CN106393911B - A kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane and its processing method - Google Patents
A kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane and its processing method Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
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- 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
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
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- 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
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
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- 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
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
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- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract
The present invention provides a kind of polyethylene terephthalate modifying linear low-density polyethylene composite membranes, including five-layer co-squeezing layer structure, the five-layer co-squeezing layer structure is followed successively by the first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer；Wherein, the material of the third enhancement layer includes polyethylene terephthalate modifying linear low-density polyethylene.Polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) composite membrane of the present invention, the transparency is good, and heat sealability is good, it is soft, it is excellent in cushion effect, tensile strength Da≤30Mpa, fracture elongation >=500%；120 DEG C or more boilings are resistant to, there is certain barriers function, -70 DEG C of low temperature etc. is resistant to, is packaging industry, a kind of preferred material of gluing industry, protective film industry.
Description
Technical field
The present invention relates to gluing industry, packaging industry, protective film industries, it particularly relates to a kind of poly terephthalic acid
Glycol ester (PET) modifying linear low-density polyethylene (LLDPE) composite membrane and its processing method.
Background technique
Linear low density polyethylene (LLDPE) is compared with low density polyethylene, softening temperature with higher and molten
Melt temperature, has the advantages that big intensity, good toughness, big, the heat-resisting good and cold resistance of rigidity are good, in addition, also having good resistance to environment
The performances such as stress cracking resistance, impact resistant strength and tear-resistant intensity.But processing performance is not so good as LDPE.
But LLDPE, compared with engineering material polyethylene terephthalate (PET), intensity is low, and heat resistance is not
Enough, barrier property is poor.And PET material have heat resistance is good, intensity is high, creep resistance, resistance to fatigue resistance, good stability of the dimension and
The advantages that price is easy, in addition, its material source is wide, can virgin material can also feed back.But PET material processing crystallinity speed is slow,
Its material stiffness is high, hardness is big, and fracture elongation is low, and material is crisp.
As it can be seen that LLDPE and two kinds of materials of PET are each advantageous, also respectively there is disadvantage, now, two kinds of bills of materials of many producers
The compound method of the film glue solely blown out, is made into composite membrane.But glue composite membrane has the following defects, comprising:
1) glue volatility is big, pollutes environment；
2) because glue is thermosetting material, reclaimed materials secondary cannot use film made of, be the unfriendly material of environment；
3) because of two kinds of material proportion differences, compound caudacoria will appear edge-curl phenomenon.
Summary of the invention
The purpose of the present invention is to provide a kind of high-temperature resistant, high-intensitive polyethylene terephthalate (PET) are modified
Linear low density polyethylene (LLDPE) composite membrane, (abbreviation HTP film).It specifically includes: increasing film strength, tensile strength has
20MPa is increased to 30MPa；Improve the heat resistance of film, fusing point is improved by original 115 DEG C -125 DEG C to 135-145 DEG C；
PET can use virgin material, it is also possible to feed back；4th, using blending and modifying, both alloy material combines advantage.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane, including five-layer co-squeezing layer knot
Structure, the five-layer co-squeezing layer structure are followed successively by the first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th
Printing layer；Wherein, the material of the third enhancement layer includes polyethylene terephthalate modifying linear low-density polyethylene.
The polyethylene terephthalate modifying linear low-density polyethylene by polyethylene terephthalate,
Linear low density polyethylene, low density polyethylene (LDPE) and second it is dilute-methyl acrylate-glycidyl methacrylate is prepared,
Wherein, the polyethylene terephthalate, the linear low density polyethylene, the low density polyethylene (LDPE) and the second
Dilute-methyl acrylate-glycidyl methacrylate weight percent is 30-45%:40-55%:5-18%:1-6%.
The material of first hot sealing layer includes low density polyethylene (LDPE) and linear low density polyethylene, second transition zone
Material include copolymerization polypropylene and linear low density polyethylene, the material of the third enhancement layer include poly terephthalic acid second
Diol ester modifying linear low-density polyethylene, the material of the 4th transition zone include copolymerization polypropylene and linear low density polyethylene
The material of alkene, the 5th printing layer includes low density polyethylene (LDPE) and linear low density polyethylene.
The material of first hot sealing layer is low density polyethylene and linear low density polyethylene LLDPE；
The material of second transition zone is copolymer polypropylene (PP-B), linear low density polyethylene (LLDPE), micron fill mother
Material；
The material of third enhancement layer be using second it is dilute-methyl acrylate-glycidyl methacrylate is as compatilizer
Polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE).
The material of 4th transition zone is copolymer polypropylene (PP-B), linear low density polyethylene (LLDPE) and micron are filled
Masterbatch；
The material of 5th printing layer is low density polyethylene and linear low density polyethylene.
Volume hundred shared by first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer
Divide than being respectively 10-20%, 18-25%, 25-40%, 18-25% and 10-20%.In one embodiment, first heat
Percent by volume shared by sealing, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer is respectively 15%,
20%, 30%, 20% and 15%.
Further, the polyethylene terephthalate modifying linear low-density polyethylene composite membrane with a thickness of
0.03-0.07。
Further, the width of the polyethylene terephthalate modifying linear low-density polyethylene composite membrane is
900-1100mm。
The polyethylene terephthalate modifying linear low-density polyethylene composite membrane with a thickness of 0.03-0.07.
In one embodiment, a kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane,
With a thickness of 0.04mm, wherein first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer
Thickness be respectively 0.006mm, 0.008mm, 0.012mm, 0.008mm and 0.006mm.
First hot sealing layer and the thickness of the 5th printing layer account for overall thickness 15% (herein, thickness ratio is equal to
Volume ratio, the same below), material is that 40% (weight ratio, the same below) linear low density polyethylene (LDPE) and 60% are low close
It spends polyethylene (LLDPE).The selection reason of this material are as follows: first is that the processing performance of low density polyethylene (LDPE) (LDPE) is good, second is that
Low density polyethylene (LDPE) (LDPE) intensity is low, and temperature tolerance is poor, and accounting should not be too many；Third is that outer layer does hot sealing layer, accounting also need not be too
It is more；Fourth is that the first hot sealing layer and the 5th printing layer take symmetrical structure, two layers of amount is consistent, and film is not in curling problems.
The thickness of second transition zone and the 4th transition zone accounts for the 20% of overall thickness, and material is that 55% copolymerization is poly-
+ 5% micro-calcium carbonate filler parent granule of+40% linea low density (LLDPE) of propylene (PP-B).The reason for this is that: first is that copolymerization poly- third
Alkene good toughness, the transparency is good, and accounting suitably increases, second is that polyacrylic brittleness is strong, it is necessary to increase LDPE dosage, play toughening to film
Effect, but the rigidity and heat resistance of expendable material are understood simultaneously, so suitably increasing micro-calcium carbonate filler parent granule, balance its toughness
And hardness.
The material of third enhancement layer is polyethylene terephthalate (PET) modifying linear low-density polyethylene
(LLDPE), thickness accounts for the 30% of overall thickness, first is that playing main resistance to mild enhancing function, it is necessary to assure functional layer thickness is big
In other layers, the enhancement of polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) could be embodied
Energy and heat resistance, second is that blending and modifying, major embodiment PET is modified to PE, so PE is continuous phase, match (weight ratio, below
It is identical) PET:LLDPE:LDPE: compatilizer=40%:47%:10%:3%.
Another object of the present invention is that providing a kind of high-temperature resistant, barriers function good polyethylene terephthalate
The processing method of ester (PET) modifying linear low-density polyethylene (LLDPE) composite membrane.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of processing of polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) composite membrane
Method includes the following steps:
Step 1: by PET, linear low density polyethylene (LLDPE), low density polyethylene (LDPE) (LDPE) and second it is dilute-acrylic acid first
Ester-glycidyl methacrylate, which is added in high speed agitator, to be stirred, and draw ratio 40 is added in the mixture stirred evenly
In above parallel dual-screw extruding machine with Strong shear and mixed element, the material for making clothes of extrusion is through cooling and dicing, vibration sieving, baking
It is dry, test moisture content to it is aqueous≤0.02% after, obtain the poly- second of polyethylene terephthalate (PET) modified linear low density
Alkene；
Step 2: each layer stirs evenly respectively according to following raw materials according and proportion, in which:
First hot sealing layer: 50-70%LDPE+30-50%LLDPE；
Second transition zone: 50-60%PPB+35-48%LLDPE+2-10% microns of filling master batch；
The third enhancement layer: 100% polyethylene terephthalate modifying linear low-density polyethylene；
4th transition zone: 50-65%PPB+30-45%LLDPE+2-8% microns of filling master batch；
5th printing layer: 50-80%LDPE+20-50%LLDPE；
Step 3: each layer raw material in step 2 is respectively put into the five-layer co-squeezing bottom blow blowout release composite membrane of high temperature resistant.
In one embodiment, the first hot sealing layer: 60%LDPE+40%LLDPE, the second transition zone: 55%PP-B+40%
LLDPE+5% microns of filling master batch, third enhancement layer: 100% polyethylene terephthalate (PET) modified linear low density
Polyethylene (LLDPE), the 4th transition zone: 55%PP-B+40%LLDPE+5% microns of filling master batch, the 5th printing layer: 60%
LDPE+40%LLDPE.
Further, PET: linear low density polyethylene (LLDPE): low density polyethylene (LDPE) (LDPE): second is dilute-acrylic acid first
Ester-glycidyl methacrylate is the weight ratio according to 40%:47%:10%:3%.
Further, the processing method further includes step 4 and step 5, in which:
The step 4 is last volume inspection；The step 5 be it is qualified after be packed and stored.
The heat-resistant, high strength degree composite membrane blown out using five-layer co-squeezing bottom blow, the transparency is good, and heat sealability is good, soft, resists
Impact strength is high, tensile strength Da≤30Mpa, fracture elongation >=500%.
LDPE is low density polyethylene (LDPE) of the melt flow rate (MFR) in 1-2g/10min (190 DEG C, 2.16kg)；
LLDPE is the linear low density polyethylene of melt flow rate (MFR) 2-3g/10min (190 DEG C, 2.16kg)；
PP-B is copolymer polypropylene of the melt flow rate (MFR) in 1-3g/10min (190 DEG C, 2.16kg)；
Polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) is that melt flow rate (MFR) exists
1-3g/10min (230 DEG C, 2.16kg) with second it is dilute-methyl acrylate-glycidyl methacrylate terpolymer
As compatilizer, the modified poly- LLDPE of PET.
Further, water content≤0.02% of the PET in step 1.
In step 1, the revolving speed 900-1400r/min of the high speed agitator, and mixing time is 5 minutes.
In step 1, the mixture stirred evenly is put into material storage tube, the parallel dual-screw extruding machine is added through feeder
In.
9 area's temperature of the parallel dual-screw extruding machine are respectively 175-185 DEG C, 195-205 DEG C, 240-250 DEG C, 250-
260 DEG C, 250-260 DEG C, 250-260 DEG C, 245-255 DEG C, 240-250 DEG C and 225-235 DEG C, melt temperature are 230-260 DEG C,
Head temperature is 220-255 DEG C, screw speed 280-350r/min.
Wherein, 9 area's temperature of the parallel dual-screw extruding machine are respectively 180 DEG C, 200 DEG C, 245 DEG C, 255 DEG C, 255
DEG C, 255 DEG C, 250 DEG C, 245 DEG C and 230 DEG C, melt temperature be 245 DEG C, head temperature be 240 DEG C, screw speed 300r/
min。
The polyethylene terephthalate (PET) modifying linear low-density polyethylene obtained in step 1 is sealed
It saves, can be incorporated in the packaging bag of liner sealing.
The micron filling master batch is micro-calcium carbonate, and the filling of polyolefin made of specially 1500 mesh activated Calcium carbonates is female
Material.
The preparation of polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) material, PET are
A kind of crystalline polymer that polarity is strong, there is good mechanical property, and impact strength is 3~5 times of other films, folding resistance
It is good；Oil resistant, resistance to fat, resistance to olefin(e) acid, diluted alkaline, resistance to most of solvents；Excellent high- and low-temperature resistance performance, can be in 120 DEG C of temperature ranges
Interior long-time service, short-period used are resistant to 150 DEG C of high temperature, are resistant to -70 DEG C of low temperature, and influence very when high and low temperature on its mechanical performance
It is small；Gas and vapor permeability are low, existing excellent resistance gas and water, oil and peculiar smell performance；Transparency is high, can stop ultraviolet light,
Glossiness is good；Nontoxic, tasteless, wholesomeness is good, can be directly used for food packaging.
Linear low density polyethylene (LLDPE), compared with LDPE, softening temperature with higher and melting temperature have for it
The advantages that intensity is big, good toughness, big, heat-resisting, cold resistance is good rigidity, also has good environmental stress crack resistance, impact resistance
The performances such as intensity, tear-resistant intensity, but there are molding shrinkages it is big, barrier property is poor, and heat distortion temperature is not high the disadvantages of.It will
The disadvantage that PET/PE blend can overcome PET and PE intrinsic is made in PET and PE blending, learns from other's strong points to offset one's weaknesses in performance.Solve the two phase
The method of capacitive be added second it is dilute-methyl acrylate-glycidyl methacrylate terpolymer, have with PET and PE
Fabulous compatible role.
It should be noted that each meaning quality percentage in the case where not illustrating about proportion or percentage composition
Than or mass content etc..
Polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) of the present invention is compound
Film, the transparency is good, and heat sealability is good, soft, excellent in cushion effect, tensile strength Da≤30Mpa, fracture elongation >=500%.
120 DEG C or more boilings are resistant to, there is certain barriers function, -70 DEG C of low temperature etc. is resistant to, is packaging industry, gluing industry, protective film
A kind of preferred material of industry.
Specific embodiment
The present invention provides a kind of polyethylene terephthalate modifying linear low-density polyethylene composite membranes, including five
Layer coextruded layer structure, the five-layer co-squeezing layer structure are followed successively by the first hot sealing layer, the second transition zone, third enhancement layer, the 4th mistake
Cross layer and the 5th printing layer；Wherein, the material of the third enhancement layer includes that polyethylene terephthalate modified linear is low
Density polyethylene.
The material of first hot sealing layer includes low density polyethylene (LDPE) and linear low density polyethylene, second transition zone
Material include copolymerization polypropylene and linear low density polyethylene, the material of the third enhancement layer include poly terephthalic acid second
Diol ester modifying linear low-density polyethylene, the material of the 4th transition zone include copolymerization polypropylene and linear low density polyethylene
The material of alkene, the 5th printing layer includes low density polyethylene (LDPE) and linear low density polyethylene.
The material of first hot sealing layer is low density polyethylene and linear low density polyethylene LLDPE；
The material of second transition zone is copolymer polypropylene (PP-B), linear low density polyethylene (LLDPE), micron fill mother
Material；
The material of third enhancement layer be using second it is dilute-methyl acrylate-glycidyl methacrylate is used as compatilizer, poly-
Ethylene glycol terephthalate (PET) modifying linear low-density polyethylene (LLDPE).
The material of 4th transition zone is copolymer polypropylene (PP-B), linear low density polyethylene (LLDPE) and micron are filled
Masterbatch；
The material of 5th printing layer is low density polyethylene and linear low density polyethylene.
Further, first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer
Shared percent by volume is respectively 15%, 20%, 30%, 20% and 15%.
Further, the polyethylene terephthalate modifying linear low-density polyethylene composite membrane with a thickness of
0.03-0.07。
Further, the width of the polyethylene terephthalate modifying linear low-density polyethylene composite membrane is
900-1100mm。
In one embodiment, a kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane,
With a thickness of 0.04mm, wherein first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer
Thickness be respectively 0.006mm, 0.008mm, 0.012mm, 0.008mm and 0.006mm.
First hot sealing layer and the thickness of the 5th printing layer account for overall thickness 15% (herein, thickness ratio is equal to
Volume ratio, the same below), material is that 40% (weight ratio, the same below) linear low density polyethylene (LDPE) and 60% are low close
It spends polyethylene (LLDPE).The selection reason of this material are as follows: first is that the processing performance of low density polyethylene (LDPE) (LDPE) is good, second is that
Low density polyethylene (LDPE) (LDPE) intensity is low, and temperature tolerance is poor, and accounting should not be too many；Third is that outer layer does hot sealing layer, accounting also need not be too
It is more；Fourth is that the first hot sealing layer and the 5th printing layer take symmetrical structure, two layers of amount is consistent, and film is not in curling problems.
The thickness of second transition zone and the 4th transition zone accounts for the 20% of overall thickness, and material is that 55% copolymerization is poly-
+ 5% micro-calcium carbonate filler parent granule of+40% linea low density (LLDPE) of propylene (PP-B).The reason for this is that: first is that copolymerization poly- third
Alkene good toughness, the transparency is good, and accounting suitably increases, second is that polyacrylic brittleness is strong, it is necessary to increase LDPE dosage, play toughening to film
Effect, but the rigidity and heat resistance of expendable material are understood simultaneously, so suitably increasing micro-calcium carbonate filler parent granule, balance its toughness
And hardness.
The material of third enhancement layer is polyethylene terephthalate (PET) modifying linear low-density polyethylene
(LLDPE), thickness accounts for the 30% of overall thickness, first is that playing main resistance to mild enhancing function, it is necessary to assure functional layer thickness is big
In other layers, the enhancement of polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) could be embodied
Energy and heat resistance, second is that blending and modifying, major embodiment PET is modified to PE, so PE is continuous phase, match (weight ratio, below
It is identical) PET:LLDPE:LDPE: compatilizer=40%:47%:10%:3%.
The present invention also provides a kind of polyethylene terephthalate (PET) modifying linear low-density polyethylenes
(LLDPE) processing method of composite membrane, includes the following steps:
Step 1: by PET: linear low density polyethylene (LLDPE): low density polyethylene (LDPE) (LDPE): second is dilute-acrylic acid first
Ester-glycidyl methacrylate is added in high speed agitator and stirs according to the weight ratio of 40%:47%:10%:3%,
The mixture stirred evenly is added in the parallel dual-screw extruding machine with Strong shear and mixed element of 40 or more draw ratio, is squeezed
Material for making clothes out through cooling and dicing, vibration sieving, drying, test moisture content to it is aqueous≤0.02% after, obtain terephthalic acid (TPA) second two
Alcohol ester (PET) modifying linear low-density polyethylene；
Step 2: each layer stirs evenly respectively according to following raw materials according and proportion, in which:
First hot sealing layer: 60%LDPE+40%LLDPE,
Second transition zone: 55%PP-B+40%LLDPE+5% microns of filling master batch,
Third enhancement layer: 100% ethylene glycol terephthalate (PET) modifying linear low-density polyethylene (LLDPE),
4th transition zone: 55%PP-B+40%LLDPE+5% microns of filling master batch,
5th printing layer: 60%LDPE+40%LLDPE；
Step 3: each layer raw material in step 2 is respectively put into the five-layer co-squeezing bottom blow blowout release composite membrane of high temperature resistant.
Further, the processing method further includes step 4 and step 5, in which:
The step 4 is last volume inspection；The step 5 be it is qualified after be packed and stored.
The heat-resistant, high strength degree composite membrane blown out using five-layer co-squeezing bottom blow, the transparency is good, and heat sealability is good, soft, resists
Impact strength is high, tensile strength Da≤30Mpa, fracture elongation >=500%.
LDPE is low density polyethylene (LDPE) of the melt flow rate (MFR) in 1-2g/10min (190 DEG C, 2.16kg)；
LLDPE is the linear low density polyethylene of melt flow rate (MFR) 2-3g/10min (190 DEG C, 2.16kg)；
PP-B is copolymer polypropylene of the melt flow rate (MFR) in 1-3g/10min (190 DEG C, 2.16kg)；
Polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) is that melt flow rate (MFR) exists
1-3g/10min (230 DEG C, 2.16kg) with second it is dilute-methyl acrylate-glycidyl methacrylate terpolymer
As compatilizer, the modified poly- LLDPE of PET.
Further, water content≤0.02% of the PET in step 1.
In step 1, the revolving speed 900-1400r/min of the high speed agitator, and mixing time is 5 minutes.
In step 1, the mixture stirred evenly is put into material storage tube, the parallel dual-screw extruding machine is added through feeder
In.
Wherein, 9 area's temperature of the parallel dual-screw extruding machine are respectively 180 DEG C, 200 DEG C, 245 DEG C, 255 DEG C, 255
DEG C, 255 DEG C, 250 DEG C, 245 DEG C and 230 DEG C, melt temperature be 245 DEG C, head temperature be 240 DEG C, screw speed 300r/
min。
The polyethylene terephthalate (PET) modifying linear low-density polyethylene obtained in step 1 is sealed
It saves, can be incorporated in the packaging bag of liner sealing.
The micron filling master batch is micro-calcium carbonate, and the filling of polyolefin made of specially 1500 mesh activated Calcium carbonates is female
Material.
The preparation of polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) material, PET are
A kind of crystalline polymer that polarity is strong, there is good mechanical property, and impact strength is 3~5 times of other films, folding resistance
It is good；Oil resistant, resistance to fat, resistance to olefin(e) acid, diluted alkaline, resistance to most of solvents；Excellent high- and low-temperature resistance performance, can be in 120 DEG C of temperature ranges
Interior long-time service, short-period used are resistant to 150 DEG C of high temperature, are resistant to -70 DEG C of low temperature, and influence very when high and low temperature on its mechanical performance
It is small；Gas and vapor permeability are low, existing excellent resistance gas and water, oil and peculiar smell performance；Transparency is high, can stop ultraviolet light,
Glossiness is good；Nontoxic, tasteless, wholesomeness is good, can be directly used for food packaging.
Linear low density polyethylene (LLDPE), compared with LDPE, softening temperature with higher and melting temperature have for it
The advantages that intensity is big, good toughness, big, heat-resisting, cold resistance is good rigidity, also has good environmental stress crack resistance, impact resistance
The performances such as intensity, tear-resistant intensity, but there are molding shrinkages it is big, barrier property is poor, and heat distortion temperature is not high the disadvantages of.It will
The disadvantage that PET/PE blend can overcome PET and PE intrinsic is made in PET and PE blending, learns from other's strong points to offset one's weaknesses in performance.Solve the two phase
The method of capacitive be added second it is dilute-methyl acrylate-glycidyl methacrylate terpolymer, have with PET and PE
Fabulous compatible role.
It should be noted that each meaning quality percentage in the case where not illustrating about proportion or percentage composition
Than or mass content etc..
Embodiment 1
A kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane, including five-layer co-squeezing layer knot
Structure, the five-layer co-squeezing layer structure are followed successively by the first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th
Printing layer.
The processing of polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) composite membrane
Method includes the following steps:
Step 1: by PET: linear low density polyethylene (LLDPE): low density polyethylene (LDPE) (LDPE): second is dilute-acrylic acid first
Ester-glycidyl methacrylate is added in high speed agitator and stirs according to the weight ratio of 40%:47%:10%:3%,
The mixture stirred evenly is added in the parallel dual-screw extruding machine with Strong shear and mixed element of 40 or more draw ratio, is squeezed
Material for making clothes out through cooling and dicing, vibration sieving, drying, test moisture content to it is aqueous≤0.02% after, obtain poly terephthalic acid second
Diol ester (PET) modifying linear low-density polyethylene；
Step 2: each layer stirs evenly respectively according to following raw materials according and proportion, in which:
First hot sealing layer: 60%LDPE+40%LLDPE,
Second transition zone: 55%PP-B+40%LLDPE+5% microns of filling master batch,
Third enhancement layer: 100% polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE),
4th transition zone: 55%PP-B+40%LLDPE+5% microns of filling master batch,
5th printing layer: 60%LDPE+40%LLDPE；
Step 3: each layer raw material in step 2 is respectively put into the five-layer co-squeezing bottom blow blowout release composite membrane of high temperature resistant；
Step 4: last volume is examined；
Step 5: being packed and stored after qualified.
Embodiment 2
A kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane, including five-layer co-squeezing layer knot
Structure, the five-layer co-squeezing layer structure are followed successively by the first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th
Printing layer.
The processing of polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE) composite membrane
Method includes the following steps:
Step 1: by PET: linear low density polyethylene (LLDPE): low density polyethylene (LDPE) (LDPE): second is dilute-acrylic acid first
Ester-glycidyl methacrylate is added in high speed agitator and stirs according to the weight ratio of 41%:48%:8%:3%,
The mixture stirred evenly is added in the parallel dual-screw extruding machine with Strong shear and mixed element of 40 or more draw ratio, is squeezed
Material for making clothes out through cooling and dicing, vibration sieving, drying, test moisture content to it is aqueous≤0.02% after, obtain poly terephthalic acid second
Diol ester (PET) modifying linear low-density polyethylene；
Step 2: each layer stirs evenly respectively according to following raw materials according and proportion, in which:
First hot sealing layer: 61%LDPE+39%LLDPE,
Second transition zone: 52%PP-B+42%LLDPE+6% microns of filling master batch,
Third enhancement layer: 100% polyethylene terephthalate (PET) modifying linear low-density polyethylene (LLDPE),
4th transition zone: 58%PP-B+35%LLDPE+7% microns of filling master batch,
5th printing layer: 62%LDPE+38%LLDPE；
Step 3: each layer raw material in step 2 is respectively put into the five-layer co-squeezing bottom blow blowout release composite membrane of high temperature resistant；
Step 4: last volume is examined；
Step 5: being packed and stored after qualified.
By examining its performance, obtain obtaining the polyethylene terephthalate modification in embodiment 1 and embodiment 2
Linear low density polyethylene composite membrane has the following characteristics that tensile strength Da≤30Mpa, elongation percentage >=500%；It is 120 DEG C of steamings
It boils；The transparency is good, and heat sealability is good, and soft, excellent in cushion effect, shrinking percentage≤2% is indeformable, not alice；There is certain resistance
Every function.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (2)
1. a kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane, which is characterized in that including five layers
Coextruded layer structure, the five-layer co-squeezing layer structure are followed successively by the first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition
Layer and the 5th printing layer；Wherein, the material of the third enhancement layer includes that polyethylene terephthalate modified linear is low close
Polyethylene is spent, the polyethylene terephthalate modifying linear low-density polyethylene passes through polyethylene terephthalate
Ester, linear low density polyethylene, low density polyethylene (LDPE) and ethylene-methyl acrylate-glyceryl methacrylate are prepared into
It arrives, wherein the polyethylene terephthalate, the linear low density polyethylene, the low density polyethylene (LDPE) and described
The weight percent of ethylene-methyl acrylate-glyceryl methacrylate is 30-45%:40-55%:5-18%:1-
6%；
Percent by volume shared by first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer
Respectively 10-20%, 18-25%, 25-40%, 18-25% and 10-20%；
The polyethylene terephthalate modifying linear low-density polyethylene composite membrane with a thickness of 0.04mm, wherein institute
State the first hot sealing layer, the second transition zone, third enhancement layer, the 4th transition zone and the 5th printing layer thickness be respectively 0.006mm,
0.008mm, 0.012mm, 0.008mm and 0.006mm；
First hot sealing layer: 50-70%LDPE+30-50%LLDPE；
Second transition zone: 50-60%PPB+35-48%LLDPE+2-10% microns of filling master batch；
The third enhancement layer: 100% polyethylene terephthalate modifying linear low-density polyethylene；
4th transition zone: 50-65%PPB+30-45%LLDPE+2-8% microns of filling master batch；
5th printing layer: 50-80%LDPE+20-50%LLDPE.
2. a kind of polyethylene terephthalate modifying linear low-density polyethylene composite membrane according to claim 1
Processing method, which comprises the steps of:
Step 1: by PET, linear low density polyethylene LLDPE, low density polyethylene and ethylene-methyl acrylate-methyl
Glycidyl acrylate, which is added in high speed agitator, to be stirred, and the mixture stirred evenly is added to the band of 40 or more draw ratio
In the parallel dual-screw extruding machine of Strong shear and mixed element, the material for making clothes of extrusion is through cooling and dicing, vibration sieving, drying, test
After moisture content to water content≤0.02%, polyethylene terephthalate modifying linear low-density polyethylene is obtained；
Step 2: each layer stirs evenly respectively according to following raw materials according and proportion, in which: first hot sealing layer: 50-70%
LDPE+30-50%LLDPE；
Second transition zone: 50-60%PPB+35-48%LLDPE+2-10% microns of filling master batch；
The third enhancement layer: 100% polyethylene terephthalate modifying linear low-density polyethylene；
4th transition zone: 50-65%PPB+30-45%LLDPE+2-8% microns of filling master batch；
5th printing layer: 50-80%LDPE+20-50%LLDPE；
Step 3: each layer raw material in step 2 being respectively put into five-layer co-squeezing bottom blow blowout polyethylene terephthalate and is changed
Property linear low density polyethylene composite membrane；
LDPE is 190 DEG C, and melt flow rate (MFR) is measured under the conditions of 2.16kg in the low density polyethylene (LDPE) of 1-2g/10min；
LLDPE is 190 DEG C, and the linear low density polyethylene of melt flow rate (MFR) 2-3g/10min is measured under the conditions of 2.16kg；PPB
It is 190 DEG C, melt flow rate (MFR) is measured under the conditions of 2.16kg in the copolymer polypropylene of 1-3g/10min；Poly terephthalic acid second two
Alcohol ester modifying linear low-density polyethylene is 230 DEG C, measure under the conditions of 2.16kg melt flow rate (MFR) 1-3g/10min with
The terpolymer of ethylene-methyl acrylate-glyceryl methacrylate is as compatilizer, poly terephthalic acid second two
Alcohol ester modifying linear low-density polyethylene；
Water content≤0.02% of the PET in step 1；
9 area's temperature of the parallel dual-screw extruding machine are respectively 175-185 DEG C, 195-205 DEG C, 240-250 DEG C, 250-260
DEG C, 250-260 DEG C, 250-260 DEG C, 245-255 DEG C, 240-250 DEG C and 225-235 DEG C, melt temperature be 230-260 DEG C, machine
Head temperature is 220-255 DEG C, screw speed 280-350r/min.
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| CN109054665B (en) * | 2018-06-25 | 2020-12-01 | 湖北工业大学 | Preparation method of high-adhesion-strength hot-water-soaking-resistant metal/plastic composite belt |
| CN109456524B (en) * | 2018-10-22 | 2021-03-23 | 佳易容聚合物(上海)有限公司 | High-barrier PE/LCP/PET resin composition and preparation method thereof |
| CN110254012B (en) * | 2019-07-20 | 2021-08-24 | 福建省凯安包装科技有限公司 | Preparation method of hydrophobic three-layer co-extrusion composite film |
| EP4204229A4 (en) * | 2020-09-10 | 2023-11-01 | Hariharan Krishnan Nair | Recyclable packaging material and process of preparation thereof |
| CN114407463B (en) * | 2021-12-22 | 2023-04-11 | 北京工商大学 | Anti-ultraviolet multilayer protective film for pipeline repair by in-situ curing method for trenchless repair and preparation method thereof |
| CN116003900B (en) * | 2023-02-22 | 2024-05-28 | 湖南优珀斯新材料科技有限公司 | Special material for regenerated PET and PE blending modified blown film, and manufacturing method and application thereof |
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