CN110655684A - Biodegradable master batch and biodegradable LDPE (Low-Density polyethylene) film containing same - Google Patents
Biodegradable master batch and biodegradable LDPE (Low-Density polyethylene) film containing same 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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- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention belongs to the technical field of plastics, in particular to a biodegradable master batch and a biodegradable LDPE film containing the master batch,the biodegradable master batch is prepared from LEPE, modified starch and modified CaCO3Polyethylene glycol acetate, ethylene acrylic acid copolymer, TiO2Mixing with promoter, and granulating; the biodegradable LDPE film is of a three-layer structure and comprises an upper surface layer, a core layer and a lower surface layer; the film prepared by the invention has high degradation rate, higher tensile strength and better puncture resistance and tear resistance.
Description
Technical Field
The invention belongs to the technical field of films, and particularly relates to a biodegradable master batch and a biodegradable LDPE film containing the same.
Background
The white pollution is an image name of people for the environment polluted by the plastic waste. It is characterized by that various domestic plastic products made of high-molecular compounds of polystyrene, polypropylene and polyvinyl chloride are discarded into solid waste after use, and because the domestic plastic products are randomly thrown away and hardly degraded, the urban environment is seriously polluted. Not only can influence agricultural development, but also can threaten animal survival, waste plastics can occupy a large amount of land along with landfill, and the occupied land can not be recovered for a long time, so that the sustainable utilization of the land is influenced. The waste plastic products entering the household garbage do not degrade within 200 years if the waste plastic products are buried.
The degradable plastics have been developed greatly in recent years, and belong to a new member in the family of plastics, a seedling in an environment-friendly product, and a new material in the high-tech field, which is listed in Japan as a fourth material following metals, inorganic materials and high molecular materials. But also has a plurality of problems and difficulties in development; the self-technology of the degradable plastics, such as a more reasonable process formula, a degradation promoter, a compatilizer technology, a bioengineering technology, an alloying technology, accurate degradation time control, rapid degradation and complete degradation after use, a scientific degradation performance test evaluation method and standard easy to operate, a corner waste recycling technology and the like, needs to be further researched, developed, perfected and improved, the price needs to be further reduced, and the application needs to be further developed.
The appearance of the degradable plastic not only expands the functions of the plastic, but also relieves and inhibits the environmental contradiction to a certain extent, and is also a supplement to the petroleum resources which are gradually exhausted.
At present, completely biodegradable plastics including natural polymers, microbial synthesis and synthetic polymers are available in the market, and can be degraded into carbon dioxide and water in a short period after being used, and the first two raw materials are from natural renewable resources every year, so that the completely biodegradable plastics are ideal substitute products with environmental protection and adaptability.
The other polylactic acid degradable plastic has defects in performance, raw materials are difficult to dry, bubbles are easy to generate during extrusion, a film is easy to break, the price difference between the polylactic acid and a common plastic product is large, and the development of the industrial market is influenced by the high price of the polylactic acid product. Generally, the price of polylactic acid is 50% -200% higher than that of the traditional plastic, taking a plastic bag as an example, the density of polylactic acid is 1.24g/ml, the density of PE and PP is 0.9g/ml, the same strength is achieved, the polylactic acid bag is thicker than a PE or PP plastic bag, and more raw materials are needed, so the polylactic acid plastic bag is more than 1 time more expensive than the PE or PP plastic bag, and many supermarkets naturally do not want to provide the expensive shopping bag for customers freely. Also, in the field of agricultural film applications, the cost difference from PE makes the polylactic acid material unacceptable to farmers.
Disclosure of Invention
The invention aims to provide a biodegradable master batch and a biodegradable LDPE film containing the same, which can improve the degradation rate of the film and recycle resources under the conditions of basically not increasing the cost and not influencing the performance of the film.
The invention provides the following technical scheme for achieving the aim:
the biodegradable master batch is prepared from the following components in parts by mass of 15 ~ 20 parts of LDPE, 35 ~ 50 parts of modified starch and 35 parts of modified CaCO315 ~ 25 parts, 5 ~ 8 parts of polyethylene acetate glycol, 4 ~ 7 parts of ethylene acrylic acid copolymer, and TiO28 ~ 10 parts and A promoter 2 ~ 3 parts.
Further, the A promoter is composed of a 2-hydroxybenzophenone photo-oxidant, a plasticizer DOP, oxidized polyethylene and the like.
Further, the B accelerator consists of a surface additive and polyacrylamide.
Further, the modified starch comprises, by mass, 80 ~ 100 parts of starch, 3 ~ 5 parts of hydroxymethyl starch, 1 ~ 2 parts of urea, 2 ~ 4 parts of polycaprolactone, 2 ~ 4 parts of a B accelerator and 1 ~ 3 parts of a castor oil ethylene oxide condensate;
further, the modified CaCO3The composition comprises the following components in parts by mass: CaCO390 ~ 100 parts, 3 ~ 5 parts of B accelerator, HSt4 ~ 6 parts, CaO14 ~ 18 parts
Further, the modified starch needs to be pretreated by adding a high-speed mixer, drying at 120 ~ 130 ℃ for 20 ~ 30 minutes until the water content is about 2%, adding urea and B accelerator, blending for 10 ~ 15 minutes, adding hydroxymethyl starch, mixing for 3 ~ 5 minutes, adding polycaprolactone, mixing for 3 ~ 5 minutes, and finally adding a castor oil ethylene oxide condensate, and mixing for 3 ~ 5 minutes.
Further, the modified CaCO3The pretreatment mode is as follows: CaCO is added into a high-speed mixer3The B promoter, HSt and CaO were added and mixed at high speed for 15 ~ 20 minutes while heating to 80 ℃.
The invention also aims to provide a biodegradable LDPE film containing the biodegradable master batch, which has a three-layer structure and comprises an upper surface layer, a core layer and a lower surface layer.
Further, the upper and lower surface layers are respectively prepared from 1 ~ 1.2.2% of biodegradable master batch, 2 ~ 3% of anti-blocking agent and the balance of LDPE, and the core layer is prepared from 1 ~ 1.2.2% of biodegradable master batch, 1 ~ 2% of antistatic agent and the balance of LDPE.
Further, the upper and lower skin layers had a thickness of 0.02 ~ 0.04.04 mm, and the core layer had a thickness of 0.1 ~ 0.12.12 mm.
Compared with the prior art, the invention has the following beneficial effects:
1. the biodegradable LDPE film has good transparency, easy processability and flexibility.
2. The biodegradable LDPE film disclosed by the invention is good in electrical insulation, moisture resistance and radiation resistance.
3. Compared with polylactic acid degradable plastics and completely biodegradable plastics, the biodegradable LDPE film has the advantages of low cost, easy production and small influence on the performance of the film.
Detailed Description
Example 1
A biodegradable master batch is prepared from the following components in parts by mass: 20 parts of LDPE, 40 parts of modified starch and modified CaCO320 parts of polyethylene acetate, 5 parts of polyethylene glycol and ethylene acrylic acid4 parts of polymer and TiO28 parts and 2 parts of A promoter.
The preparation process of the master batch comprises 1, pretreating the modified starch, namely adding the modified starch into a high-speed mixer, drying the modified starch at 120 ~ 130 ℃ for 20 ~ 30 minutes until the water content is about 2 percent, adding the urea and the B accelerator for blending for 10 ~ 15 minutes, adding the hydroxymethyl starch for mixing for 3 ~ 5 minutes, adding the polycaprolactone for mixing for 3 ~ 5 minutes, adding the castor oil ethylene oxide condensate for mixing for 3 ~ 5 minutes, and finally adding the modified CaCO3The pretreatment mode is as follows: CaCO is added into a high-speed mixer3Heating to 80 ℃, adding B accelerator, HSt and CaO, mixing at high speed for 15 ~ 20 minutes, 3, fully mixing all the components in a low-speed mixer according to the proportion, and performing melt extrusion and granulation in a double-screw extruder, wherein the melting temperature is 148 ℃, the melt pressure is 2.4MPa, and the rotating speed is 150 r/min.
The biodegradable LDPE film is of a three-layer structure and comprises an upper surface layer, a core layer and a lower surface layer.
The upper surface layer and the lower surface layer are respectively prepared from 1% of biodegradable master batch, 2% of anti-blocking agent and the balance of LDPE, and the core layer is prepared from 1.2% of biodegradable master batch, 1% of antistatic agent and the balance of LDPE.
The thicknesses of the upper surface layer and the lower surface layer are 0.02 mm, and the thickness of the core layer is 0.1 mm.
The preparation method of the biodegradable LDPE film comprises the following steps:
1. the core layer raw materials, namely the biodegradable master batch, the antistatic agent and the LDPE, are dried and proportioned and then melted and extruded on a main extruder, the upper surface layer raw material and the lower surface layer raw material are respectively dried and proportioned and melted and extruded on two extruders, and then are converged and extruded from a three-layer structure die head, wherein the temperature of the die head is 250 ℃.
2. The extruded composite film is air-cooled for 35-50s at the air speed of 1-2 m/s.
3. The resin from the die was cooled to a sheet with a casting roll temperature of 22 ~ 26 ℃.
4. And a synchronous stretching system of a magnetic suspension linear motor is adopted for synchronous stretching.
5. And cooling the film, and then feeding the film into a traction system for surface layer corona treatment and rolling.
Example 2
A biodegradable master batch is prepared from the following components in parts by mass: 18 parts of LDPE, 36 parts of modified starch and modified CaCO322 parts of polyethylene glycol, 7 parts of polyethylene acetate, 6 parts of ethylene acrylic acid copolymer and TiO29 parts and 2 parts of A promoter.
The preparation process of the master batch comprises 1, pretreating the modified starch, namely adding the modified starch into a high-speed mixer, drying the modified starch at 120 ~ 130 ℃ for 20 ~ 30 minutes until the water content is about 2 percent, adding the urea and the B accelerator for blending for 10 ~ 15 minutes, adding the hydroxymethyl starch for mixing for 3 ~ 5 minutes, adding the polycaprolactone for mixing for 3 ~ 5 minutes, adding the castor oil ethylene oxide condensate for mixing for 3 ~ 5 minutes, and finally adding the modified CaCO3The pretreatment mode is as follows: CaCO is added into a high-speed mixer3Heating to 80 ℃, adding B accelerator, HSt and CaO, mixing at high speed for 15 ~ 20 minutes, 3, fully mixing all the components in a low-speed mixer according to the proportion, and performing melt extrusion and granulation in a double-screw extruder, wherein the melting temperature is 148 ℃, the melt pressure is 2.4MPa, and the rotating speed is 150 r/min.
The biodegradable LDPE film is of a three-layer structure and comprises an upper surface layer, a core layer and a lower surface layer.
The upper surface layer and the lower surface layer are respectively prepared from 1.2% of biodegradable master batch, 2.2% of anti-blocking agent and the balance LDPE, and the core layer is prepared from 1.1% of biodegradable master batch, 1.5% of antistatic agent and the balance LDPE.
The thicknesses of the upper surface layer and the lower surface layer are 0.02 mm, and the thickness of the core layer is 0.1 mm.
The preparation method of the biodegradable LDPE film comprises the following steps:
1. the core layer raw materials, namely the biodegradable master batch, the antistatic agent and the LDPE, are dried and proportioned and then melted and extruded on a main extruder, the upper surface layer raw material and the lower surface layer raw material are respectively dried and proportioned and melted and extruded on two extruders, and then are converged and extruded from a three-layer structure die head, wherein the temperature of the die head is 250 ℃.
2. And (3) carrying out air cooling on the extruded composite film for 35-50s at the air speed of 1-2 m/s.
3. The resin from the die was cooled to a sheet with a casting roll temperature of 22 ~ 26 ℃.
4. And a synchronous stretching system of a magnetic suspension linear motor is adopted for synchronous stretching.
5. And cooling the film, and then feeding the film into a traction system for surface layer corona treatment and rolling.
Example 3
A biodegradable master batch is prepared from the following components in parts by mass: 19 parts of LDPE, 45 parts of modified starch and modified CaCO324 parts of polyethylene glycol, 5 parts of polyethylene acetate, 4 parts of ethylene acrylic acid copolymer and TiO28 parts and 2 parts of A promoter.
The preparation process of the master batch comprises 1, pretreating the modified starch, namely adding the modified starch into a high-speed mixer, drying the modified starch at 120 ~ 130 ℃ for 20 ~ 30 minutes until the water content is about 2 percent, adding the urea and the B accelerator for blending for 10 ~ 15 minutes, adding the hydroxymethyl starch for mixing for 3 ~ 5 minutes, adding the polycaprolactone for mixing for 3 ~ 5 minutes, adding the castor oil ethylene oxide condensate for mixing for 3 ~ 5 minutes, and finally adding the modified CaCO3The pretreatment mode is as follows: CaCO is added into a high-speed mixer3Heating to 80 ℃, adding B accelerator, HSt and CaO, mixing at high speed for 15 ~ 20 minutes, 3, fully mixing all the components in a low-speed mixer according to the proportion, and performing melt extrusion and granulation in a double-screw extruder, wherein the melting temperature is 148 ℃, the melt pressure is 2.4MPa, and the rotating speed is 150 r/min.
The biodegradable LDPE film is of a three-layer structure and comprises an upper surface layer, a core layer and a lower surface layer.
The upper surface layer and the lower surface layer are respectively prepared from 1.1% of biodegradable master batch, 2.5% of anti-blocking agent and the balance of LDPE, and the core layer is prepared from 1% of biodegradable master batch, 1% of antistatic agent and the balance of LDPE.
The thicknesses of the upper surface layer and the lower surface layer are 0.02 mm, and the thickness of the core layer is 0.1 mm.
The preparation method of the biodegradable LDPE film comprises the following steps:
1. the core layer raw materials, namely the biodegradable master batch, the antistatic agent and the LDPE, are dried and proportioned and then melted and extruded on a main extruder, the upper surface layer raw material and the lower surface layer raw material are respectively dried and proportioned and melted and extruded on two extruders, and then are converged and extruded from a three-layer structure die head, wherein the temperature of the die head is 250 ℃.
2. And (3) carrying out air cooling on the extruded composite film for 35-50s at the air speed of 1-2 m/s.
3. The resin from the die was cooled to a sheet with a casting roll temperature of 22 ~ 26 ℃.
4. And a synchronous stretching system of a magnetic suspension linear motor is adopted for synchronous stretching.
5. And cooling the film, and then feeding the film into a traction system for surface layer corona treatment and rolling.
The biodegradable LDPE film prepared in the above example 1.2.3 is tested for correlation performance, and the comprehensive performance of the biodegradable LDPE film prepared in the above example is found to be good.
Claims (8)
1. The biodegradable LDPE film is of a three-layer structure and comprises an upper surface layer, a core layer and a lower surface layer, and is characterized in that the upper surface layer and the lower surface layer are both prepared from 1 ~ 1.2.2% of biodegradable master batch, 2 ~ 3% of anti-blocking agent and the balance of LDPE, the core layer is prepared from 1 ~ 1.2.2% of biodegradable master batch, 1 ~ 2% of antistatic agent and the balance of LDPE, and the biodegradable master batch comprises, by mass, 15 ~ 20 parts of LDPE, 35 ~ 50 parts of modified starch, 35 ~ parts of modified CaCO315 ~ 25 parts, 5 ~ 8 parts of polyethylene acetate glycol, 4 ~ 7 parts of ethylene acrylic acid copolymer, and TiO28 ~ 10 parts and A promoter 2 ~ 3 parts.
2. The biodegradable LDPE film of claim 1, wherein the upper and lower skin layers have a thickness of 0.02 ~ 0.04.04 mm and the core layer has a thickness of 0.1 ~ 0.12.12 mm.
3. The biodegradable LDPE film of claim 1 wherein the a promoter is comprised of 2-hydroxybenzophenone photo-oxidant, plasticizer DOP, oxidized polyethylene, and the like.
4. The biodegradable LDPE film of claim 1 wherein the B promoter is comprised of a surface additive, polyacrylamide.
5. The biodegradable LDPE film according to claim 1, wherein the modified starch comprises, by mass, 80 ~ 100 parts of starch, 3 ~ 5 parts of hydroxymethyl starch, 1 ~ 2 parts of urea, 2 ~ 4 parts of polycaprolactone, 2 ~ 4 parts of B accelerator, and 1 ~ 3 parts of castor oil ethylene oxide condensate.
6. The biodegradable LDPE film of claim 1, wherein said modified CaCO3The composition comprises the following components in parts by mass: CaCO390 ~ 100 parts, 3 ~ 5 parts of B accelerator, HSt4 ~ 6 parts and 14 ~ 18 parts of CaO.
7. The biodegradable LDPE film of claim 1 wherein the modified starch is pre-treated by adding a high speed mixer, drying at 120 ~ 130 ℃ for 20 ~ 30 minutes to a moisture content of 2% or less, adding urea and B promoter, blending for 10 ~ 15 minutes, adding hydroxymethyl starch, mixing for 3 ~ 5 minutes, adding polycaprolactone, mixing for 3 ~ 5 minutes, and adding castor oil ethylene oxide condensate, mixing for 3 ~ 5 minutes.
8. The biodegradable LDPE film of claim 1, wherein said modified CaCO3The pretreatment mode is as follows: CaCO is added into a high-speed mixer3The B promoter, HSt and CaO were added and mixed at high speed for 15 ~ 20 minutes while heating to 80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810690250.0A CN110655684A (en) | 2018-06-28 | 2018-06-28 | Biodegradable master batch and biodegradable LDPE (Low-Density polyethylene) film containing same |
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| CN201810690250.0A CN110655684A (en) | 2018-06-28 | 2018-06-28 | Biodegradable master batch and biodegradable LDPE (Low-Density polyethylene) film containing same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113043701A (en) * | 2021-04-22 | 2021-06-29 | 青岛海益塑业有限责任公司 | Composite degradable mulching film and preparation method thereof |
| CN116970238A (en) * | 2023-09-22 | 2023-10-31 | 淄博鑫业达新材料科技有限公司 | High-concentration white master batch and preparation method thereof |
-
2018
- 2018-06-28 CN CN201810690250.0A patent/CN110655684A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113043701A (en) * | 2021-04-22 | 2021-06-29 | 青岛海益塑业有限责任公司 | Composite degradable mulching film and preparation method thereof |
| CN116970238A (en) * | 2023-09-22 | 2023-10-31 | 淄博鑫业达新材料科技有限公司 | High-concentration white master batch and preparation method thereof |
| CN116970238B (en) * | 2023-09-22 | 2023-12-26 | 淄博鑫业达新材料科技有限公司 | High-concentration white master batch and preparation method thereof |
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