CN106519474B - A kind of environmentally friendly heat shrink films and preparation method thereof of the high grade of transparency and high tenacity - Google Patents
A kind of environmentally friendly heat shrink films and preparation method thereof of the high grade of transparency and high tenacity Download PDFInfo
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- CN106519474B CN106519474B CN201611145454.3A CN201611145454A CN106519474B CN 106519474 B CN106519474 B CN 106519474B CN 201611145454 A CN201611145454 A CN 201611145454A CN 106519474 B CN106519474 B CN 106519474B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The invention discloses the environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, are made of the raw material below according to parts by weight：100 110 parts of polystyrene, 35 parts of calcium stearate, 1.5 2.5 parts of antioxidant, 1.2 1.6 parts of light stabilizer, 2.5 3.0 parts of decabromodiphenylethane, 25 parts of Polystyrene Sulronate, 1.0 1.4 parts of nano-calcium carbonate, 0.7 1.3 parts of ethyoxyl cocoalkyl amines.The invention also discloses the preparation methods of the environmentally friendly heat shrink films of the high grade of transparency and high tenacity.Heat shrink films prepared by the present invention, raw material are mainly polystyrene, meet environmental requirement, have very high toughness, and transparency has preferably packaging effect, good market prospect more than existing environmentally friendly heat shrink films in the market.
Description
Technical field
The present invention relates to heat-shrinkable film technology field, specifically a kind of high grade of transparency and the environmentally friendly heat shrink films of high tenacity and
Preparation method.
Background technology
Heat shrink films are a kind of good film packing materials, are longitudinally and/or laterally drawn under elastomeric state using film
The energy storage stretched in the film, imitate by the memory that the form before the bi-directionally or uni-directionally stretching having using thermoplastic has
It answers, the function of the form before stretching can be restored when encountering heat again to reach packaging purpose.Heat shrink films should have good
Bright property, can allow customer to be immediately seen the commodity being packaged, and be convenient for customer's picking commodities.
Heat shrink films have obtained answering extensively because of its excellent stability and safety, in fields such as food, drug, beverages
With.The type of heat shrink films is various, such as PE heat shrink films, PVC heat shrink films, POF heat shrink films, OPS heat shrink films, different
Heat shrink films there is different performances, such as OPS heat shrink films are exactly a kind of heat shrink films meeting environmental requirement, it is not only
The energy can be transformed into even if printing later trade mark and can burn, due to the non-toxic and tasteless of it so not producing with recycling
Raw any pernicious gas, therefore not will produce any pollution.Opposite PVC can not just be burned because containing chlorine（The chlorine generated after burning
Gas can destroy ozone layer）Even if recycling larger if the cost because of recycling, and the gold content utilized again is too low, and must not repay
It loses.Although OPS heat shrink films meet environmental requirement, OPS heat shrink films need to be mentioned in aspect of performance, such as part OPS heat
Shrink film transparency is bad, although part OPS heat shrink films transparencies are fine, performs poor in terms of toughness.
Invention content
The purpose of the present invention is to provide the environmentally friendly heat shrink films and preparation method thereof of a kind of high grade of transparency and high tenacity, with
Solve the problems mentioned above in the background art.
To achieve the above object, the present invention provides the following technical solutions：
The environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, are made of the raw material below according to parts by weight：Polyphenyl second
100-110 parts of alkene, 3-5 parts of calcium stearate, 1.5-2.5 parts of antioxidant, 1.2-1.6 parts of light stabilizer, decabromodiphenylethane 2.5-
3.0 parts, 2-5 parts of Polystyrene Sulronate, 1.0-1.4 parts of nano-calcium carbonate, 0.7-1.3 parts of ethyoxyl cocoalkyl amines.
As a further solution of the present invention：It is made of the raw material below according to parts by weight：103-108 parts of polystyrene,
3.4-4.7 parts of calcium stearate, 1.3-1.5 parts of light stabilizer, 2.6-2.8 parts of decabromodiphenylethane, gathers 1.7-2.3 parts of antioxidant
3-4 parts of sulphur styrene, 1.1-1.3 parts of nano-calcium carbonate, 0.8-1.1 parts of ethyoxyl cocoalkyl amines.
As further scheme of the invention：It is made of the raw material below according to parts by weight：It is 106 parts of polystyrene, hard
3.9 parts of resin acid calcium, 2.1 parts of antioxidant, 1.4 parts of light stabilizer, 2.7 parts of decabromodiphenylethane, Polystyrene Sulronate 3.3 part, nanometer
1.2 parts of calcium carbonate, 0.9 part of ethyoxyl cocoalkyl amines.
As further scheme of the invention：The antioxidant is antioxidant 1076.
As further scheme of the invention：The light stabilizer is light stabilizer 944.
The preparation method of the environmentally friendly heat shrink films of the high grade of transparency and high tenacity, steps are as follows：
1）Polystyrene Sulronate and nano-calcium carbonate are weighed, after Polystyrene Sulronate heating in vacuum to complete melting, addition is received
Rice calcium carbonate, is stirred 3-5h, then ultrasonication 50-60min, obtains additive；
2）Polystyrene and ethyoxyl cocoalkyl amines are weighed, polystyrene is added to reaction kettle, is warming up to 260-
265 DEG C, ethyoxyl cocoalkyl amines are put into, are stirred 20-30min, obtain the first mixture；
3）Reaction kettle is cooled to 240-245 DEG C, additive is added, is stirred 10-20min, obtains the second mixture；
4）Reaction kettle is warming up to 250-255 DEG C, weighs calcium stearate, antioxidant, light stabilizer and decabromodiphenylethane,
And all put into reaction kettle, it is stirred 40-50min, obtains third mixture；
5）Third mixture is first passed through screw extruder to squeeze out, then is squeezed out by single layer inflation film manufacturing machine, after dry, is managed
Base；
6）It after pipe is preheated, is sent into and stretches in case, carry out biaxial tension processing, obtain film, you can, the two-way drawing
The temperature stretched is 110-115 DEG C.
Compared with prior art, the beneficial effects of the invention are as follows：
1, heat shrink films prepared by the present invention, raw material is mainly polystyrene, meets environmental requirement, fracture tensile strength
73.1MPa or more is reached, there is very high toughness, and transparency has reached 89.2% or more, has been more than existing environmental protection in the market
Heat shrink films have preferably packaging effect, good market prospect.
2, the present invention can improve the toughness and transparency of heat shrink films by adding Polystyrene Sulronate.
Specific implementation mode
Technical scheme of the present invention is described in more detail With reference to embodiment.
Embodiment 1
The environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, are made of the raw material below according to parts by weight：Polyphenyl second
100 parts of alkene, 3 parts of calcium stearate, 1.5 parts of antioxidant, 1.2 parts of light stabilizer, 2.5 parts of decabromodiphenylethane, Polystyrene Sulronate 2
Part, 1.0 parts of nano-calcium carbonate, 0.7 part of ethyoxyl cocoalkyl amines；Wherein, the antioxidant is antioxidant 1076, and the light is steady
It is light stabilizer 944 to determine agent.
In the present embodiment, the preparation method of the environmentally friendly heat shrink films of the high grade of transparency and high tenacity, steps are as follows：
1）Polystyrene Sulronate and nano-calcium carbonate are weighed, after Polystyrene Sulronate heating in vacuum to complete melting, addition is received
Rice calcium carbonate, is stirred 3h, then ultrasonication 50min, obtains additive；
2）Polystyrene and ethyoxyl cocoalkyl amines are weighed, polystyrene is added to reaction kettle, is warming up to 260
DEG C, ethyoxyl cocoalkyl amines are put into, 20min is stirred, obtain the first mixture；
3）Reaction kettle is cooled to 240 DEG C, additive is added, is stirred 10min, obtains the second mixture；
4）Reaction kettle is warming up to 250 DEG C, weighs calcium stearate, antioxidant, light stabilizer and decabromodiphenylethane, and complete
Portion is put into reaction kettle, is stirred 40min, obtains third mixture；
5）Third mixture is first passed through screw extruder to squeeze out, then is squeezed out by single layer inflation film manufacturing machine, after dry, is managed
Base；
6）It after pipe is preheated, is sent into and stretches in case, carry out biaxial tension processing, obtain film, you can, the two-way drawing
The temperature stretched is 110 DEG C.
Embodiment 2
The environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, are made of the raw material below according to parts by weight：Polyphenyl second
103 parts of alkene, 3.4 parts of calcium stearate, 1.9 parts of antioxidant, 1.3 parts of light stabilizer, 2.8 parts of decabromodiphenylethane, Polystyrene Sulronate 4
Part, 1 part of nano-calcium carbonate, 0.9 part of ethyoxyl cocoalkyl amines；Wherein, the antioxidant is antioxidant 1076, and the light is stablized
Agent is light stabilizer 944.
In the present embodiment, the preparation method of the environmentally friendly heat shrink films of the high grade of transparency and high tenacity, steps are as follows：
1）Polystyrene Sulronate and nano-calcium carbonate are weighed, after Polystyrene Sulronate heating in vacuum to complete melting, addition is received
Rice calcium carbonate, is stirred 3.5h, then ultrasonication 53min, obtains additive；
2）Polystyrene and ethyoxyl cocoalkyl amines are weighed, polystyrene is added to reaction kettle, is warming up to 262
DEG C, ethyoxyl cocoalkyl amines are put into, 25min is stirred, obtain the first mixture；
3）Reaction kettle is cooled to 240 DEG C, additive is added, is stirred 15min, obtains the second mixture；
4）Reaction kettle is warming up to 253 DEG C, weighs calcium stearate, antioxidant, light stabilizer and decabromodiphenylethane, and complete
Portion is put into reaction kettle, is stirred 42min, obtains third mixture；
5）Third mixture is first passed through screw extruder to squeeze out, then is squeezed out by single layer inflation film manufacturing machine, after dry, is managed
Base；
6）It after pipe is preheated, is sent into and stretches in case, carry out biaxial tension processing, obtain film, you can, the two-way drawing
The temperature stretched is 112 DEG C.
Embodiment 3
The environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, are made of the raw material below according to parts by weight：Polyphenyl second
106 parts of alkene, 3.9 parts of calcium stearate, 2.1 parts of antioxidant, 1.4 parts of light stabilizer, 2.7 parts of decabromodiphenylethane, Polystyrene Sulronate
3.3 parts, 1.2 parts of nano-calcium carbonate, 0.9 part of ethyoxyl cocoalkyl amines；Wherein, the antioxidant is antioxidant 1076, described
Light stabilizer is light stabilizer 944.
In the present embodiment, the preparation method of the environmentally friendly heat shrink films of the high grade of transparency and high tenacity, steps are as follows：
1）Polystyrene Sulronate and nano-calcium carbonate are weighed, after Polystyrene Sulronate heating in vacuum to complete melting, addition is received
Rice calcium carbonate, is stirred 4h, then ultrasonication 56min, obtains additive；
2）Polystyrene and ethyoxyl cocoalkyl amines are weighed, polystyrene is added to reaction kettle, is warming up to 264
DEG C, ethyoxyl cocoalkyl amines are put into, 25min is stirred, obtain the first mixture；
3）Reaction kettle is cooled to 243 DEG C, additive is added, is stirred 16min, obtains the second mixture；
4）Reaction kettle is warming up to 252 DEG C, weighs calcium stearate, antioxidant, light stabilizer and decabromodiphenylethane, and complete
Portion is put into reaction kettle, is stirred 44min, obtains third mixture；
5）Third mixture is first passed through screw extruder to squeeze out, then is squeezed out by single layer inflation film manufacturing machine, after dry, is managed
Base；
6）It after pipe is preheated, is sent into and stretches in case, carry out biaxial tension processing, obtain film, you can, the two-way drawing
The temperature stretched is 113 DEG C.
Embodiment 4
The environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, are made of the raw material below according to parts by weight：Polyphenyl second
107 parts of alkene, 4.2 parts of calcium stearate, 2 parts of antioxidant, 1.5 parts of light stabilizer, 2.6 parts of decabromodiphenylethane, Polystyrene Sulronate 2
Part, 1.1 parts of nano-calcium carbonate, 1.2 parts of ethyoxyl cocoalkyl amines；Wherein, the antioxidant is antioxidant 1076, and the light is steady
It is light stabilizer 944 to determine agent.
In the present embodiment, the preparation method of the environmentally friendly heat shrink films of the high grade of transparency and high tenacity, steps are as follows：
1）Polystyrene Sulronate and nano-calcium carbonate are weighed, after Polystyrene Sulronate heating in vacuum to complete melting, addition is received
Rice calcium carbonate, is stirred 4h, then ultrasonication 57min, obtains additive；
2）Polystyrene and ethyoxyl cocoalkyl amines are weighed, polystyrene is added to reaction kettle, is warming up to 264
DEG C, ethyoxyl cocoalkyl amines are put into, 26min is stirred, obtain the first mixture；
3）Reaction kettle is cooled to 245 DEG C, additive is added, is stirred 13min, obtains the second mixture；
4）Reaction kettle is warming up to 254 DEG C, weighs calcium stearate, antioxidant, light stabilizer and decabromodiphenylethane, and complete
Portion is put into reaction kettle, is stirred 48min, obtains third mixture；
5）Third mixture is first passed through screw extruder to squeeze out, then is squeezed out by single layer inflation film manufacturing machine, after dry, is managed
Base；
6）It after pipe is preheated, is sent into and stretches in case, carry out biaxial tension processing, obtain film, you can, the two-way drawing
The temperature stretched is 110 DEG C.
Embodiment 5
The environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, are made of the raw material below according to parts by weight：Polyphenyl second
110 parts of alkene, 5 parts of calcium stearate, 2.5 parts of antioxidant, 1.6 parts of light stabilizer, 3.0 parts of decabromodiphenylethane, Polystyrene Sulronate 5
Part, 1.4 parts of nano-calcium carbonate, 1.3 parts of ethyoxyl cocoalkyl amines；Wherein, the antioxidant is antioxidant 1076, and the light is steady
It is light stabilizer 944 to determine agent.
In the present embodiment, the preparation method of the environmentally friendly heat shrink films of the high grade of transparency and high tenacity, steps are as follows：
1）Polystyrene Sulronate and nano-calcium carbonate are weighed, after Polystyrene Sulronate heating in vacuum to complete melting, addition is received
Rice calcium carbonate, is stirred 5h, then ultrasonication 60min, obtains additive；
2）Polystyrene and ethyoxyl cocoalkyl amines are weighed, polystyrene is added to reaction kettle, is warming up to 265
DEG C, ethyoxyl cocoalkyl amines are put into, 30min is stirred, obtain the first mixture；
3）Reaction kettle is cooled to 245 DEG C, additive is added, is stirred 20min, obtains the second mixture；
4）Reaction kettle is warming up to 255 DEG C, weighs calcium stearate, antioxidant, light stabilizer and decabromodiphenylethane, and complete
Portion is put into reaction kettle, is stirred 50min, obtains third mixture；
5）Third mixture is first passed through screw extruder to squeeze out, then is squeezed out by single layer inflation film manufacturing machine, after dry, is managed
Base；
6）It after pipe is preheated, is sent into and stretches in case, carry out biaxial tension processing, obtain film, you can, the two-way drawing
The temperature stretched is 115 DEG C.
Comparative example
Compared with Example 3, Polystyrene Sulronate is free of, other are same as Example 3.
Environmentally friendly heat shrink films prepared by embodiment 1-5 and comparative example are tested for the property, test result such as 1 institute of table
Show.
1 performance test table of table
As can be seen from the above table, the heat shrink films that prepared by the present invention, raw material are mainly polystyrene, meet environmental protection and want
It asks, fracture tensile strength has reached 73.1MPa or more, has very high toughness, and transparency has reached 89.2% or more, is more than
Existing environmentally friendly heat shrink films in the market, have preferably packaging effect, good market prospect.
Embodiment 3 is compared with comparative example, and in terms of fracture tensile strength, embodiment 3 is better than comparative example, in elongation at break
Aspect, without apparent difference between embodiment 3 and comparative example, in terms of light transmittance, embodiment 3 is slightly better than comparative example.Due to
Comparative example compared with Example 3, is free of Polystyrene Sulronate, other are same as Example 3, it can therefore be seen that the present invention passes through
Polystyrene Sulronate is added, the toughness and transparency of heat shrink films can be improved.
The better embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula, one skilled in the relevant art within the scope of knowledge, can also be without departing from the purpose of the present invention
Various changes can be made.
Claims (6)
1. the environmentally friendly heat shrink films of a kind of high grade of transparency and high tenacity, which is characterized in that by below according to the raw material group of parts by weight
At：100-110 parts of polystyrene, 3-5 parts of calcium stearate, 1.5-2.5 parts of antioxidant, 1.2-1.6 parts of light stabilizer, decabrominated dipheny
2.5-3.0 parts of ethane, 2-5 parts of Polystyrene Sulronate, 1.0-1.4 parts of nano-calcium carbonate, 0.7-1.3 parts of ethyoxyl cocoalkyl amines.
2. the environmentally friendly heat shrink films of the high grade of transparency according to claim 1 and high tenacity, which is characterized in that by below according to
The raw material of parts by weight forms：103-108 parts of polystyrene, 3.4-4.7 parts of calcium stearate, 1.7-2.3 parts of antioxidant, light stabilizer
1.3-1.5 parts, 2.6-2.8 parts of decabromodiphenylethane, 3-4 parts of Polystyrene Sulronate, 1.1-1.3 parts of nano-calcium carbonate, ethyoxyl coconut palm
Oily alkylamine 0.8-1.1 parts.
3. the environmentally friendly heat shrink films of the high grade of transparency according to claim 2 and high tenacity, which is characterized in that by below according to
The raw material of parts by weight forms：106 parts of polystyrene, 3.9 parts of calcium stearate, 2.1 parts of antioxidant, 1.4 parts of light stabilizer, ten bromines two
2.7 parts of vinylbenzene, 3.3 parts of Polystyrene Sulronate, 1.2 parts of nano-calcium carbonate, 0.9 part of ethyoxyl cocoalkyl amines.
4. the environmentally friendly heat shrink films of the high grade of transparency according to claim 3 and high tenacity, which is characterized in that the antioxidant
For antioxidant 1076.
5. the environmentally friendly heat shrink films of the high grade of transparency according to claim 4 and high tenacity, which is characterized in that the light is stablized
Agent is light stabilizer 944.
6. a kind of preparation method of the environmentally friendly heat shrink films of high grade of transparency according to any one of claims 1 to 5 and high tenacity,
It is characterized in that, steps are as follows：
1）Polystyrene Sulronate and nano-calcium carbonate are weighed, after Polystyrene Sulronate heating in vacuum to complete melting, nano-sized carbon is added
Sour calcium is stirred 3-5h, then ultrasonication 50-60min, obtains additive；
2）Polystyrene and ethyoxyl cocoalkyl amines are weighed, polystyrene is added to reaction kettle, is warming up to 260-265
DEG C, ethyoxyl cocoalkyl amines are put into, 20-30min is stirred, obtain the first mixture；
3）Reaction kettle is cooled to 240-245 DEG C, additive is added, is stirred 10-20min, obtains the second mixture；
4）Reaction kettle is warming up to 250-255 DEG C, weighs calcium stearate, antioxidant, light stabilizer and decabromodiphenylethane, and complete
Portion is put into reaction kettle, is stirred 40-50min, obtains third mixture；
5）Third mixture is first passed through screw extruder to squeeze out, then is squeezed out by single layer inflation film manufacturing machine, after dry, obtains pipe；
6）It after pipe is preheated, is sent into and stretches in case, carry out biaxial tension processing, obtain film, you can, the biaxial tension
Temperature is 110-115 DEG C.
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| JP4560704B2 (en) * | 2003-04-08 | 2010-10-13 | 東洋紡績株式会社 | Multilayer Syndiotactic Polystyrene Stretched Film for Packaging Materials |
| CN103483796A (en) * | 2013-09-29 | 2014-01-01 | 太仓市鸿运包装材料有限公司 | Scratching-resistant and flame-retardant PC (polycarbonate) film material and preparation method thereof |
| CN103834086B (en) * | 2014-03-19 | 2016-08-17 | 华南农业大学 | A kind of efficiently controllable light oxidation-biodegradable plastic film and preparation method thereof |
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