CN108299725A - A kind of high-strength and high-ductility stretch wrap film and preparation method thereof - Google Patents
A kind of high-strength and high-ductility stretch wrap film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of high-strength and high-ductility stretch wrap films and preparation method thereof, and preparation method is as follows：（1）Low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol, nano zinc oxide powder, titanium nitride is taken fully to carry out heating stirring；（2）Continue to heat up, epoxidized soybean oil, epoxidized soybean oil phenolic aldehyde benzoxazine ternary polymerization phenol-formaldehyde resin modified, Cyanate Resin Modified by Prepolymer of Bismaleimide is added, then kept the temperature again after being sufficiently stirred；（3）By step（2）Stretch wrap film material carry out Couble screw rod high-temp extruding；（4）Casting film-forming finally is carried out with casting machine again, stretch wrap film material is obtained after curtain coating.The high-strength and high-ductility stretch wrap film of the present invention not only has very high tearing strength, but also tensile strength is good and good toughness.
Description
Technical field
The present invention relates to packaging material fields, and in particular to a kind of high-strength and high-ductility stretch wrap film and preparation method thereof.
Background technology
Polyethylene (PE) stretch wrap film due to production efficiency height, good environmental adaptability, high quality,
It is considered as the important development direction of film production from now on.PE stretch wrap films are mainly used in various packaging films, have and are suitble to
Large volume packaging, it is renewable, safely, quickly the features such as, be widely used at present.China is in late 1980s
Develop PE stretch wrap films, and early 1990s obtain it is relatively broad apply, develop in recent years more rapid.Industry
Film for packaging is the maximum purposes of PE stretch wrap films, and dosage accounts for 50% or more of total dosage.Currently, China is every year due to packet
Dress the reasons such as is not good at and economic loss is caused to reach over ten billion Yuan, wherein because the loss of the improper generation of transportation and packing accounts for 80% or so.Make
The generation of such loss can be reduced by being packed with stretch wrap film, can effectively protect commodity, play rain-proof, waterproof, moisture-proof effect,
And packing cost can be reduced.But the tensile strength and toughness of common winding membrane material are poor on the market at present, need to carry
Therefore the mechanical properties such as the tensile strength and toughness of height winding membrane material are improved stretch wrap film film in the prior art
It is very necessary to develop the film with new capability.
Invention content
Technical problems to be solved：The object of the present invention is to provide a kind of high-strength and high-ductility stretch wrap films, meet market
Demand, not only there is very high tearing strength, but also tensile strength is good and good toughness.
Technical solution：A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：Low-density is poly-
30-50 parts of ethylene, 50-70 parts of linear low density polyethylene (LLDPE), 0.2-5 parts of polyisobutene, 5-12 parts of silica, precipitated calcium carbonate
3-10 parts, 2-6 parts of epoxidized soybean oil, 1.8-3.2 parts of zinc stearate, antioxidant 1010 be 0.1-0.5 parts, 3-7 parts of polyethylene glycol,
- 10-20 parts of benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, Cyanate Resin Modified by Prepolymer of Bismaleimide
5-10 parts, 3-8 parts of nano zinc oxide powder, 3-8 parts of titanium nitride.
It is further preferred that a kind of high-strength and high-ductility stretch wrap film, prepared by weight by following component and
At：35-45 parts of low density polyethylene (LDPE), 55-65 parts of linear low density polyethylene (LLDPE), 1-4 parts of polyisobutene, 7-10 parts of silica,
5-8 parts of precipitated calcium carbonate, 3-5 parts of epoxidized soybean oil, 2.2-2.8 parts of zinc stearate, antioxidant 1010 are 0.2-0.4 parts, poly- second
It is 4-6 parts of glycol, -13-18 parts of benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, bi-maleimide modified
6-8 parts of cyanate ester resin, 4-7 parts of nano zinc oxide powder, 4-7 parts of titanium nitride.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film, which is characterized in that include the following steps：
（1）Take low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polyisobutene, silica, precipitated calcium carbonate, zinc stearate,
Antioxidant 1010, polyethylene glycol, nano zinc oxide powder, titanium nitride are fully stirred, and are warming up to 75-95 DEG C and are stirred evenly, stir
It is 30-60min to mix the time；
（2）100-120 DEG C is raised the temperature to, epoxidized soybean oil is added, the-benzoxazine ternary polymerization of epoxidized soybean oil-phenolic aldehyde changes
Property phenolic resin, Cyanate Resin Modified by Prepolymer of Bismaleimide, then be sufficiently stirred, stir 60-120min, protected again after stirring
Warm 3h；
（3）By step（2）Stretch wrap film material carry out Couble screw rod high-temp extruding；
（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 185-205 DEG C, and stretch wrap film material is obtained after curtain coating
Material.
Further, the preparation method of a kind of high-strength and high-ductility stretch wrap film, the step（1）In be warming up to
80-90 DEG C, mixing time 40-50min.
Further, the preparation method of a kind of high-strength and high-ductility stretch wrap film, the step（2）Middle temperature liter
Up to 105-115 DEG C, mixing time 80-100min.
Further, the preparation method of a kind of high-strength and high-ductility stretch wrap film, the step（3）Middle twin-screw
The control of extruder barrel back segment temperature is at 170-190 DEG C, and at 160-200 DEG C, head temperature control exists the control of barrel front-end temperature
170-180℃。
Further, the preparation method of a kind of high-strength and high-ductility stretch wrap film, the step（4）Middle curtain coating temperature
Degree is 190-200 DEG C.
Advantageous effect：The high-strength and high-ductility stretch wrap film of the present invention has very high tearing strength, machine direction tear
For 135Nmm-1, cross direction tear strength 460Nmm-1；Longitudinal tensile strength reaches as high as 32.6MPa, and cross directional stretch is strong
Degree is up to 29.3MPa；Longitudinal stretching breaking strain is 610%, is laterally 815%.
Specific implementation mode
Embodiment 1
A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：30 parts of low density polyethylene (LDPE), line style
70 parts of low density polyethylene (LDPE), 0.2 part of polyisobutene, 5 parts of silica, 10 parts of precipitated calcium carbonate, 2 parts of epoxidized soybean oil, tristearin
1.8 parts of sour zinc, antioxidant 1010 be 0.5 part, 7 parts of polyethylene glycol, the-benzoxazine ternary polymerization of epoxidized soybean oil-phenolic aldehyde be modified phenol
10 parts of urea formaldehyde, 10 parts of Cyanate Resin Modified by Prepolymer of Bismaleimide, 3 parts of nano zinc oxide powder, 8 parts of titanium nitride.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film is：（1）Take the poly- second of low density polyethylene (LDPE), linear, low density
Alkene, polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol, nano zinc oxide powder, nitrogen
Change titanium to be fully stirred, is warming up to 75 DEG C and stirs evenly, mixing time 60min；（2）100 DEG C are raised the temperature to, is added
Epoxidized soybean oil ,-benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, bi-maleimide modified cyanate
Resin, then be sufficiently stirred, 60min is stirred, keeps the temperature 3h after stirring again；（3）By step（2）Stretch wrap film material carry out
Couble screw rod high-temp squeezes；（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 185 DEG C, and stretching is obtained after curtain coating and is twined
Around membrane material.
Embodiment 2
A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：50 parts of low density polyethylene (LDPE), line style
50 parts of low density polyethylene (LDPE), 5 parts of polyisobutene, 2 parts of silica 1,3 parts of precipitated calcium carbonate, 6 parts of epoxidized soybean oil, stearic acid
3.2 parts of zinc, antioxidant 1010 be 0.1 part, 3 parts of polyethylene glycol ,-benzoxazine ternary polymerization modified phenolic of epoxidized soybean oil-phenolic aldehyde
20 parts of resin, 5 parts of Cyanate Resin Modified by Prepolymer of Bismaleimide, 8 parts of nano zinc oxide powder, 3 parts of titanium nitride.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film is：（1）Take the poly- second of low density polyethylene (LDPE), linear, low density
Alkene, polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol, nano zinc oxide powder, nitrogen
Change titanium to be fully stirred, is warming up to 95 DEG C and stirs evenly, mixing time 30min；（2）120 DEG C are raised the temperature to, is added
Epoxidized soybean oil ,-benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, bi-maleimide modified cyanate
Resin, then be sufficiently stirred, 120min is stirred, keeps the temperature 3h after stirring again；（3）By step（2）Stretch wrap film material into
Row Couble screw rod high-temp squeezes；（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 205 DEG C, is stretched after curtain coating
Wind membrane material.
Embodiment 3
A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：35 parts of low density polyethylene (LDPE), line style
65 parts of low density polyethylene (LDPE), 1 part of polyisobutene, 0 part of silica 1,5 parts of precipitated calcium carbonate, 5 parts of epoxidized soybean oil, stearic acid
2.2 parts of zinc, antioxidant 1010 be 0.2 part, 6 parts of polyethylene glycol ,-benzoxazine ternary polymerization modified phenolic of epoxidized soybean oil-phenolic aldehyde
18 parts of resin, 6 parts of Cyanate Resin Modified by Prepolymer of Bismaleimide, 4 parts of nano zinc oxide powder, 7 parts of titanium nitride.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film is：（1）Take the poly- second of low density polyethylene (LDPE), linear, low density
Alkene, polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol, nano zinc oxide powder, nitrogen
Change titanium to be fully stirred, is warming up to 80 DEG C and stirs evenly, mixing time 50min；（2）105 DEG C are raised the temperature to, is added
Epoxidized soybean oil ,-benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, bi-maleimide modified cyanate
Resin, then be sufficiently stirred, 80min is stirred, keeps the temperature 3h after stirring again；（3）By step（2）Stretch wrap film material carry out
Couble screw rod high-temp squeezes；（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 190 DEG C, and stretching is obtained after curtain coating and is twined
Around membrane material.
Embodiment 4
A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：45 parts of low density polyethylene (LDPE), line style
55 parts of low density polyethylene (LDPE), 4 parts of polyisobutene, 7 parts of silica, 8 parts of precipitated calcium carbonate, 3 parts of epoxidized soybean oil, zinc stearate
2.8 parts, antioxidant 1010 be 0.4 part, 4 parts of polyethylene glycol ,-benzoxazine ternary polymerization modified phenolic resin of epoxidized soybean oil-phenolic aldehyde
13 parts of fat, 8 parts of Cyanate Resin Modified by Prepolymer of Bismaleimide, 7 parts of nano zinc oxide powder, 4 parts of titanium nitride.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film is：（1）Take the poly- second of low density polyethylene (LDPE), linear, low density
Alkene, polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol, nano zinc oxide powder, nitrogen
Change titanium to be fully stirred, is warming up to 80 DEG C and stirs evenly, mixing time 40min；（2）115 DEG C are raised the temperature to, is added
Epoxidized soybean oil ,-benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, bi-maleimide modified cyanate
Resin, then be sufficiently stirred, 100min is stirred, keeps the temperature 3h after stirring again；（3）By step（2）Stretch wrap film material into
Row Couble screw rod high-temp squeezes；（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 200 DEG C, is stretched after curtain coating
Wind membrane material.
Embodiment 5
A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：40 parts of low density polyethylene (LDPE), line style
60 parts of low density polyethylene (LDPE), 3 parts of polyisobutene, 9 parts of silica, 6 parts of precipitated calcium carbonate, 4 parts of epoxidized soybean oil, zinc stearate
2.5 parts, antioxidant 1010 be 0.3 part, 5 parts of polyethylene glycol ,-benzoxazine ternary polymerization modified phenolic resin of epoxidized soybean oil-phenolic aldehyde
15 parts of fat, 7 parts of Cyanate Resin Modified by Prepolymer of Bismaleimide, 5 parts of nano zinc oxide powder, 6 parts of titanium nitride.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film is：（1）Take the poly- second of low density polyethylene (LDPE), linear, low density
Alkene, polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol, nano zinc oxide powder, nitrogen
Change titanium to be fully stirred, is warming up to 85 DEG C and stirs evenly, mixing time 45min；（2）110 DEG C are raised the temperature to, is added
Epoxidized soybean oil ,-benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, bi-maleimide modified cyanate
Resin, then be sufficiently stirred, 90min is stirred, keeps the temperature 3h after stirring again；（3）By step（2）Stretch wrap film material carry out
Couble screw rod high-temp squeezes；（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 195 DEG C, and stretching is obtained after curtain coating and is twined
Around membrane material.
Comparative example 1
A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：30 parts of low density polyethylene (LDPE), line style
70 parts of low density polyethylene (LDPE), 0.2 part of polyisobutene, 5 parts of silica, 10 parts of precipitated calcium carbonate, 2 parts of epoxidized soybean oil, tristearin
1.8 parts of sour zinc, antioxidant 1010 be 0.5 part, 7 parts of polyethylene glycol, the-benzoxazine ternary polymerization of epoxidized soybean oil-phenolic aldehyde be modified phenol
10 parts of urea formaldehyde, 10 parts of Cyanate Resin Modified by Prepolymer of Bismaleimide.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film is：（1）Take the poly- second of low density polyethylene (LDPE), linear, low density
Alkene, polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol are fully stirred, heating
It is stirred evenly to 75 DEG C, mixing time 60min；（2）100 DEG C are raised the temperature to, epoxidized soybean oil, epoxidized soybean oil-is added
- benzoxazine ternary polymerization phenol-formaldehyde resin modified of phenolic aldehyde, Cyanate Resin Modified by Prepolymer of Bismaleimide, then be sufficiently stirred,
60min is stirred, keeps the temperature 3h after stirring again；（3）By step（2）Stretch wrap film material carry out Couble screw rod high-temp extruding；（4）Most
Casting film-forming is carried out with casting machine again afterwards, casting temperature is 185 DEG C, and stretch wrap film material is obtained after curtain coating.
Comparative example 2
A kind of high-strength and high-ductility stretch wrap film is prepared by weight by following component：50 parts of low density polyethylene (LDPE), line style
50 parts of low density polyethylene (LDPE), 5 parts of polyisobutene, 2 parts of silica 1,3 parts of precipitated calcium carbonate, 6 parts of epoxidized soybean oil, stearic acid
3.2 parts of zinc, antioxidant 1010 be 0.1 part, 3 parts of polyethylene glycol, 8 parts of nano zinc oxide powder, 3 parts of titanium nitride.
The preparation method of above-mentioned high-strength and high-ductility stretch wrap film is：（1）Take the poly- second of low density polyethylene (LDPE), linear, low density
Alkene, polyisobutene, silica, precipitated calcium carbonate, zinc stearate, antioxidant 1010, polyethylene glycol, nano zinc oxide powder, nitrogen
Change titanium to be fully stirred, is warming up to 95 DEG C and stirs evenly, mixing time 30min；（2）120 DEG C are raised the temperature to, is added
Epoxidized soybean oil, then be sufficiently stirred, 120min is stirred, keeps the temperature 3h after stirring again；（3）By step（2）Stretch wrap film
Material carries out Couble screw rod high-temp extruding；（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 205 DEG C, after curtain coating
To stretch wrap film material.
The property indices of material of the present invention see the table below, it may be seen that this high-strength and high-ductility stretch wrap film has
Very high tearing strength, machine direction tear 135Nmm-1, cross direction tear strength 460Nmm-1；Longitudinal tensile strength
32.6MPa is reached as high as, transverse tensile strength is up to 29.3MPa；Longitudinal stretching breaking strain is 610%, is laterally 815%.
The property indices of 1 high-strength and high-ductility stretch wrap film of table
Claims (7)
1. a kind of high-strength and high-ductility stretch wrap film, which is characterized in that be prepared by weight by following component：Low-density is poly-
30-50 parts of ethylene, 50-70 parts of linear low density polyethylene (LLDPE), 0.2-5 parts of polyisobutene, 5-12 parts of silica, precipitated calcium carbonate
3-10 parts, 2-6 parts of epoxidized soybean oil, 1.8-3.2 parts of zinc stearate, antioxidant 1010 be 0.1-0.5 parts, 3-7 parts of polyethylene glycol,
- 10-20 parts of benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, Cyanate Resin Modified by Prepolymer of Bismaleimide
5-10 parts, 3-8 parts of nano zinc oxide powder, 3-8 parts of titanium nitride.
2. a kind of high-strength and high-ductility stretch wrap film according to claim 1, which is characterized in that by weight by following component
Part is prepared：35-45 parts of low density polyethylene (LDPE), 55-65 parts of linear low density polyethylene (LLDPE), 1-4 parts of polyisobutene, silica
7-10 parts, 5-8 parts of precipitated calcium carbonate, 3-5 parts of epoxidized soybean oil, 2.2-2.8 parts of zinc stearate, antioxidant 1010 0.2-0.4
Part, 4-6 parts of polyethylene glycol, -13-18 parts of benzoxazine ternary polymerization phenol-formaldehyde resin modified of epoxidized soybean oil-phenolic aldehyde, bismaleimide
6-8 parts of amine modified cyanic acid ester resin, 4-7 parts of nano zinc oxide powder, 4-7 parts of titanium nitride.
3. a kind of preparation method of high-strength and high-ductility stretch wrap film, which is characterized in that include the following steps：
（1）Take low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polyisobutene, silica, precipitated calcium carbonate, zinc stearate,
Antioxidant 1010, polyethylene glycol, nano zinc oxide powder, titanium nitride are fully stirred, and are warming up to 75-95 DEG C and are stirred evenly, stir
It is 30-60min to mix the time；
（2）100-120 DEG C is raised the temperature to, epoxidized soybean oil is added, the-benzoxazine ternary polymerization of epoxidized soybean oil-phenolic aldehyde changes
Property phenolic resin, Cyanate Resin Modified by Prepolymer of Bismaleimide, then be sufficiently stirred, stir 60-120min, protected again after stirring
Warm 3h；
（3）By step（2）Stretch wrap film material carry out Couble screw rod high-temp extruding；
（4）Casting film-forming finally is carried out with casting machine again, casting temperature is 185-205 DEG C, and stretch wrap film material is obtained after curtain coating
Material.
4. a kind of preparation method of high-strength and high-ductility stretch wrap film according to claim 3, it is characterised in that：The step
Suddenly（1）In be warming up to 80-90 DEG C, mixing time 40-50min.
5. a kind of preparation method of high-strength and high-ductility stretch wrap film according to claim 3, it is characterised in that：The step
Suddenly（2）Middle temperature is increased to 105-115 DEG C, mixing time 80-100min.
6. a kind of preparation method of high-strength and high-ductility stretch wrap film according to claim 3, it is characterised in that：The step
Suddenly（3）The control of middle twin screw extruder barrel back segment temperature is at 170-190 DEG C, and the control of barrel front-end temperature is at 160-200 DEG C, head
Temperature is controlled at 170-180 DEG C.
7. a kind of preparation method of high-strength and high-ductility stretch wrap film according to claim 3, it is characterised in that：The step
Suddenly（4）Middle casting temperature is 190-200 DEG C.
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