CN116003900B - Special material for regenerated PET and PE blending modified blown film, and manufacturing method and application thereof - Google Patents
Special material for regenerated PET and PE blending modified blown film, and manufacturing method and application thereof Download PDFInfo
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- CN116003900B CN116003900B CN202310149461.4A CN202310149461A CN116003900B CN 116003900 B CN116003900 B CN 116003900B CN 202310149461 A CN202310149461 A CN 202310149461A CN 116003900 B CN116003900 B CN 116003900B
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002156 mixing Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims abstract description 56
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 52
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000010096 film blowing Methods 0.000 claims abstract description 27
- -1 acrylic ester Chemical class 0.000 claims abstract description 26
- 238000005469 granulation Methods 0.000 claims abstract description 25
- 230000003179 granulation Effects 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 229920001897 terpolymer Polymers 0.000 claims abstract description 9
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 54
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 54
- 239000000155 melt Substances 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 229920000428 triblock copolymer Polymers 0.000 claims description 8
- 238000004078 waterproofing Methods 0.000 claims description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- 239000002313 adhesive film Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 22
- 238000012986 modification Methods 0.000 abstract description 22
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 98
- 229920000139 polyethylene terephthalate Polymers 0.000 description 96
- 239000010410 layer Substances 0.000 description 20
- 238000007664 blowing Methods 0.000 description 16
- 238000004064 recycling Methods 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 10
- 238000010998 test method Methods 0.000 description 9
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920004933 Terylene® Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of polymer films, and relates to a special material for a regenerated PET and PE blending modified blown film, and a manufacturing method and application thereof. The special material for film blowing adopts a composite compatilizer consisting of a compatilizer A and a compatilizer B, and is mixed with regenerated PET bottle flakes and PE raw materials for modification and granulation, and the special material for film blowing is obtained after drying; wherein, the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA. The invention expands the application range of the regenerated PET bottle flakes, greatly improves the temperature resistance, shrinkage and tensile strength of the PE film by utilizing the high strength and ageing resistance of the regenerated PET material, solves the problems of poor LDPE strength and poor ageing resistance, and has low production cost and good economic benefit.
Description
Technical Field
The invention belongs to the technical field of polymer films, relates to recycling of PET bottle flakes, and relates to a special material for blending and modifying recycled PET and PE and a manufacturing method and application thereof.
Background
PET (PolyEthylene Terephthalate ) is one of the most widely used plastics, which has good ductility, high transparency and good safety, and is often used for making beverage bottles or other food packaging materials. The weight of the consumed beverage PET bottle in China reaches 450 ten thousand tons. However, PET can be decomposed completely under natural conditions for at least hundreds of years, and is a burden for environment and economy.
From an economic standpoint, the PET plastic is disposed of after a single use, losing 95% of its value for use. From the environmental protection perspective, the problems of crop yield reduction, marine pollution and the like can be caused. If the used PET plastic bottle, especially beverage bottle, is recycled for regeneration treatment, the method has important significance from the aspects of environmental protection, economy and society
The waste PET plastic bottle can be reprocessed after being treated, and can be used for manufacturing sleeping bags, pillow cores, automobile wheel covers and the like besides being manufactured. The consumption of PET plastic bottles in China is very high, and the PET plastic bottles can be reprocessed and changed into valuable, so that the problem of recycling is solved, and the environmental pollution and the resource waste are reduced. The recycling technology has very broad prospect.
The traditional PET recycling bottle flakes are basically used for PET terylene chemical fibers, but the quantity of the recycling PET bottle flakes is large, and although the quantity of the recycling PET bottle flakes is large for PET terylene chemical fibers, only one way is calculated after all, and the PET bottle flakes cannot be completely digested, so that new application is required to be found, and the recycling of the PET recycling bottle flakes can be effectively solved.
At present, no blending modification is performed on recycled PET bottle flakes and PE (polyethylene), a film blowing method is used for producing PET bottle flakes and PE (polyethylene) blending modification films, and the PET and PE (polyethylene) blending modification films are good in temperature resistance, high in strength, low in shrinkage and good in ageing resistance, can be used for agricultural films and industrial packaging films, but LDPE and PET are poor in compatibility, after being mixed, films cannot be blown normally, and special compatibilization means are required to improve the compatibility of the two materials, so that PET bottle flakes and PE (polyethylene) blending modification special materials are prepared and used for film blowing products.
Disclosure of Invention
The invention aims to provide a special material for blending and modifying recycled PET and PE, a manufacturing method and application thereof, which are used for blowing films, so that the application range of recycled PET bottle flakes is expanded, and the special material is suitable for national industrial policies of circulation, environmental protection and double reduction, and has economic benefits and more important social benefits.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the first aspect of the invention provides a manufacturing method of a special material for blending and modifying a blown film of regenerated PET and PE, wherein a composite compatilizer consisting of compatilizer A and compatilizer B is adopted to blend and modify and granulate with regenerated PET bottle flakes and PE raw materials, and the special material for blowing film is obtained after drying;
Wherein, the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA.
Preferably, in the compatilizer A, the weight percentage of ethylene is 20-30%, the weight percentage of glycidyl acrylate is 5-15%, and the weight percentage of acrylic ester is 55-75%.
More preferably, in the compatilizer A, the ethylene weight percentage is 22-28%, the glycidyl acrylate weight percentage is 6-12%, and the acrylic ester weight percentage is 58-70%.
More preferably, in the compatilizer A, the ethylene weight percentage is 25-38%, the glycidyl acrylate weight percentage is 8-10%, and the acrylic ester weight percentage is 60-65%.
Preferably, in the compatilizer B, SEBS-g-GMA is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block.
More preferably, the SEBS does not contain unsaturated double bonds, and the grafting rate of the SEBS-g-GMA is 1-2%.
More preferably, the SEBS-g-GMA is used in daily litersSAG series.
Preferably, the mass ratio of the compatilizer A to the compatilizer B is 3:2 to 4:1.
Preferably, the mass ratio of the compatilizer A to the compatilizer B is 3:2.
Preferably, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene);
Wherein the LDPE material is of a film blowing grade, and the melt flow rate is 0.2-0.8 g/10min; the melt index of the (linear low density polyethylene) is 1 to 4/10min.
Preferably, the regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.60-0.80 dl/g (test method ASTM D-4603).
More preferably, the regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.60-0.70 dl/g (test method ASTM D-4603).
Preferably, the following components are used in the following amounts by mass fraction:
20-30 parts of regenerated PET bottle flakes, 50-70 parts of LDPE, 10-15 parts of LLDPE, 5-10 parts of composite compatilizer and 1-2 parts of antioxidant master batch.
More preferably, the following components are used in the following amounts by mass fraction:
22-28 parts of regenerated PET bottle flakes, 55-65 parts of LDPE, 10-13 parts of LLDPE, 5-8 parts of composite compatilizer and 1.5-2 parts of antioxidant master batch.
More preferably, the following components are used in the following amounts by mass fraction:
25 parts of regenerated PET bottle flakes, 58 parts of LDPE, 10 parts of LLDPE, 5 parts of composite compatilizer and 2 parts of antioxidant master batch.
Preferably, the blending modification granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600 r/min, and the belt is subjected to vacuum exhaust;
And drying the PET bottle flakes by a vacuum dryer, wherein the moisture content of the PET bottle flakes after drying is less than or equal to 0.05 percent.
Preferably, the technological parameters of the modified granulation are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250;
melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
The second aspect of the invention is to provide a special material for the recycled PET and PE blending modified blown film manufactured by the method.
The third aspect of the invention is to provide an application of the special material for the recycled PET and PE blending modified blown film for producing a single layer or multiple layers of multilayer co-extruded films in the preparation of building waterproof films, agricultural waterproof films and adhesive films.
Preferably, a film blowing machine with three layers or more is adopted, the special material for blending and modifying the regenerated PET and PE is blended with LDPE raw materials according to a proportion to be placed in a film blowing middle layer, and multi-layer film blowing is carried out, so that the substrate film layer is prepared.
Preferably, the total thickness of the substrate film layer is 0.03 to-0.1 mm, wherein: the thickness of the middle layer is 0.02-0.08 mm, and the thicknesses of the surface layer and the bottom layer are 0.005-0.01 mm.
The fourth aspect of the invention provides a production system for multilayer film blowing by adopting the special material for blending and modifying the regenerated PET and PE, which comprises a (middle) 2 extruder, an automatic feeding system, a dryer, a die head and air ring system, a propeller strut, a rotating frame, a film blowing frame, a corona machine, a deviation correcting machine, a slitting mechanism and a winding mechanism, wherein the 1st layer and the 3 rd layer (surface and bottom layer) screw extruder. The structural arrangement is shown in fig. 3.
The production system for carrying out multilayer film blowing on the special material for blending and modifying the regenerated PET and PE comprises the following working procedures:
Layer 2 (middle layer) extrusion procedure: PET and PE (polyethylene) are blended, modified and blown into a film special material, a feeding machine is vacuumized and sucked into a dryer 3, the PET bottle flakes and other main materials reach the requirements after drying, and the PET bottle flakes and other main materials enter a double-screw extruder 1 through an automatic feeding system 3;
Layer 1 and layer 3 extrusion procedure: LDPE, LLDPE and antioxidant enter a single screw extruder 12 from respective automatic feeding systems;
The extruded film is formed into a film gun through a die head and a cooling air circulation system 4, and the film gun is divided into two rolls through a propeller strut 5, an upper rotating frame 6, a corona machine 8, a deviation correcting machine 9 and a slitting mechanism 10, and is rolled into a final product through a rolling mechanism 11, and after inspection, the final product is packaged and put in storage.
Compared with the prior art, the invention has the following technical effects:
The invention utilizes the regenerated PET bottle flakes, adopts the composite compatilizer and PE to blend, modify and granulate to produce the special material for film blowing, and utilizes the high strength and ageing resistance of the regenerated PET material to solve the problems of poor LDPE strength and poor ageing resistance; the special material for film blowing manufactured by the regenerated PET bottle flake material is used for film blowing products, so that the temperature resistance of a PE film can be improved to 150 ℃ from the original 120 ℃, and the shrinkage rate is reduced to 1% from the original 2-3%; the tensile strength is improved to more than 25MPa from 15-18 MPa. The special material for film blowing produced by blending and modifying the regenerated PET bottle flakes and PE (polyethylene) has the advantages of expanding the application range of the regenerated PET bottle flakes, adapting to the national industrial policies of cyclic utilization, environmental protection and double reduction, having economic benefit and more important having larger social benefit.
Drawings
FIG. 1 is a schematic diagram of a film layer structure of an agricultural film by adopting a regenerated PET and PE blending modified film blowing special material;
FIG. 2 is a schematic diagram of a film layer structure of the recycled PET and PE blended modified blown film special material for building waterproof coiled materials;
FIG. 3 is a schematic diagram of a production system for multilayer blown film by blending and modifying special materials for blown film with recycled PET and PE.
Detailed Description
The present invention will be described in detail and in detail by way of the following examples, which are not intended to limit the scope of the invention, for better understanding of the invention.
Example 1 preparation of Special Material for blend modification of recycled PET and PE blown film
Preparing a composite compatilizer by respectively taking a compatilizer A and a compatilizer B, wherein the mass ratio of the compatilizer A to the compatilizer B is 3:2. the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate, which is obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA.
Wherein, in the compatilizer A, the weight percentage of ethylene is 24%, the weight percentage of acrylic acid glycidyl ester is 8%, and the weight percentage of acrylic ester is 68%. In the compatilizer B, SEBS-g-GMA is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block.
Then respectively weighing the following components in proportion: 20 parts of regenerated PET bottle flakes, 55 parts of LDPE, 15 parts of LLDPE, 9 parts of composite compatilizer and 1 part of antioxidant master batch.
Wherein, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene); the LDPE material is of a film blowing grade, and the melt flow rate is 0.6g/10min; the melt index of the (linear low density polyethylene) was 4/10min. The regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.70dl/g (test method ASTM D-4603).
According to the component proportions, the special material for blowing the film is obtained by adopting equipment shown in figure 3 to carry out blending modification granulation firstly and then drying, and specifically comprises the following steps:
the special material S1 for blowing film is obtained by the steps of recycling PET bottle flakes, LDPE, LLDPE, composite compatilizer, antioxidant master batch, weight loss measurement, parallel double-screw granulator, granulating, drying, checking and packaging.
The used modified granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600r/min, and the belt is subjected to vacuum exhaust. The dryer is a vacuum dryer, and the moisture content of PET after drying is less than or equal to 0.05%.
The granulation process optimization parameters are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250.
Melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
Example 2 preparation of Special Material for blend modification of recycled PET and PE blown film
Preparing a composite compatilizer by respectively taking a compatilizer A and a compatilizer B, wherein the mass ratio of the compatilizer A to the compatilizer B is 3:2. the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate, which is obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA.
Wherein, in the compatilizer A, the weight percentage of ethylene is 20 percent, the weight percentage of acrylic acid glycidyl ester is 15 percent, and the weight percentage of acrylic ester is 65 percent. In the compatilizer B, SEBS-g-GMA is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block.
Then respectively weighing the following components in proportion: 25 parts of regenerated PET bottle flakes, 59 parts of LDPE, 10 parts of LLDPE, 5 parts of composite compatilizer and 1 part of antioxidant master batch.
Wherein, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene); the LDPE material is of a film blowing grade, and the melt flow rate is 0.6g/10min; the melt index of the (linear low density polyethylene) was 4/10min. The regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.70dl/g (test method ASTM D-4603).
According to the component proportions, the special material for blowing the film is obtained by adopting equipment shown in figure 3 to carry out blending modification granulation firstly and then drying, and specifically comprises the following steps:
The special material S2 for blowing film is obtained by the steps of recycling PET bottle flakes, LDPE, LLDPE, composite compatilizer, antioxidant master batch, weight loss measurement, parallel double-screw granulator, granulating, drying, checking and packaging.
The used modified granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600r/min, and the belt is subjected to vacuum exhaust. The dryer is a vacuum dryer, and the moisture content of PET after drying is less than or equal to 0.05%.
The granulation process optimization parameters are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250.
Melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
Example 3 preparation of Special Material for blend modification of recycled PET and PE blown film
Preparing a composite compatilizer by respectively taking a compatilizer A and a compatilizer B, wherein the mass ratio of the compatilizer A to the compatilizer B is 3:2. the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate, which is obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA.
Wherein, in the compatilizer A, the weight percentage of ethylene is 30%, the weight percentage of acrylic acid glycidyl ester is 10%, and the weight percentage of acrylic ester is 60%. In the compatilizer B, SEBS-g-GMA is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block.
Then respectively weighing the following components in proportion: 28 parts of recycled PET bottle flakes, 54 parts of LDPE, 10 parts of LLDPE, 6.5 parts of composite compatilizer and 1.5 parts of antioxidant master batch.
Wherein, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene); the LDPE material is of a film blowing grade, and the melt flow rate is 0.6g/10min; the melt index of the (linear low density polyethylene) was 4/10min. The regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.70dl/g (test method ASTM D-4603).
According to the component proportions, the special material for blowing the film is obtained by adopting equipment shown in figure 3 to carry out blending modification granulation firstly and then drying, and specifically comprises the following steps:
The special material S3 for blowing film is obtained by the steps of recycling PET bottle flakes, LDPE, LLDPE, composite compatilizer, antioxidant master batch, weight loss measurement, parallel double-screw granulator, granulating, drying, checking and packaging.
The used modified granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600r/min, and the belt is subjected to vacuum exhaust. The dryer is a vacuum dryer, and the moisture content of PET after drying is less than or equal to 0.05%.
The granulation process optimization parameters are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250.
Melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
Example 4 preparation of Special Material for blend modification of recycled PET and PE blown film
Preparing a composite compatilizer by respectively taking a compatilizer A and a compatilizer B, wherein the mass ratio of the compatilizer A to the compatilizer B is 3:2. the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate, which is obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA.
Wherein, in the compatilizer A, the weight percentage of ethylene is 35%, the weight percentage of acrylic acid glycidyl ester is 10%, and the weight percentage of acrylic ester is 55%. In the compatilizer B, SEBS-g-GMA is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block.
Then respectively weighing the following components in proportion: 30 parts of recycled PET bottle flakes, 55 parts of LDPE, 10 parts of LLDPE and 5 parts of composite compatilizer.
Wherein, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene); the LDPE material is of a film blowing grade, and the melt flow rate is 0.6g/10min; the melt index of the (linear low density polyethylene) was 3/10min. The regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.70dl/g (test method ASTM D-4603).
According to the component proportions, the special material for blowing the film is obtained by adopting equipment shown in figure 3 to carry out blending modification granulation firstly and then drying, and specifically comprises the following steps:
The special material S4 for blowing film is obtained by the steps of recycling PET bottle flakes, LDPE, LLDPE, composite compatilizer, antioxidant master batch, weight loss measurement, parallel double-screw granulator, granulating, drying, checking and packaging.
The used modified granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600r/min, and the belt is subjected to vacuum exhaust. The dryer is a vacuum dryer, and the moisture content of PET after drying is less than or equal to 0.05%.
The granulation process optimization parameters are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250.
Melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
Example 5 preparation of Special Material for blend modification of recycled PET and PE blown film
Preparing a composite compatilizer by respectively taking a compatilizer A and a compatilizer B, wherein the mass ratio of the compatilizer A to the compatilizer B is 3:2. the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate, which is obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA.
Wherein, in the compatilizer A, the weight percentage of ethylene is 22%, the weight percentage of acrylic acid glycidyl ester is 8%, and the weight percentage of acrylic ester is 70%. In the compatilizer B, SEBS-g-GMA is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block.
Then respectively weighing the following components in proportion: 20 parts of recycled PET bottle flakes, 65 parts of LDPE, 10 parts of LLDPE and 5 parts of composite compatilizer.
Wherein, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene); the LDPE material is of a film blowing grade, and the melt flow rate is 0.8g/10min; the melt index of the (linear low density polyethylene) was 34/10min. The regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.70dl/g (test method ASTM D-4603).
According to the component proportions, the special material for blowing the film is obtained by adopting equipment shown in figure 3 to carry out blending modification granulation firstly and then drying, and specifically comprises the following steps:
The special material S5 for blowing film is obtained by the steps of recycling PET bottle flakes, LDPE, LLDPE, composite compatilizer, antioxidant master batch, weight loss measurement, parallel double-screw granulator, granulating, drying, checking and packaging.
The used modified granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600r/min, and the belt is subjected to vacuum exhaust. The dryer is a vacuum dryer, and the moisture content of PET after drying is less than or equal to 0.05%.
The granulation process optimization parameters are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250.
Melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
Example 6 preparation of Special Material for blend modification of recycled PET and PE blown film
And taking the compatilizer A as a composite compatilizer, wherein the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate, which is obtained through a high-pressure polymerization process. Wherein, in the compatilizer A, the weight percentage of ethylene is 24%, the weight percentage of acrylic acid glycidyl ester is 8%, and the weight percentage of acrylic ester is 68%.
Then respectively weighing the following components in proportion: 20 parts of regenerated PET bottle flakes, 55 parts of LDPE, 15 parts of LLDPE, 9 parts of composite compatilizer and 1 part of antioxidant master batch.
Wherein, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene); the LDPE material is of a film blowing grade, and the melt flow rate is 0.6g/10min; the melt index of the (linear low density polyethylene) was 4/10min. The regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.70dl/g (test method ASTM D-4603).
According to the component proportions, the special material for blowing the film is obtained by adopting equipment shown in figure 3 to carry out blending modification granulation firstly and then drying, and specifically comprises the following steps:
The special material S6 for blowing film is obtained by the steps of recycling PET bottle flakes, LDPE, LLDPE, composite compatilizer, antioxidant master batch, weight loss measurement, parallel double-screw granulator, granulating, drying, checking and packaging.
The used modified granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600r/min, and the belt is subjected to vacuum exhaust. The dryer is a vacuum dryer, and the moisture content of PET after drying is less than or equal to 0.05%.
The granulation process optimization parameters are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250.
Melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
Example 7 preparation of Special Material for blend modification of recycled PET and PE blown film
Taking a compatilizer B as a composite compatilizer, wherein the compatilizer B is epoxy type compatilizer SEBS-g-GMA. Wherein, in the compatilizer B, SEBS-g-GMA is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as an intermediate elastic block.
Then respectively weighing the following components in proportion: 20 parts of regenerated PET bottle flakes, 55 parts of LDPE, 15 parts of LLDPE, 9 parts of composite compatilizer and 1 part of antioxidant master batch.
Wherein, the PE raw material adopts one or two of LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and M-LLDPE (metallocene polyethylene); the LDPE material is of a film blowing grade, and the melt flow rate is 0.6g/10min; the melt index of the (linear low density polyethylene) was 4/10min. The regenerated PET bottle flakes are PET transparent bottle flakes with a viscosity of 0.70dl/g (test method ASTM D-4603).
According to the component proportions, the special material for blowing the film is obtained by adopting equipment shown in figure 3 to carry out blending modification granulation firstly and then drying, and specifically comprises the following steps:
The special material S7 for blowing film is obtained by the steps of recycling PET bottle flakes, LDPE, LLDPE, composite compatilizer, antioxidant master batch, weight loss measurement, parallel double-screw granulator, granulating, drying, checking and packaging.
The used modified granulating equipment is a double-screw flat double-co-extrusion granulator with the length-diameter ratio of 44-48:1 and the screw diameterThe rotating speed of the screw is 300-600r/min, and the belt is subjected to vacuum exhaust. The dryer is a vacuum dryer, and the moisture content of PET after drying is less than or equal to 0.05%.
The granulation process optimization parameters are as follows:
Granulation temperature (c): 160, 200, 250, 260, 270, 270, 270, 260, 250.
Melt temperature (DEG C): 250. melt pressure: 4-6 Mpa, rotating speed: 300-400 r/min.
Performance test:
The special materials for blending and modifying the recycled PET and PE prepared in the above examples 1 to 7 are taken as experimental groups, and the three-layer film blowing machine is adopted to blow films respectively, so that the total thickness of the substrate film layer is required to be 0.06mm as a building waterproof film, wherein: the thickness of the middle layer is 0.046mm, and the thickness of the surface layer and the bottom layer are both 0.007mm. And are labeled as building waterproofing membranes S1 to S7, respectively, with the same film thickness. Meanwhile, pure PE original films were used as comparative examples, and the film thicknesses were the same as those of the building waterproofing films S1 to S7.
The building waterproofing membranes S1 to S7 were respectively tested for solubility, shrinkage, stretch resistance and production cost, and the test results are shown in table 1 below.
TABLE 1 Membrane Performance data for pure PE raw membranes and building Water-repellent membranes
As shown in the test results in the table 1, compared with the conventional pure PE original film, the temperature resistance of the building waterproof film prepared by blending, modifying and granulating is improved to 150 ℃ from the original 120 ℃, and the shrinkage rate is reduced to 1% from the original 2-3%; the tensile strength is improved to more than 25MPa from 15-18 MPa, so that the problems of poor LDPE strength and poor ageing resistance are effectively solved, the production cost is low, and the social benefit is high.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (5)
1. A manufacturing method of a special material for a regenerated PET and PE blending modified blown film is characterized in that a composite compatilizer consisting of a compatilizer A and a compatilizer B is adopted, and the special material for the blown film is obtained after blending modified granulation is carried out on the composite compatilizer, a regenerated PET bottle flake material and PE raw materials and drying;
Wherein, the compatilizer A is a random terpolymer of ethylene, acrylic ester and glycidyl acrylate obtained by a high-pressure polymerization process; the compatilizer B is epoxy type compatilizer SEBS-g-GMA;
in the compatilizer A, the weight percentage of ethylene is 20-30%, the weight percentage of glycidyl acrylate is 5-15%, and the weight percentage of acrylic ester is 55-75%;
in the compatilizer B, SEBS is a linear triblock copolymer taking polystyrene as a terminal block and taking an ethylene-butene copolymer obtained by hydrogenation of polybutadiene as a middle elastic block;
The SEBS does not contain unsaturated double bonds, and the grafting rate of the SEBS-g-GMA is 1-2%;
the mass ratio of the compatilizer A to the compatilizer B is 3: 2-4: 1, a step of;
The PE raw material adopts LDPE (low density polyethylene) and LLDPE (linear low density polyethylene);
The mass fractions of the components are as follows:
20-30 parts of recycled PET bottle flakes, 50-70 parts of LDPE, 10-15 parts of LLDPE, 5-10 parts of a composite compatilizer and 1-2 parts of an antioxidant master batch.
2. The method for manufacturing the recycled PET and PE blending modified film blowing special material according to claim 1, wherein the LDPE material is of a film blowing grade, and the melt index of the LDPE material is 0.2-0.8 g/10min; the melt index of the LLDPE is 1-4 g/10min.
3. The method for manufacturing the recycled PET and PE blending modified film blowing special material according to claim 1, wherein the recycled PET bottle flakes adopt PET transparent bottle flakes with the viscosity of 0.60-0.80 dl/g.
4. A recycled PET and PE blend modified blown film material produced by the process of any one of claims 1 to 3.
5. The use of a recycled PET and PE blend modified blown film material as defined in claim 4 for the production of building waterproofing, agricultural greenhouse and adhesive films in single or multiple layers of multilayer co-extruded films.
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