CN110406223B - Degradable environment-friendly polyolefin heat shrinkable film and preparation method thereof - Google Patents
Degradable environment-friendly polyolefin heat shrinkable film and preparation method thereof Download PDFInfo
- Publication number
- CN110406223B CN110406223B CN201910736159.2A CN201910736159A CN110406223B CN 110406223 B CN110406223 B CN 110406223B CN 201910736159 A CN201910736159 A CN 201910736159A CN 110406223 B CN110406223 B CN 110406223B
- Authority
- CN
- China
- Prior art keywords
- master batch
- multilayer
- cooling
- heat shrinkable
- degradable environment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
- B32B2307/736—Shrinkable
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a degradable environment-friendly polyolefin heat shrinkable film and a preparation method thereof. The degradable environment-friendly polyolefin heat shrinkable film comprises an outer layer, a core layer and an inner layer which are sequentially stacked. The preparation method of the degradable environment-friendly polyolefin heat shrinkable film comprises the following steps: mixing raw materials of each layer in proportion, respectively carrying out melting plasticization by using a single-screw extruder, then carrying out multilayer co-extrusion lamination by using a multilayer parallel conical die head to obtain multilayer melt, inflating the multilayer melt to obtain film bubbles, and then carrying out cooling shaping by using a shaping water jacket to obtain a primary blown film tube with a multilayer structure; after dewatering, the primary blown film tube is heated by a far infrared ceramic oven, then is blown by bubbling and inflating, and is longitudinally stretched to the required size by a synchronous machine to be sized and cooled; and finally, annealing and cooling, flattening, trimming and rolling. The degradable environment-friendly polyolefin heat shrinkable film provided by the application can be subjected to photo/biological double degradation, is good in mechanical strength and flexibility, and has good heat shrinkage performance.
Description
Technical Field
The invention relates to the field of polyolefin heat shrinkable films, in particular to a degradable environment-friendly polyolefin heat shrinkable film and a preparation method thereof.
Background
With the development of commodity economy, the packaging industry is rapidly changing greatly. The environmental pressure caused by economic growth is increasingly paid attention by people of all levels of society.
Polyolefin heat shrinkable films are widely used for the sale and transportation of various products because of their light weight and good mechanical properties. With the large-scale application of polyolefin heat shrinkable films, the recycling treatment thereof becomes a problem to be solved urgently. However, since the thin film type solar cell is generally thin and has a wide application range, the total application amount is large but the single application quality is low, the centralized treatment has high cost, and the concentrated treatment is scattered in places such as land, rivers, lakes and the like, so that a large environmental problem is caused.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a degradable environment-friendly polyolefin heat shrinkable film, which can be subjected to light/biological dual degradation, has good mechanical strength and flexibility and good heat shrinkage performance.
The second purpose of the invention is to provide a preparation method of the degradable environment-friendly polyolefin heat shrinkable film, which has simple process and stable product quality.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a degradable environment-friendly polyolefin heat shrinkable film comprises an outer layer, a core layer and an inner layer which are sequentially laminated,
the outer layer and the inner layer comprise the following raw materials in percentage by mass: PP 30-50%, mLDPE 25-30%, degradable master batch 10-20%, kaolin master batch 10-15%, silicone anti-blocking master batch 1-3%, erucamide smooth master batch 1-3% and surfactant type antistatic agent master batch 1-3%;
the core layer comprises the following raw materials in percentage by mass: 35-60% of LDPE, 15-20% of mLDPE, 10-20% of degradation master batch, 10-15% of kaolin master batch and 5-10% of erucamide smooth master batch;
the degradation master batch comprises the following components in percentage by mass: 5-20 wt% of nano titanium dioxide, 10-30 wt% of polyoxyethylene and the balance of LDPE;
the kaolin master batch comprises the following components in percentage by mass: 30-50 wt% of kaolin and 50-70 wt% of LDPE.
The nano titanium dioxide has the advantages of high photocatalytic activity, no toxicity, economic price and high photochemical stability, and is a good choice for polyethylene degradation photocatalysts. However, common titanium dioxide is difficult to disperse uniformly in polyethylene, and the photodegradation effect is influenced; the invention uses PEO (polyoxyethylene) to mix the nano titanium dioxide to obtain the modification effect, obtains the degradation master batch with good dispersion effect in the polyolefin thermal shrinkage film, and then is used for production. The kaolin is used as a biodegradation accelerator, and the addition of the kaolin can not only accelerate the photodegradation of the polymer film, but also accelerate the biodegradation of the residue of the polymer film.
Preferably, the melt index of PP in the outer layer and the melt index of PP in the inner layer are both 0.4-1.0g/10min and the melt index of LDPE in the core layer is 0.25-3g/10min under the condition of 190 ℃ under the condition of 2.16kg pressure.
Preferably, the melt index of mLDPE in the outer layer, the core layer and the inner layer is 0.5-5g/10min under the condition of 190 ℃ and 2.16kg pressure.
The preparation method of the degradable environment-friendly polyolefin heat shrinkable film comprises the following steps:
A. mixing raw materials of each layer in proportion, respectively carrying out melting plasticization by using a single-screw extruder, then carrying out multilayer co-extrusion lamination by using a multilayer parallel conical die head to obtain multilayer melt, inflating the multilayer melt to obtain film bubbles, and then carrying out cooling shaping by using a shaping water jacket to obtain a primary blown film tube with a multilayer structure;
B. the primary blown film tube is heated by a far infrared ceramic oven after water removal, then is blown by bubbling and inflating, is longitudinally stretched to a required size by a synchronous machine, and is subjected to sizing cooling to perform sizing cooling;
C. and finally, annealing and cooling, flattening, trimming and rolling to obtain the degradable environment-friendly polyolefin thermal shrinkage film.
Preferably, the temperature of the screw extruder is set to: the feeding section is 160-180 ℃, the melting section is 160-190 ℃ and the homogenizing section is 190-220 ℃; the temperature range of the multilayer parallel tapered die head is 190 ℃ to 220 ℃, and the die lip gap is 1.0-2.5 mm.
Preferably, the diameter of the film bubble is 400-560 mm.
Preferably, the temperature of the cooling water in the shaping water jacket is 10-17 ℃; the temperature of the primary blown film tube after being heated by the far infrared ceramic oven is 85-110 ℃.
Preferably, the mechanical longitudinal stretching has a ratio of 4.0 to 6.5 times in the transverse stretching and a ratio of 4.8 to 6.8 times in the longitudinal stretching.
Preferably, the sizing cooling is performed by using a 5-level cooling air ring, and the air volume of the 1 st-level air ring is 1000-3H, the air volume of the 2 nd-stage air ringIs 1000-3The air volume of the 3 rd level air ring is 1000-2000m3The air volume of the 4 th-level air ring and the 5 th-level air ring is 500-3/h。
Optionally, in the step C, the annealing temperature is 60 to 80 ℃, and the cooling medium used for cooling has a temperature of 10 to 30 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the degradable environment-friendly polyolefin heat shrinkable film provided by the application can be subjected to photo/biological double degradation, has good mechanical strength and flexibility, and has good heat shrinkage performance;
the preparation method of the degradable environment-friendly polyolefin heat shrinkable film provided by the application is stable in process.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The degradable environment-friendly polyolefin heat shrinkable film comprises an outer layer, a core layer and an inner layer which are arranged in a laminated manner, wherein the raw materials of each layer are as follows:
outer layer:
44 wt% PP (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
30 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 2g/10min)
10 wt% degradation master batch
10 wt% kaolin master batch
2 wt% silicone anti-blocking masterbatch
2 wt% erucamide smooth master batch
2 wt% of surfactant type antistatic agent master batch;
core layer:
52 wt% LDPE (2.16kg pressure, melt index at 190 ℃ 1.5g/10min)
20 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 2g/10min)
10 wt% degradation master batch
10 wt% kaolin master batch
8 wt% of erucamide smooth master batch;
inner layer:
44 wt% PP (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
30 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 2g/10min)
10 wt% degradation master batch
10 wt% kaolin master batch
2 wt% silicone anti-blocking masterbatch
2 wt% erucamide smooth master batch
2 wt% of surfactant type antistatic agent master batch.
The degradation master batch comprises the following components in percentage by mass: 5 wt% of nano titanium dioxide, 30 wt% of polyoxyethylene and 65 wt% of LDPE;
the kaolin master batch comprises the following components in percentage by mass: 30 wt% of kaolin and 70 wt% of LDPE.
The preparation process comprises the following steps:
respectively using a single-screw extruder to perform melting plasticization after mixing the raw materials of each layer in proportion, wherein the temperature of the screw extruder is set as follows: the feeding section is 160-180 ℃, the melting section is 160-190 ℃ and the homogenizing section is 190-220 ℃; then multilayer co-extrusion lamination is carried out by using a multilayer parallel conical die head to obtain multilayer melt, the temperature range of the multilayer parallel conical die head is 190 ℃, the die lip gap is 2.5mm, the multilayer melt is inflated to obtain a film bubble with the diameter of 560mm, then the multilayer structure film tube is cooled and shaped by using a shaping water jacket to obtain a multilayer structure primary blown film tube, and the temperature of cooling water in the shaping water jacket is 17 ℃.
After dewatering, the primary blown film tube is heated to 110 ℃ by a far infrared ceramic oven, then is blown by bubbling and inflating, is longitudinally stretched to the required size by a synchronous machine, and is sized and cooled, wherein the blowing transverse stretching multiple is 4.0 times, and the longitudinal stretching multiple is 6.8 times; sizing cooling adopts 5 gradesCooling wind ring is carried out, and the wind quantity of the 1 st level wind ring is 2500m3H, the air volume of the 2 nd-stage air ring is 2000m3H, the air volume of the 3 rd level air ring is 1000m3H, the air volume of the 4 th and 5 th wind rings is 500m3/h。
Finally, annealing and cooling are carried out, wherein the annealing temperature is 60 ℃, and the temperature of a cooling medium used for cooling is 30 ℃; flattening, trimming and rolling to obtain the degradable environment-friendly polyolefin thermal shrinkage film.
Example 2
The degradable environment-friendly polyolefin heat shrinkable film comprises an outer layer, a core layer and an inner layer which are arranged in a laminated manner, wherein the raw materials of each layer are as follows:
outer layer:
34 wt% PP (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
25 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 1.5g/10min)
20 wt% degradation master batch
15 wt% kaolin master batch
2 wt% silicone anti-blocking masterbatch
2 wt% erucamide smooth master batch
2 wt% of surfactant type antistatic agent master batch;
core layer:
42 wt% LDPE (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
15 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 1.5g/10min)
20 wt% degradation master batch
15 wt% kaolin master batch
8 wt% of erucamide smooth master batch;
inner layer:
34 wt% PP (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
25 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 1.5g/10min)
20 wt% degradation master batch
15 wt% kaolin master batch
2 wt% silicone anti-blocking masterbatch
2 wt% erucamide smooth master batch
2 wt% of surfactant type antistatic agent master batch.
The degradation master batch comprises the following components in percentage by mass: 20 wt% of nano titanium dioxide, 10 wt% of polyoxyethylene and 70 wt% of LDPE;
the kaolin master batch comprises the following components in percentage by mass: 50 wt% of kaolin and 50wt wt% of LDPE.
The preparation process comprises the following steps:
respectively using a single-screw extruder to perform melting plasticization after mixing the raw materials of each layer in proportion, wherein the temperature of the screw extruder is set as follows: the feeding section is 160-180 ℃, the melting section is 160-190 ℃ and the homogenizing section is 190-220 ℃; then multilayer co-extrusion lamination is carried out by using a multilayer parallel conical die head to obtain multilayer melt, the temperature range of the multilayer parallel conical die head is 220 ℃, the die lip gap is 1.0mm, the multilayer melt is inflated to obtain a film bubble with the diameter of 400mm, then the multilayer structure film tube is cooled and shaped by using a shaping water jacket to obtain a multilayer structure primary blown film tube, and the temperature of cooling water in the shaping water jacket is 10 ℃.
After dewatering, the primary blown film tube is heated to 85 ℃ by a far infrared ceramic oven, then is blown by bubbling and inflating, is longitudinally stretched to the required size by a synchronous machine, and is sized and cooled, wherein the blowing transverse stretching multiple is 6.5 times, and the longitudinal stretching multiple is 4.8 times; the sizing cooling is carried out by adopting a 5-grade cooling air ring, and the air volume of a 1 st-grade air ring is 2200m3H, the air volume of the 2 nd-level air ring is 2500m3H, the air volume of the 3 rd level wind ring is 2000m3The air volume of 4 th and 5 th wind rings is 1000m3/h。
Finally, annealing and cooling are carried out, wherein the annealing temperature is 80 ℃, and the temperature of a cooling medium used for cooling is 10 ℃; flattening, trimming and rolling to obtain the degradable environment-friendly polyolefin thermal shrinkage film.
Example 3
The degradable environment-friendly polyolefin heat shrinkable film comprises an outer layer, a core layer and an inner layer which are arranged in a laminated manner, wherein the raw materials of each layer are as follows:
outer layer:
49 wt% PP (2.16kg pressure, melt index at 190 ℃ 1.0g/10min)
26 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 3g/10min)
11 wt% degradable mother particle
11 wt% kaolin masterbatch
1 wt% silicone anti-blocking masterbatch
1 wt% erucamide smooth master batch
1 wt% of surfactant type antistatic agent master batch;
core layer:
37 wt% LDPE (2.16kg pressure, melt index at 190 ℃ 1.0g/10min)
19 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 3g/10min)
19 wt% degradation master batch
14 wt% kaolin master batch
9 wt% of erucamide smooth master batch;
inner layer:
49 wt% PP (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
26 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 3g/10min)
11 wt% degradable mother particle
11 wt% kaolin masterbatch
1 wt% silicone anti-blocking masterbatch
1 wt% erucamide smooth master batch
1 wt% of surfactant type antistatic agent master batch.
The degradation master batch comprises the following components in percentage by mass: 15 wt% of nano titanium dioxide, 20 wt% of polyoxyethylene and 65 wt% of LDPE;
the kaolin master batch comprises the following components in percentage by mass: kaolin 40 wt% and LDPE60 wt%.
The preparation process comprises the following steps:
respectively using a single-screw extruder to perform melting plasticization after mixing the raw materials of each layer in proportion, wherein the temperature of the screw extruder is set as follows: the feeding section is 160-180 ℃, the melting section is 160-190 ℃ and the homogenizing section is 190-220 ℃; and then carrying out multilayer co-extrusion lamination by using a multilayer parallel conical die head to obtain a multilayer melt, wherein the temperature range of the multilayer parallel conical die head is 200 ℃, the die lip gap is 2mm, the multilayer melt is inflated to obtain a film bubble with the diameter of 500mm, then cooling and shaping are carried out by using a shaping water jacket to obtain a primary blown film tube with a multilayer structure, and the temperature of cooling water in the shaping water jacket is 15 ℃.
After dewatering, the primary blown film tube is heated to 100 ℃ by a far infrared ceramic oven, then is blown by bubbling and inflating, is longitudinally stretched to the required size by a synchronous machine, and is sized and cooled, wherein the blowing transverse stretching multiple is 5 times, and the longitudinal stretching multiple is 5 times; the sizing cooling is carried out by adopting 5-grade cooling air rings, and the air quantity of the 1 st-grade air ring is 1000m3H, the air volume of the 2 nd-stage air ring is 1000m3The air volume of the 3 rd level air ring is 1200m3The air volume of 4 th and 5 th wind rings is 800m3/h。
Finally, annealing and cooling are carried out, wherein the annealing temperature is 70 ℃, and the temperature of a cooling medium used for cooling is 20 ℃; flattening, trimming and rolling to obtain the degradable environment-friendly polyolefin thermal shrinkage film.
Example 4
The degradable environment-friendly polyolefin heat shrinkable film comprises an outer layer, a core layer and an inner layer which are arranged in a laminated manner, wherein the raw materials of each layer are as follows:
outer layer:
30 wt% PP (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
30 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 4g/10min)
20 wt% degradation master batch
11 wt% kaolin masterbatch
3 wt% silicone anti-blocking masterbatch
3 wt% erucamide smooth master batch
3 wt% of surfactant type antistatic agent master batch;
core layer:
60 wt% LDPE (2.16kg pressure, melt index at 190 ℃ 1.5g/10min)
15 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 4g/10min)
10 wt% degradation master batch
10 wt% kaolin master batch
5 wt% of erucamide smooth master batch;
inner layer:
30 wt% PP (2.16kg pressure, melt index at 190 ℃ 0.5g/10min)
30 wt% mLDPE (2.16kg pressure, melt index at 190 ℃ 4g/10min)
20 wt% degradation master batch
11 wt% kaolin masterbatch
3 wt% silicone anti-blocking masterbatch
3 wt% erucamide smooth master batch
3 wt% of surfactant type antistatic agent master batch.
The degradation master batch comprises the following components in percentage by mass: 10 wt% of nano titanium dioxide, 25 wt% of polyoxyethylene and 65 wt% of LDPE;
the kaolin master batch comprises the following components in percentage by mass: 35 wt% of kaolin and 65 wt% of LDPE.
The preparation process comprises the following steps:
respectively using a single-screw extruder to perform melting plasticization after mixing the raw materials of each layer in proportion, wherein the temperature of the screw extruder is set as follows: the feeding section is 160-180 ℃, the melting section is 160-190 ℃ and the homogenizing section is 190-220 ℃; then multilayer co-extrusion lamination is carried out by using a multilayer parallel conical die head to obtain multilayer melt, the temperature range of the multilayer parallel conical die head is 210 ℃, the gap between die lips is 1.5mm, the multilayer melt is inflated to obtain a film bubble with the diameter of 450mm, then the multilayer structure primary blown film tube is obtained by using a shaping water jacket for cooling and shaping, and the temperature of cooling water in the shaping water jacket is 12 ℃.
After dewatering, the primary blown film tube is heated to 90 ℃ by a far infrared ceramic oven, then is blown by bubbling and inflating, is longitudinally stretched to the required size by a synchronous machine, and is sized and cooled, wherein the blowing transverse stretching multiple is 6 times, and the longitudinal stretching multiple is 6 times; the sizing cooling is carried out by adopting a 5-grade cooling air ring, and the air volume of a 1 st-grade air ring is 1500m3H, the air volume of the 2 nd-stage air ring is 1500m3H, the air volume of the 3 rd level air ring is 1500m3The air volume of 4 th and 5 th wind rings is 1000m3/h。
Finally, annealing and cooling are carried out, wherein the annealing temperature is 65 ℃, and the temperature of a cooling medium used for cooling is 15 ℃; flattening, trimming and rolling to obtain the degradable environment-friendly polyolefin thermal shrinkage film.
To further illustrate the effect of the degradable environmentally friendly polyolefin heat shrinkable film provided by the present application, the following control experiment was performed:
comparative example 1
Compared with the example 1, the difference is that the outer layer, the core layer and the inner layer do not contain the degradation master batch and the kaolin master batch.
Comparative example 2
Compared with example 2, the difference is that the outer layer, the core layer and the inner layer do not contain the degradation master batch.
Comparative example 3
Compared with example 3, the difference is that the outer layer, the core layer and the inner layer do not contain kaolin master batch.
Comparative example 4
The difference compared to example 4 is that no annealing treatment was performed.
The degradable environmentally friendly polyolefin heat shrinkable films obtained in examples 1 to 4 and comparative examples 1 to 4 were tested for mechanical properties, and ratios were calculated based on the properties of example 1; the results of testing each of the examples and comparative examples using light for 240h and sealed compost for 180 days are shown in table 1 below:
TABLE 1 test results
As can be seen from the data in the table above, the addition of the degradation master batch and the kaolin master batch in the formula is beneficial to the degradation, and the degradation master batch and the kaolin master batch have a synergistic effect. The annealing treatment can improve the mechanical property of the film and has little influence on the degradation property of the film.
The degradable environment-friendly polyolefin heat shrinkable film provided by the application has good mechanical property, can be subjected to photo/biological double degradation, has good mechanical strength and flexibility, and has good heat shrinkable property.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A degradable environment-friendly polyolefin heat shrinkable film is characterized by comprising an outer layer, a core layer and an inner layer which are sequentially laminated,
the outer layer and the inner layer comprise the following raw materials in percentage by mass: PP 30-50%, mLDPE 25-30%, degradable master batch 10-20%, kaolin master batch 10-15%, silicone anti-blocking master batch 1-3%, erucamide smooth master batch 1-3% and surfactant type antistatic agent master batch 1-3%;
the core layer comprises the following raw materials in percentage by mass: 35-60% of LDPE, 15-20% of mLDPE, 10-20% of degradation master batch, 10-15% of kaolin master batch and 5-10% of erucamide smooth master batch;
the degradation master batch comprises the following components in percentage by mass: 5-20 wt% of nano titanium dioxide, 10-30 wt% of polyoxyethylene and the balance of LDPE;
the kaolin master batch comprises the following components in percentage by mass: 30-50 wt% of kaolin and 50-70 wt% of LDPE;
the preparation method of the degradable environment-friendly polyolefin heat shrinkable film comprises the following steps:
A. mixing raw materials of each layer in proportion, respectively carrying out melting plasticization by using a single-screw extruder, then carrying out multilayer co-extrusion lamination by using a multilayer parallel conical die head to obtain multilayer melt, inflating the multilayer melt to obtain film bubbles, and then carrying out cooling shaping by using a shaping water jacket to obtain a primary blown film tube with a multilayer structure;
B. the primary blown film tube is heated by a far infrared ceramic oven after water removal, then is blown by bubbling and inflating, is longitudinally stretched to a required size by a synchronous machine and then is sized and cooled, and the temperature of the primary blown film tube heated by the far infrared ceramic oven is 85-110 ℃;
C. and finally, annealing and cooling, flattening, trimming and rolling to obtain the degradable environment-friendly polyolefin thermal shrinkage film.
2. The degradable environment-friendly polyolefin heat shrinkable film according to claim 1, wherein the melt index of PP in the outer layer and the melt index of PP in the inner layer are both 0.4-1.0g/10min and the melt index of LDPE in the core layer is 0.25-3g/10min under the condition of 190 ℃ and 2.16kg pressure.
3. The degradable environment-friendly polyolefin heat shrinkable film according to claim 1 or 2, wherein the melt index of mLDPE in the outer layer, the core layer and the inner layer is 0.5-5g/10min under the condition of 190 ℃ and 2.16kg pressure.
4. A method for preparing degradable environment-friendly polyolefin heat shrinkable film according to any one of claims 1 to 3, which comprises the following steps:
A. mixing raw materials of each layer in proportion, respectively carrying out melting plasticization by using a single-screw extruder, then carrying out multilayer co-extrusion lamination by using a multilayer parallel conical die head to obtain multilayer melt, inflating the multilayer melt to obtain film bubbles, and then carrying out cooling shaping by using a shaping water jacket to obtain a primary blown film tube with a multilayer structure;
B. the primary blown film tube is heated by a far infrared ceramic oven after water removal, then is blown up by bubbling and inflating, is longitudinally stretched to a required size by a synchronous machine, and is sized and cooled;
C. and finally, annealing and cooling, flattening, trimming and rolling to obtain the degradable environment-friendly polyolefin thermal shrinkage film.
5. The method of claim 4, wherein the temperature of the screw extruder is set to: the feeding section is 160-180 ℃, the melting section is 160-190 ℃ and the homogenizing section is 190-220 ℃; the temperature range of the multilayer parallel tapered die head is 190 ℃ to 220 ℃, and the die lip gap is 1.0-2.5 mm.
6. The method as claimed in claim 4, wherein the diameter of the film bubble is 400-560 mm.
7. The manufacturing method according to claim 4, wherein the temperature of the cooling water in the shaped water jacket is 10-17 ℃.
8. The method according to claim 4, wherein the mechanical longitudinal stretching is performed at a ratio of 4.0 to 6.5 times in the transverse direction and 4.8 to 6.8 times in the longitudinal direction.
9. The preparation method as claimed in claim 4, wherein the sizing cooling is performed by using 5-grade cooling air ring, and the air volume of the 1 st-grade air ring is 1000-3The air volume of the 2 nd level air ring is 1000-2500m3The air volume of the 3 rd level air ring is 1000-2000m3The air volume of the 4 th-level air ring and the 5 th-level air ring is 500-3/h。
10. The method according to any one of claims 4 to 9, wherein in the step C, the annealing temperature is 60 to 80 ℃, and the cooling medium used for cooling has a temperature of 10 to 30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910736159.2A CN110406223B (en) | 2019-08-09 | 2019-08-09 | Degradable environment-friendly polyolefin heat shrinkable film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910736159.2A CN110406223B (en) | 2019-08-09 | 2019-08-09 | Degradable environment-friendly polyolefin heat shrinkable film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110406223A CN110406223A (en) | 2019-11-05 |
| CN110406223B true CN110406223B (en) | 2021-08-06 |
Family
ID=68366753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910736159.2A Active CN110406223B (en) | 2019-08-09 | 2019-08-09 | Degradable environment-friendly polyolefin heat shrinkable film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110406223B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409995A (en) * | 2022-02-16 | 2022-04-29 | 山东国智新材料科技有限公司 | Multilayer-stacked degradable flame-retardant antirust heat shrinkable film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009285892A (en) * | 2008-05-27 | 2009-12-10 | Ps Japan Corp | Heat-shrinkable multi-layer film |
| CN103834086A (en) * | 2014-03-19 | 2014-06-04 | 华南农业大学 | Efficient controllable photooxidation-biodegradable plastic film and preparation method thereof |
| CN104231385A (en) * | 2014-08-28 | 2014-12-24 | 天津市利顺塑料制品有限公司 | Multi-degradable plastic film and preparation method thereof |
| CN108943929A (en) * | 2018-06-08 | 2018-12-07 | 黄山至德新材料科技有限公司 | A kind of Polyolefin Heat Shrinkable Film and its preparation method and application |
-
2019
- 2019-08-09 CN CN201910736159.2A patent/CN110406223B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009285892A (en) * | 2008-05-27 | 2009-12-10 | Ps Japan Corp | Heat-shrinkable multi-layer film |
| CN103834086A (en) * | 2014-03-19 | 2014-06-04 | 华南农业大学 | Efficient controllable photooxidation-biodegradable plastic film and preparation method thereof |
| CN104231385A (en) * | 2014-08-28 | 2014-12-24 | 天津市利顺塑料制品有限公司 | Multi-degradable plastic film and preparation method thereof |
| CN108943929A (en) * | 2018-06-08 | 2018-12-07 | 黄山至德新材料科技有限公司 | A kind of Polyolefin Heat Shrinkable Film and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110406223A (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110774713B (en) | Coating type high-barrier bidirectional-stretching polylactic acid film and preparation method thereof | |
| CN107652670B (en) | Toughened biaxially oriented polyamide film and preparation method thereof | |
| CN109720066B (en) | Polyvinyl alcohol/polypropylene composite film and preparation method thereof | |
| CN101838445A (en) | PETG blow molding film and preparation method thereof | |
| CN109720055B (en) | Polyvinyl alcohol/polylactic acid composite film and preparation method thereof | |
| CN104212059B (en) | A kind of biodegradable master batch and the biodegradable BOPP film containing the biodegradable master batch | |
| CN110421939B (en) | Polyolefin hot-slip heat shrinkable film with excellent slipping performance and preparation method thereof | |
| CN110328942B (en) | Antistatic crosslinked heat shrinkable film and preparation method thereof | |
| CN110341273B (en) | Polyolefin heat shrinkable film and preparation method thereof | |
| CN111231470A (en) | Multilayer co-extruded polyethylene heat shrinkable film and preparation method thereof | |
| CN109616005B (en) | Milky-white PE label film and production method thereof | |
| CN112976744A (en) | Polyethylene composite membrane and preparation method and application thereof | |
| CN109721905B (en) | Polyvinyl alcohol film, composition and preparation method thereof | |
| CN109720060B (en) | Polyvinyl alcohol/polyethylene composite film and preparation method thereof | |
| CN111016359B (en) | PE low-temperature packaging film and preparation method and application thereof | |
| CN110406223B (en) | Degradable environment-friendly polyolefin heat shrinkable film and preparation method thereof | |
| CN110303748B (en) | Thinner polyolefin shrink film and production process thereof | |
| CN109721910B (en) | Plasticizer, polyvinyl alcohol composition, polyvinyl alcohol film and preparation method thereof | |
| JP5376773B2 (en) | Polyamide resin film | |
| JP6588720B2 (en) | Easy tear biaxially stretched polybutylene terephthalate film | |
| CN113895126A (en) | High-shrinkage biaxially-oriented polylactic acid film and preparation method thereof | |
| CN106065103A (en) | A kind of production technology of high tenacity high impact heat shrink films packaging bag | |
| CN109280273B (en) | High melt strength polypropylene film compositions and films and uses thereof | |
| CN110920188A (en) | Bio-based PTT/PLA heat-shrinkable label film and preparation method thereof | |
| CN113843999B (en) | Preparation method of poly (adipic acid)/poly (butylene terephthalate) film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |