than that of polyethylene, and even the antirust films show certain colors due to the structural change of partial antirust components. In order to compensate or cover up the phenomenon, certain color is added when the gas-phase antirust film is generally produced. The rust-proof core component added in the existing gas-phase rust-proof film can cause the color of the rust-proof film to change under two conditions, and firstly, partial components are influenced by ultraviolet rays in natural light, the structure of the rust-proof film gradually changes, and a certain color is presented; secondly, under the influence of high temperature in the processing process, the structure of the original colorless partial component is changed, so that the anti-rust film has abnormal color (light yellow or pink), and the anti-rust film is possibly uneven, thereby reducing the appearance quality of the product. And thirdly, in the processing process, under the action of high temperature, the polymerization degree and the crystallinity of a polyethylene polymer chain are reduced, so that the transparency is reduced.
However, as the application range of the gas-phase anti-rust film is wider and wider, users have higher requirements on transparency, the traditional gas-phase anti-rust film cannot meet the requirements, but the composition of the anti-rust additive needs to be changed through a large amount of formula screening tests, and the input research and development cost is very high, so that the requirements on improving the transparency of the gas-phase anti-rust film are provided for the users and manufacturers.
Therefore, it is a problem to be solved at present to prepare a product capable of improving the transparency of a gas phase rust preventive film.
Disclosure of Invention
In view of the above, the present invention provides a transparency modifier for a gas phase rust preventive film. The transparency of the gas-phase antirust film is improved, and the yellowish or blackish color of the gas-phase antirust film can be changed into colorless and transparent by about 2 percent of a small amount of addition.
The transparency modifier for the gas-phase anti-rust film, which is prepared by the invention, comprises the following raw materials:
FLAMESTAB NOR 116 60~76%，
10 to 24 percent of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole,
5-18% of peroxide cross-linked polyethylene,
3-8% of a copolymerization modifier.
FLAMESTAB NOR 116 is a hindered amine with large molecular weight, and has a structural formula shown as formula (I),
in the formula (I), the structural formula of R is shown as the formula (II),
when exposed to UV radiation, FLAMESTANOR 116 can preferentially absorb UV radiation by changing its structure, thereby protecting the composition of the rust inhibitor from changing. When high temperature is met, free radicals or other active groups generated by heating other components are firstly absorbed by the antirust agent and consumed through the change of the structure of the antirust agent, and the structure of other components in the antirust agent is protected.
The 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole is a derivative of benzotriazole, is a heterocyclic compound with a good light stability effect, absorbs photon energy, and is structurally changed to form a new colorless structure, so that the benzotriazole which is a color-variable component in an antirust additive (which is a main component in a gas-phase antirust master batch and is prepared from molybdate, benzoate and benzotriazole according to the formula of the corrosion inhibitor in the invention patent 201110262905.2) has a stabilizing effect.
Preferably, the peroxide crosslinked polyethylene is crosslinked polyethylene prepared by using peroxide as an initiator, wherein the peroxide is cumene peroxide; or the same peroxide crosslinked polyethylene commercially available. Peroxide crosslinked polyethylene can improve the temperature resistance of polyethylene polymers.
Preferably, the copolymerization modifier is prepared from acrylonitrile, styrene and ethylene according to the weight ratio of 1-2: 4-5: 3-4 by mass ratio; during the processing of polyethylene products, a certain amount of copolymerization modifier is added, which is beneficial to improving the stability of the polyethylene products at high temperature and reducing the polymerization degree (molecular weight) under the action of high temperature.
The invention also aims to provide a preparation method of the transparency modifier for the gas-phase anti-rust film, which is characterized in that the temperature of a double-screw extruder is set to be 140 ℃, FLAMESTANOR 116, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, peroxide crosslinked polyethylene and a copolymerization modifier are added into the mixture according to the proportion, and the mixture is mixed, extruded and granulated to obtain the transparency modifier.
The gas-phase antirust film is prepared by applying the transparency modifier, and the raw materials of the gas-phase antirust film comprise:
28-30% of high-pressure polyethylene, 38-40% of linear polyethylene, 18-20% of metallocene polyethylene, 8-10% of gas-phase antirust master batch and 1-2% of transparency improver.
Preferably, the preparation method of the gas-phase antirust film comprises the following steps: the stock was placed in a blown film apparatus at a temperature of 150 ℃ and blown into a film having a thickness of 0.1 mm.
Compared with the prior art, the invention has the following beneficial effects:
under the combined action of FLAMESTAB NOR 116 and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, the antirust additive in the gas phase antirust film keeps stable in structure in the film blowing process and later use, and does not generate colored substances; under the combined action of peroxide crosslinked polyethylene and copolymerization modifier, the polyethylene resin keeps its crystallinity and regularity in the film blowing process, thereby keeping its own higher transparency.
Detailed Description
The invention provides a transparency modifier for a gas-phase anti-rust film, which consists of the following raw materials:
FLAMESTAB NOR 116 60~76%，
10 to 24 percent of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole,
5-18% of peroxide cross-linked polyethylene,
3-8% of a copolymerization modifier.
The transparency modifier is used for preparing the gas-phase anti-rust film, and the raw materials are as follows: 28-30% of high-pressure polyethylene, 38-40% of linear polyethylene, 18-20% of metallocene polyethylene, 8-10% of gas-phase antirust master batch and 1-2% of transparency improver.
In an embodiment of the present invention, the peroxide crosslinked polyethylene was purchased from Shandong Taikai Cable company, Inc. with a type YJ-35 peroxide crosslinked polyethylene insulation; the copolymerization modifier is prepared from acrylonitrile, styrene and ethylene according to the weight ratio of 2: 5: 3 in a mass ratio of the copolymer; the high-pressure polyethylene is high-pressure polyethylene 2426 (purchased from Yanshan petrochemical); the linear polyethylene is linear polyethylene 7042 (purchased from the comforting petrochemical); the metallocene polyethylene (purchased from exxon); the gas phase rust-proof master batch (prepared by the preparation method of example 1 in the patent 201110262905.2).
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a gas-phase antirust film comprises the following steps:
(1) preparing a transparency modifier: weighing raw materials according to the proportion of FLAMESTAB NOR 11660%, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole 14%, peroxide crosslinked polyethylene 18% and copolymerization modifier 8%, setting the temperature of a double-screw extruder to be 140 ℃, adding the raw materials, mixing, extruding and granulating to obtain the transparency modifier;
(2) preparing a gas-phase antirust film: according to the high-pressure polyethylene 242629%, the linear polyethylene 704239%, the metallocene polyethylene 20%, the gas-phase rust-proof master batch 10% and the transparency improver 2%, the raw materials are placed in a film blowing device at the temperature of 150 ℃ and blown into a film with the thickness of 0.1 mm.
Example 2
A preparation method of a gas-phase antirust film comprises the following steps:
(1) preparing a transparency modifier: weighing raw materials according to the proportion of FLAMESTAB NOR 11672%, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole 10%, peroxide crosslinked polyethylene 12% and copolymerization modifier 6%, setting the temperature of a double-screw extruder to be 140 ℃, adding the raw materials, mixing, extruding and granulating to obtain the transparency modifier;
(2) preparing a gas-phase antirust film: according to the high-pressure polyethylene 242629%, the linear polyethylene 704239%, the metallocene polyethylene 20%, the gas-phase rust-proof master batch 10% and the transparency improver 2%, the raw materials are placed in a film blowing device at the temperature of 150 ℃ and blown into a film with the thickness of 0.1 mm.
Comparative example 1
A preparation method of a gas-phase antirust film comprises the following steps:
according to the high-pressure polyethylene 242630%, the linear polyethylene 704240%, the metallocene polyethylene 20% and the gas-phase antirust master batch 10%, the raw materials are placed in a film blowing device at the temperature of 150 ℃ and blown into a film with the thickness of 0.1 mm.
Comparative example 2
A preparation method of a gas-phase antirust film comprises the following steps:
according to the high-pressure polyethylene 242630%, the linear polyethylene 704250% and the metallocene polyethylene 20%, the raw materials are placed in a film blowing device at the temperature of 150 ℃ and blown into a film with the thickness of 0.1 mm.
After the gas-phase anti-rust films prepared in examples 1-2 and comparative examples 1-2 are blown and irradiated under ultraviolet light for 24 hours, transparency test is carried out according to the GB/T2410-2008 spectrophotometer method standard, and chromaticity test is carried out according to the GJB 1253-91 standard, and the results are shown in Table 1. When testing the chromaticity, the wavelength of the spectrophotometer is selected to be 570 nm.
TABLE 1
| Index name | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Transparency | 88% | 90% | 65% | 98% |
| Color intensity | 88% | 86% | 70% | 98% |
As can be seen from the results in Table 1, the addition of the gas-phase rust-preventive masterbatch can seriously reduce the transparency and chromaticity of the gas-phase rust-preventive film, and the transparency and chromaticity of the gas-phase rust-preventive film can be obviously improved by adding the transparency modifier prepared by the method.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A transparency modifier for a gas-phase antirust film is characterized by comprising the following raw materials:
the copolymerization modifier is a high-molecular polymer copolymerized by acrylonitrile, styrene and ethylene according to the mass ratio of 1-2: 4-5: 3-4.
2. The transparency modifier for a gas-phase antirust film according to claim 1, characterized in that the peroxide crosslinked polyethylene is a crosslinked polyethylene prepared by using a peroxide as an initiator, and the peroxide is cumene peroxide.
3. The method for preparing the transparency modifier for a gas-phase rust preventive film according to any one of claims 1 to 2, characterized by comprising the steps of:
setting the temperature of a double-screw extruder to be 140 ℃, adding FLAMESTANOR 116, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, peroxide crosslinked polyethylene and a copolymerization modifier in proportion, mixing, extruding and granulating to obtain the transparency modifier.
4. A gas-phase antirust film, which is characterized by being prepared from the transparency modifier according to any one of claims 1 to 2, and which is prepared from the following raw materials:
28-30% of high-pressure polyethylene, 38-40% of linear polyethylene, 18-20% of metallocene polyethylene, 8-10% of gas-phase antirust master batch and 1-2% of transparency improver.
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| CN202111545555.0A CN113930004B (en) | 2021-12-17 | 2021-12-17 | Transparency modifier for gas-phase anti-rust film |
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Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE239052T1 (en) * | 1998-11-10 | 2003-05-15 | Procter & Gamble | FILM WITH UV BARRIER PROPERTIES |
| CN101323956A (en) * | 2007-06-14 | 2008-12-17 | 熊小勇 | Composite gas-phase anti-rust master batch and preparing process thereof |
| CN102391548B (en) * | 2011-09-07 | 2013-06-19 | 中国人民解放军军械工程学院 | Biodegradable starch-based molybdate gas-phase rust-preventing masterbatch |
| CN104212160A (en) * | 2014-09-18 | 2014-12-17 | 苏州市雄林新材料科技有限公司 | Transparent TPU (thermoplastic polyurethane) film with high yellowing-resistance and preparation method thereof |
| CN106751559A (en) * | 2016-11-16 | 2017-05-31 | 华南理工大学 | A kind of ultraviolet aging resistance PBAT thin-film materials and preparation method thereof |
| CN110835464B (en) * | 2019-11-13 | 2021-12-28 | 东莞市雄林新材料科技股份有限公司 | Never-yellowing TPU film and preparation method thereof |
| CN110903536A (en) * | 2019-11-26 | 2020-03-24 | 沈阳防锈包装材料有限责任公司 | Antirust packaging material and preparation method thereof |
| CN113087932A (en) * | 2021-04-01 | 2021-07-09 | 布兰诺工业包装材料(上海)有限公司 | Gas-phase antirust master batch and preparation method thereof |
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