CN114149634A - Natural ecological degradation master batch for high-transparency BOPP (biaxially-oriented Polypropylene) film and preparation method thereof - Google Patents
Natural ecological degradation master batch for high-transparency BOPP (biaxially-oriented Polypropylene) film and preparation method thereof Download PDFInfo
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- C08J2323/12—Polypropene
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- 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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K5/00—Use of organic ingredients
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Abstract
The natural ecological degradable master batch for the high-transparency BOPP film comprises a BOPP carrier, zinc stearate, a plasticizer, a compatilizer, ferric acetate, methyl salicylate, a lubricant, calcium oxide, cellulose and gelatin. After the BOPP is mixed with the natural ecological degradation master batch, the produced product has the biodegradation performance, the biodegradation rate is about 60 percent after 180 days, the biodegradation rate required by 38082 in China is achieved, and the national standard requirement of China is met. Can be completely biodegraded whether being discarded in the open air, landfilled or aerobic compost.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to a natural ecological degradation master batch for a high-transparency BOPP film and a preparation method thereof.
Background
The BOPP plastic is an important flexible packaging material and has wide application. BOPP is colorless, odorless, tasteless, non-toxic, and has high tensile strength, impact strength, rigidity, toughness, and good transparency. The BOPP film has good printing adaptability after corona treatment, and can be subjected to chromatography printing to obtain a fine appearance effect, so that the BOPP film is often used as a surface layer material of a composite film. BOPP films also have disadvantages such as easy accumulation of static electricity, no heat sealability, etc. In a production line running at high speed, the BOPP film is easy to generate static electricity, and a static electricity remover is required to be installed. In order to obtain the heat-sealable BOPP film, heat-sealable resin glue solution, such as PVDC latex, EVA latex and the like, can be coated on the surface of the BOPP film after corona treatment, solvent glue can also be coated on the surface of the BOPP film, and the heat-sealable BOPP film can also be produced by adopting an extrusion coating or co-extrusion compounding method. The film is widely applied to packages of bread, clothes, shoes and socks and the like, and covers of cigarettes and books. The BOPP can be coated with the adhesive sticker to produce the box sealing adhesive tape, and the box sealing adhesive tape is a market with larger BOPP consumption.
The BOPP film is widely applied to the industries of packaging, printing and the like and is known as the packaging empress. Because PP has no degradability, the use of a large amount of BOPP films causes environmental pollution and ecological damage. The environment-friendly degradable plastic requires that the product can be rapidly embrittled and fragmented under outdoor exposure or burying conditions, and meanwhile, the degraded product must be easily invaded and phagocytized by microorganisms, so that the product is converted into environment-friendly and nontoxic biomass.
The development trend of future packaging technology is expected, and the packaging material is generally considered to be developed towards high barrier property, low weight and greenness, so that the BOPP with the degradation function becomes an important development direction, and the development of the special degradation master batch meeting the production requirement of the BOPP film is a necessary way for realizing the function.
Disclosure of Invention
Based on the above, the invention aims to provide a natural ecological degradation master batch for a high-transparency BOPP film and a preparation method thereof, the prepared master batch meets the requirements of GB/T20197-.
The technical scheme adopted by the invention for realizing the purpose is as follows: the natural ecological degradable master batch for the high-transparency BOPP film comprises a BOPP carrier, zinc stearate, a plasticizer, a compatilizer and ferric acetate.
In the invention, the ferric acetate has a certain photosensitization effect and can promote the plastic to be continuously oxidized and degraded in a dark place after being initiated by illumination.
The zinc stearate has a certain photosensitization effect, but has another important performance on the carboxylic acid rare earth photosensitizer, namely, the zinc stearate can promote the plastic to continue oxidative degradation in the dark after being initiated by light.
Wherein the master batch also comprises methyl salicylate, lubricant, calcium oxide, cellulose and gelatin.
Methyl salicylate has a certain photosensitization effect, but has another important property for carboxylic acid rare earth photosensitizer, namely, the plastic can be promoted to be continuously oxidized and degraded in the dark after being initiated by light.
In the invention, the master batch sequentially comprises 35-40 parts by weight, 1-5 parts by weight, 1-3 parts by weight and 5-15 parts by weight of BOPP carrier, zinc stearate, plasticizer, compatilizer and ferric acetate.
In the invention, the master batch contains 1-3 parts of methyl salicylate, 1-3 parts of lubricant, 25-35 parts of calcium oxide, 1-10 parts of cellulose and 5-10 parts of gelatin in sequence by weight.
In a preferred embodiment of the present invention, the plasticizer is one or more of aliphatic diamide diol, triethanolamine, trimethylolpropane, and sorbitol.
In a preferred embodiment of the present invention, the compatibilizer is a grafted combination of BOPP and maleic anhydride or itaconic anhydride.
In a preferred embodiment of the present invention, the lubricant is one or more of PE wax, calcium stearate, and iron dimethyldithiocarbamate
The preparation method of the natural ecological degradation master batch for the high-transparency BOPP film comprises the following steps of mixing the master batch into the BOPP according to the mass ratio of 0.1-1.5%, uniformly mixing, and carrying out melt extrusion and grain cutting by a double-screw extruder to form the master batch, wherein the conditions of the extruder are as follows: the first zone is 100-.
The master batch can also be used for CPP films, PS films or sheets and PE films or sheets. And replacing the corresponding carrier with a corresponding film material.
The invention relates to an innovative technology for degrading BOPP films under the condition of discarding natural environment, the design aim of the degradation technology of the natural ecological degradation BOPP films is to keep the service life of the BOPP films in the whole life cycle and the commercial properties of mechanics, obstruction, transparency and the like required by the BOPP films as commodities, and the BOPP films can be biodegraded under the natural condition after being discarded.
The degradation principle of the BOPP film by natural ecological degradation is that the natural ecological degradation master batch is added into the BOPP film to enable the BOPP film to be acted to become a BOPP film product capable of being degraded by natural ecological degradation. The degradation of the BOPP film added with the natural ecological degradation master batch is divided into two stages:
the first stage is as follows: the BOPP film added with the natural ecological degradation assistant reacts with oxygen in the air to trigger the additive to attack the carbon chain of the polymer, and the carbon main chain is oxidized to form molecular fragments with the molecular weight less than or equal to 10000 or less (European and Japanese scientists believe that oligomers with the molecular weight less than 40000 can be phagocytized by microorganisms). Degradation at this stage is a non-biological process that promotes the insertion of oxygen atoms into the carbon backbone at the polymer break to form various functional groups (e.g., carboxylic acids, esters, aldehydes, alcohols, etc.). The compound is changed from a hydrophobic macromolecular chain to a hydrophilic micromolecular chain, so that molecular chain fragments are more easily eroded and digested by bacteria;
and a second stage: BOPP films are phagocytosed and decomposed by microorganisms (bacteria, fungi and algae) that are ubiquitous in nature as a nutrient source, and finally decomposed into carbon dioxide, water and biomass, and this stage of degradation is called biodegradation process.
Meanwhile, after absorbing Ultraviolet (UV) and other radiation energy, plastics form an electronic excited state to initiate a photochemical reaction, so that the structure of the plastics is damaged, and in a natural environment, plastic products are influenced by oxygen at the same time, so that photooxidation degradation is caused.
Meanwhile, the invention utilizes calcium oxide, cellulose and gelatin to construct a powder-silk-colloid diversified structure, so that the finished film has good contractibility. Meanwhile, after the degradation in the two stages, the diversified structure is easier to disassemble, and the degradation is further promoted.
The requirement of more than 60% of degradation rate can be achieved no matter in open air or in a laboratory state (the highest detection requirement of the national standards 20197 and 19277 on the biodegradation rate is 60%). In the laboratory state, for films with a thickness of less than 0.15, the biodegradation stage is carried out after ageing in a natural environment simulating 3 months. The simulated aging can be ultraviolet or xenon lamp aging. Entering the biodegradation stage, the international polyolefin degradation standard (PAS 9017: 2020) requires a degradation rate of more than 90% in 730 days. This is much higher than the national standard of China.
The natural ecological degradation BOPP film technology greatly exceeds the national standard and is in accordance with the international polyolefin degradation standard (PAS 9017: 2020).
Based on this, after the BOPP is mixed with the natural ecological degradation master batch, the produced product has the biodegradation performance, the biodegradation rate is about 60 percent after 180 days, the biodegradation rate required by 38082 in China is achieved, and the national standard requirement in China is met. Can be completely biodegraded whether being discarded in the open air, landfilled or aerobic compost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
The following description is only exemplary of the present application and should not be taken as limiting the present application, the scope of the present application is defined by the appended claims, and all changes that come within the meaning and range of equivalency of the specification are therefore intended to be embraced therein.
The natural ecological degradation master batch for the high-transparency BOPP film comprises a BOPP carrier, zinc stearate, a plasticizer, a compatilizer, iron acetate, methyl salicylate, a lubricant, calcium oxide, cellulose and gelatin. The weight portions are 35-40, 1-5, 1-3, 5-15, 1-3, 25-35, 1-10 and 5-10 in sequence.
Mixing the master batch into BOPP according to the mass ratio of 0.1-1.5%, after uniformly mixing, carrying out melt extrusion and grain cutting by a double-screw extruder to form the master batch, wherein the conditions of the extruder are as follows: the first zone is 100-. And (3) bracing the extrudate, cooling the extrudate at 25 ℃, then air-drying, granulating, vibrating and screening, drying, homogenizing and packaging to obtain a finished product.
Example 1
The natural ecological degradation master batch for the high-transparency BOPP film comprises 40 parts of BOPP carrier, 2 parts of zinc stearate, 1 part of plasticizer, 3 parts of compatilizer, 10 parts of ferric acetate, 1 part of methyl salicylate, 2 parts of lubricant, 35 parts of calcium oxide, 5 parts of cellulose and 10 parts of gelatin.
The master batch of the embodiment is added into a BOPP film, and is detected according to the ISO 14616 standard, which specifies the detection method of the shrinkage rate, the thermal shrinkage force, the cold shrinkage force and other performance parameters of the shrink film, and the following are measured: the transverse shrinkage rate was 14.89%, the cold shrinkage force was 1.3N, and the heat shrinkage force was 2.8N. The longitudinal shrinkage was 8.2%, the cold shrinkage was 0.07N, and the thermal shrinkage was 0.3N. High transparency of more than 90% and high optical haze of more than 80% are simultaneously achieved in the wavelength range of the visible spectrum of 370-780 nm.
Example 2
The natural ecological degradation master batch for the high-transparency BOPP film comprises 36 parts of BOPP carrier, 5 parts of zinc stearate, 2 parts of plasticizer, 2 parts of compatilizer, 12 parts of iron acetate, 2 parts of methyl salicylate, 1 part of lubricant, 30 parts of calcium oxide, 3 parts of cellulose and 8 parts of gelatin.
The master batch of the embodiment is added into a BOPP film, and is detected according to the ISO 14616 standard, which specifies the detection method of the shrinkage rate, the thermal shrinkage force, the cold shrinkage force and other performance parameters of the shrink film, and the following are measured: the transverse shrinkage rate is 14.9 percent, and the longitudinal shrinkage rate is 8.22 percent; high transparency exceeding 90.2% and high optical haze exceeding 81% are simultaneously achieved in the wavelength range of the visible spectrum of 370-780 nm.
Example 3
The natural ecological degradation master batch for the high-transparency BOPP film comprises 35 parts of BOPP carrier, 3 parts of zinc stearate, 3 parts of plasticizer, 1 part of compatilizer, 15 parts of iron acetate, 3 parts of methyl salicylate, 2 parts of lubricant, 33 parts of calcium oxide, 10 parts of cellulose and 6 parts of gelatin.
The master batch of the embodiment is added into a BOPP film, and is detected according to the ISO 14616 standard, which specifies the detection method of the shrinkage rate, the thermal shrinkage force, the cold shrinkage force and other performance parameters of the shrink film, and the following are measured: the transverse shrinkage rate is 15.0 percent, and the longitudinal shrinkage rate is 8.19 percent; high transparency exceeding 90.1% and high optical haze exceeding 80% are simultaneously achieved in the wavelength range of the visible spectrum of 370-780 nm.
Example 4
The natural ecological degradation master batch for the high-transparency BOPP film comprises 40 parts of BOPP carrier, 1 part of zinc stearate, 2.5 parts of plasticizer, 1.5 parts of compatilizer, 5 parts of iron acetate, 1 part of methyl salicylate, 3 parts of lubricant, 25 parts of calcium oxide, 2 parts of cellulose and 5 parts of gelatin.
The master batch of the embodiment is added into a BOPP film, and is detected according to the ISO 14616 standard, which specifies the detection method of the shrinkage rate, the thermal shrinkage force, the cold shrinkage force and other performance parameters of the shrink film, and the following are measured: the transverse shrinkage rate is 15.1 percent, and the longitudinal shrinkage rate is 8.32 percent; high transparency exceeding 90.2% and high optical haze exceeding 80% are simultaneously achieved in the wavelength range of the visible spectrum of 370-780 nm.
Claims (8)
1. The natural ecological degradation master batch for the high-transparency BOPP film is characterized by comprising a BOPP carrier, zinc stearate, a plasticizer, a compatilizer and iron acetate.
2. The natural ecological degradation master batch for the high transparent BOPP film according to claim 1, wherein: the master batch also comprises methyl salicylate, a lubricant, calcium oxide, cellulose and gelatin.
3. The natural ecological degradation master batch for the high transparent BOPP film according to claim 1, wherein: the master batch sequentially comprises 35-40 parts of BOPP carrier, 1-5 parts of zinc stearate, 1-3 parts of plasticizer, 1-3 parts of compatilizer and 5-15 parts of ferric acetate by weight.
4. The natural ecological degradation master batch for the high transparent BOPP film according to claim 2, wherein: the master batch comprises 1-3 parts of methyl salicylate, 1-3 parts of lubricant, 25-35 parts of calcium oxide, 1-10 parts of cellulose and 5-10 parts of gelatin in sequence by weight.
5. The natural ecological degradation master batch for a highly transparent BOPP film according to claim 1 or 3, wherein: the plasticizer is one or more of aliphatic diamide diol, triethanolamine, trimethylolpropane, sorbitol, etc.
6. The natural ecological degradation master batch for a highly transparent BOPP film according to claim 1 or 3, wherein: the compatilizer is a grafted combination of BOPP and maleic anhydride or itaconic anhydride.
7. The natural ecological degradation master batch for a highly transparent BOPP film according to claim 1 or 4, wherein: the lubricant is one or more of PE wax, calcium stearate and iron dimethyldithiocarbamate.
8. The method for preparing the natural ecological degradation master batch for the high transparent BOPP film according to claim 1, wherein the natural ecological degradation master batch comprises the following steps: mixing the master batch into BOPP according to the mass ratio of 0.1-1.5%, after uniformly mixing, carrying out melt extrusion and grain cutting by a double-screw extruder to form the master batch, wherein the conditions of the extruder are as follows: the first zone is 100-.
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Citations (6)
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| CN112143101A (en) * | 2020-09-24 | 2020-12-29 | 广东德冠薄膜新材料股份有限公司 | Degradation master batch for BOPP film, preparation method of degradation master batch and BOPP film |
| CN113617390A (en) * | 2021-08-17 | 2021-11-09 | 上海奥巴迪环保科技有限公司 | Efficient composite catalyst for biodegradable BOPP film and preparation method and application thereof |
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Patent Citations (6)
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| CN102634094A (en) * | 2012-03-31 | 2012-08-15 | 许昌学院 | Optical and thermal-oxidative dual-degradation plastic thin film and manufacturing method thereof |
| CN103895298A (en) * | 2014-04-12 | 2014-07-02 | 广东威孚包装材料有限公司 | Completely-biodegradable casting polypropylene film and manufacturing method thereof |
| CN105482486A (en) * | 2015-12-29 | 2016-04-13 | 王丽萍 | Novel high-performance plastic additive |
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