CN118063877B - Metallocene polyethylene ultrathin film and preparation method and application thereof - Google Patents
Metallocene polyethylene ultrathin film and preparation method and application thereof Download PDFInfo
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- CN118063877B CN118063877B CN202410462828.2A CN202410462828A CN118063877B CN 118063877 B CN118063877 B CN 118063877B CN 202410462828 A CN202410462828 A CN 202410462828A CN 118063877 B CN118063877 B CN 118063877B
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- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 14
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 14
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 14
- 239000004611 light stabiliser Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 79
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 54
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 26
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 19
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 16
- -1 amine compounds Chemical class 0.000 claims description 15
- 238000010096 film blowing Methods 0.000 claims description 15
- 238000013329 compounding Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 238000000071 blow moulding Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000009408 flooring Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 18
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical compound NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229960001340 histamine Drugs 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010019909 Hernia Diseases 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
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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
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/02—Flooring or floor layers composed of a number of similar elements
- E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- 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
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- 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
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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Abstract
The invention provides a metallocene polyethylene ultrathin film, a preparation method and application thereof, and belongs to the technical field of plastic modification. The metallocene polyethylene ultrathin film comprises the following components in parts by weight: 30-60 parts of first metallocene polyethylene; 20-30 parts of a second metallocene polyethylene; 10-20 parts of low-density polyethylene; 4-5 parts of compound antioxidant; 4-5 parts of light stabilizer; 2-3 parts of other auxiliary agents; wherein the sequence proportion of the methylene sequence length of 40-50 in the first metallocene polyethylene is 20-25%, and the branching degree is 3.2-4.0; the sequence proportion of the methylene sequence length of the second metallocene polyethylene is between 30 and 35 percent, and the branching degree is between 4.3 and 5.0. The thickness of the metallocene polyethylene ultrathin film can reach 0.003mm, the cost is low, and the metallocene polyethylene ultrathin film has excellent scratch resistance, ageing resistance and good processing stability.
Description
Technical Field
The invention belongs to the technical field of plastic modification, and particularly relates to a metallocene polyethylene ultrathin film, and a preparation method and application thereof.
Background
The floor material is mainly a thin sheet, a floor leather, a ceramic tile and the like which are used for the purpose of building floors, and the front surface of the floor material is easy to generate scratches due to friction and scraping in the packaging, transportation and construction processes due to high front surface glossiness, smoothness and low hardness, so that the quality and the service life of products are affected. At present, the main method for improving the scratch resistance of the floor material is to attach a layer of polymer film on the front surface of the floor material, but the mechanical property and the scratch resistance of the polymer film material which is traditionally used for the front surface of the floor material are obviously reduced under the condition of lower film thickness, so that the problems of thicker film thickness, higher cost, poor scratch resistance and the like of the polymer film on the front surface of the existing floor material generally exist.
Metallocene polyethylene is a novel thermoplastic plastic, is the most important technical development of polyolefin industry in the 90 th year, and is an important innovation following LLDPE production technology. Since it is a polyethylene produced using Metallocene (MAO) as a polymerization catalyst, it is significantly different in performance from PE polymerized by conventional Ziegler-Natta catalysts. The metallocene polyethylene has excellent mechanical property, and the film made of the metallocene polyethylene is used for floor boards, so that the method is an effective method for solving the problems of the polymer film on the front surface of the floor boards. However, the metallocene polyethylene has a narrow molecular weight distribution, so that melt fracture is easy to occur during high-speed processing, and the processing stability of the metallocene polyethylene is obviously reduced.
Patent CN1927897a discloses that 0.1 to 3 parts by weight of an antioxidant is added to mLLDPE (100 parts by weight), and after being uniformly mixed, the mixture is put into a reactor and subjected to chemical reaction treatment at 15 to 35 ℃ to prepare mLLDPE resin which can be smoothly molded and processed on general extrusion and injection processing equipment.
Patent CN102167855B discloses a metallocene polyethylene greenhouse film resin composition, comprising, in weight percent, metallocene linear low density polyethylene: (1) Metallocene linear low density polyethylene (mLLDPE) 100%; (2) 0.05-0.35% (wt) of di-tert-butyl hydroperoxide; (3) 0.005-0.041% (wt) of tert-butyl peroxybenzoate; the metallocene linear low-density polyethylene is prepared by adopting a metallocene catalytic system, is obtained by homopolymerizing ethylene or is obtained by copolymerizing ethylene and butene-1 or hexene-1, has a weight average molecular weight Mw of 6-15 multiplied by 10 4, has a molecular weight distribution MWD of less than or equal to 2.2, has a density of 0.865-0.941g/cm 3 and has a melt flow rate of 0.5-10g/10min.
The prior art is a polyethylene film modified by single metallocene polyethylene, and the film produced by the method cannot have excellent initial mechanical property and ageing resistance, and simultaneously ensures good processing stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the metallocene polyethylene ultrathin film, and the preparation method and the application thereof, wherein the thickness of the metallocene polyethylene ultrathin film can reach 0.003mm, the cost is low, and the metallocene polyethylene ultrathin film has excellent scratch resistance, ageing resistance and good processing stability.
In order to achieve the above object, according to one aspect of the present invention, there is provided a metallocene polyethylene ultrathin film, which comprises the following components in parts by weight:
30-60 parts of first metallocene polyethylene;
20-30 parts of a second metallocene polyethylene;
10-20 parts of low-density polyethylene;
4-5 parts of compound antioxidant;
4-5 parts of light stabilizer;
2-3 parts of other auxiliary agents;
wherein the sequence proportion of the methylene sequence length of 40-50 in the first metallocene polyethylene is 20-25%, and the branching degree is 3.2-4.0; the sequence proportion of the methylene sequence length of the second metallocene polyethylene is between 30 and 35 percent, and the branching degree is between 4.3 and 5.0.
In some embodiments, the low density polyethylene has a density of 0.92 to 0.93g/cm 2 and a melt mass flow rate MFR of 1.85 to 1.90g/10min at 190℃under a load of 2.16kg test.
In some embodiments, the first metallocene polyethylene is a copolymer of ethylene and 1-hexene, the mass content of 1-hexene being from 2.0 to 2.5%; the second metallocene polyethylene is a copolymer of ethylene and 1-octene, and the mass content of the 1-octene is 2.7-3.2%.
In some embodiments, the mass ratio of the first metallocene polyethylene to the second metallocene polyethylene is from 1.5 to 2:1.
In some embodiments, the compound antioxidant is formed by compounding a first hindered phenol, a second hindered phenol and barium sulfate, and the mass ratio of the first hindered phenol to the second hindered phenol to the barium sulfate is 1-3:1-3:10-30 parts of a base; wherein the first hindered phenol comprises at least one of hindered phenol 3114, hindered phenol 1330, and hindered phenol 1010, and the second hindered phenol comprises at least one of hindered phenol 300, hindered phenol 1076, and hindered phenol 1024.
In some embodiments, the light stabilizer comprises at least one of histamine-based compounds; the other auxiliary agent comprises one or more of an ultraviolet absorbent and a lubricant.
According to another aspect of the present invention, there is also provided a method for preparing the metallocene polyethylene ultra-thin film as described above, comprising the steps of:
(1) The raw materials are added into a high-speed mixer according to a proportion to be mixed uniformly, then added into a double-screw extruder to be extruded, granulated and dried, and master batch is obtained;
(2) And adding the master batch into a blow molding machine, and preparing the metallocene polyethylene film through a film blowing process.
In some embodiments, in step (2), the film blowing process is: the temperature of the feeding section is 90-130 ℃, the temperature of the melting section is 150-170 ℃, the temperature of the homogenizing section is 180-190 ℃, the temperature of the machine head is 160-170 ℃, the temperature of the die is 160-170 ℃, the blowing ratio is 2-2.5, and the draft ratio is 2-3.
According to another aspect of the invention, the invention also provides an application of the metallocene polyethylene ultrathin film or the metallocene polyethylene ultrathin film prepared by the preparation method in a floor material.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) According to the invention, metallocene polyethylenes with different structural characteristics are selected for compounding, and the different metallocene polyethylenes have synergistic effect, so that the crystallization behavior of the polyethylene is effectively regulated, the comprehensive performance of the film is obviously improved, the thickness of the film can reach 0.003mm, the cost is low, and meanwhile, the film has excellent scratch resistance, ageing resistance and good processing stability.
(2) According to the invention, different antioxidants are utilized to separate out different speeds in the resin, and specific antioxidants are selected for compounding, so that the first hindered phenol has a relatively high migration rate in an initial oxidation resisting stage and can effectively capture free radicals, and the second hindered phenol has relatively good migration resistance and heat resistance and relatively good compatibility with the resin, so that the long-acting oxidation resistance is excellent, and meanwhile, the oxidation induction period can be effectively improved by adding the barium sulfate, so that the prepared metallocene polyethylene ultrathin film has excellent ageing resistance.
Detailed Description
The invention provides a metallocene polyethylene ultrathin film, which comprises the following components: the high-strength polyethylene comprises a first metallocene polyethylene, a second metallocene polyethylene, a low-density polyethylene, a compound antioxidant, a light stabilizer and other auxiliary agents.
The film thickness of the metallocene polyethylene ultrathin film is 0.002-0.003mm, and more preferably 0.0027-0.003mm. According to the invention, metallocene polyethylenes with different structural characteristics are selected for compounding, and the different metallocene polyethylenes have synergistic effects, so that the crystallization behavior of the polyethylene is effectively regulated, the comprehensive performance of the film is obviously improved, the film thickness of the film is ultrathin, the cost is low, and meanwhile, the ultrathin film has excellent scratch resistance, ageing resistance and good processing stability.
In the invention, the weight part of the first metallocene polyethylene is 30-60 parts, preferably 40-50 parts. The ratio of the sequences with the length of the methylene sequence of 40-50 in the first metallocene polyethylene is 20-25%, and it is understood that the ratio can be any specific value of 20%, 21%, 22%, 23%, 24%, 25% or any value in the range of 20-25%; the first metallocene polyethylene has a branching degree of 3.2 to 4.0 (branch number per 1000 carbons), it being understood that the branching degree may be any specific value of 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0 or any value in the range of 3.2 to 4.0.
In the present invention, the second metallocene polyethylene is 20 to 30 parts by weight, preferably 25 to 30 parts by weight. The ratio of the sequences with the length of the methylene sequence of 40-50 in the second metallocene polyethylene is 30-35%, and it is understood that the ratio can be any specific value of 30%, 31%, 32%, 33%, 34%, 35% or any value in the range of 30-35%; the second metallocene polyethylene has a degree of branching of 4.3 to 5.0 (branches per 1000 carbons), it being understood that the degree of branching may be any particular value of 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0 or any value in the range of 4.3 to 5.0.
In some embodiments of the present invention, the mass ratio of the first metallocene polyethylene to the second metallocene polyethylene is from 1.5 to 2:1, it can be appreciated that the mass ratio can be 1.5: 1. 1.6: 1. 1.7: 1. 1.8: 1. 1.9: 1. 2:1 or 1.5-2: any number within the range of 1.
In some embodiments of the present invention, the first metallocene polyethylene is a copolymer of ethylene and 1-hexene, the 1-hexene being present in an amount of 2.0 to 2.5%, it being understood that the amount can be any specific value in the range of 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5% or any value in the range of 2.0 to 2.5%; the second metallocene polyethylene is a copolymer of ethylene and 1-octene, the 1-octene content being from 2.7 to 3.2%, it being understood that the content may be any particular value of 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2% or any value in the range of 2.7 to 3.2%.
The inventor finds that metallocene polyethylene with different structural characteristics has different influences on the performance of the film, and further researches find that different duty ratios and branching degrees of which the length of a methylene sequence in the metallocene polyethylene is 40-50 have larger influence on regulating and controlling the comprehensive mechanical property and processing stability of the film. The inventor of the invention further selects a specific first metallocene polyethylene and a specific second metallocene polyethylene to compound, so that the crystallization behavior of the polyethylene can be effectively regulated and controlled, and the comprehensive performance of the film is further improved, so that the film has good scratch resistance, weather resistance and processing stability under the condition of low film thickness.
In the present invention, the weight part of the low-density polyethylene is 10 to 20 parts, preferably 15 to 20 parts. The low-density polyethylene is common low-density polyethylene, namely common low-density polyethylene synthesized without using a metallocene catalyst, the density of the low-density polyethylene is 0.92-0.93g/cm 2, the melt mass flow rate MFR under the test condition of 190 ℃ and 2.16kg load is 1.85-1.90g/10min, and the melt mass flow rate MFR can be 1.85g/10min, 1.86g/10min, 1.87g/10min, 1.88g/10min, 1.89g/10min, 1.90g/10min or any specific value in the range of 1.85-1.90g/10 min. The low-density polyethylene is added into the metallocene polyethylene system, so that the processing performance of the system can be regulated and controlled, and the low-density polyethylene has relatively high melt strength, so that the stability of a film bubble in the film blowing process is directly influenced, and the processing process is more stable.
In the invention, the weight part of the compound antioxidant is 4-5 parts. In some embodiments, the compound antioxidant is formed by compounding a first hindered phenol, a second hindered phenol and barium sulfate, and the mass ratio of the first hindered phenol to the second hindered phenol to the barium sulfate is 1-3:1-3:10-30 parts of a base; wherein the first hindered phenol comprises at least one of hindered phenol 3114, hindered phenol 1330, and hindered phenol 1010, and the second hindered phenol comprises at least one of hindered phenol 300, hindered phenol 1076, and hindered phenol 1024.
The inventor of the invention discovers that the migration rates of different antioxidants in the resin are greatly different, the first hindered phenol has a faster migration rate in an initial oxidation resisting stage and can effectively capture free radicals, but the first hindered phenol is easy to migrate from inside to outside under the action of various environmental factors along with the increase of aging time, and the thermo-oxidative stabilization efficiency is reduced due to loss; the second hindered phenol has better migration resistance and heat resistance, and has better compatibility with resin, so that the long-acting oxidation resistance is excellent, meanwhile, the oxidation induction period of the first hindered phenol and the second hindered phenol can be effectively improved by adding the barium sulfate, and the three components are synergistic, so that the prepared metallocene polyethylene film has excellent ageing resistance.
In the invention, the weight part of the light stabilizer is 4-5 parts. In some embodiments, the light stabilizer includes at least one of histamine-based compounds, such as may be at least one of hindered amine 944, hindered amine 622; in the invention, the weight part of the other auxiliary agent is 2-3 parts. The other auxiliary agent comprises one or more of an ultraviolet absorbent and a lubricant, the type of the ultraviolet absorbent is not particularly limited, and the ultraviolet absorbent conventional in the art can be adopted, including but not limited to an ultraviolet absorbent UV-531 and the like; the present invention is not particularly limited in the kind of the lubricant, and lubricants conventional in the art, including but not limited to calcium stearate and the like, may be employed.
The inventor of the invention also finds that the compound antioxidant and the light stabilizer can greatly improve the ageing resistance of the film, and the reason is probably that in the thermo-oxidative photo-ageing stage, after the nitrogen hydrogen bond in the light stabilizer hindered amine is oxidized into a nitrogen-oxygen bond, the nitrogen-oxygen bond reacts with peroxy radical (ROO.) and hydroperoxide (ROOH) generated by the growth of polyethylene chain to generate transitional product alkyl hydroxylamine of the hindered amine, and the transitional product alkyl hydroxylamine can react with the phenol oxygen radical to regenerate the hindered phenol in the compound antioxidant, so that positive synergistic effect is generated.
According to another aspect of the present invention, there is also provided a method for preparing the metallocene polyethylene ultra-thin film as described above, comprising the steps of:
(1) The raw materials are added into a high-speed mixer according to a proportion to be mixed uniformly, then added into a double-screw extruder to be extruded, granulated and dried, and master batch is obtained;
(2) And adding the master batch into a blow molding machine, and preparing the metallocene polyethylene ultrathin film through a film blowing process.
In the invention, the raw materials are firstly added into a high-speed mixer according to a proportion to be mixed uniformly, then added into a double-screw extruder to be extruded, granulated and dried, thus obtaining master batch. The type of the high-speed mixer is not particularly limited, the rotating speed of the mixer is 1000-1500r/min, and the mixing time is 5-10min. The invention is not particularly limited to the type of the twin-screw extruder, and a twin-screw extruder conventional in the art can be used, and the conditions for extrusion and granulation are as follows: the temperature of the twin-screw extruder is set to 140-220 ℃ and the screw rotating speed is 100-500rpm.
In the invention, the master batch is further added into a blowing machine, and the metallocene polyethylene ultrathin film is prepared through a film blowing process. According to the preparation method of the present invention, in some embodiments, in step (2), the film blowing process is: the temperature of the feeding section is 90-130 ℃, the temperature of the melting section is 150-170 ℃, the temperature of the homogenizing section is 180-190 ℃, the temperature of the machine head is 160-170 ℃, the temperature of the die is 160-170 ℃, the blowing ratio is 2-2.5, and the draft ratio is 2-3.
According to another aspect of the invention, the invention also provides an application of the metallocene polyethylene ultrathin film or the metallocene polyethylene ultrathin film prepared by the preparation method in a floor material.
Further, the metallocene polyethylene ultrathin film or the metallocene polyethylene ultrathin film prepared by the preparation method can be used as a protective film to be attached to the front surface of the floor material. Still further, the flooring material may be tile, flooring, or other sheet for use as a floor.
The present invention will be described in detail by examples. It should be understood that the following examples are illustrative only and are not intended to limit the invention.
The raw materials used in the examples and comparative examples of the present invention are all commercially available, and specific information is as follows:
A first metallocene polyethylene (mPE 1-1), a sequence ratio of 40-50 methylene sequences of 20%, a branching degree of 3.2, 1-hexene as a comonomer, a comonomer mass ratio of 2.0%, and a manufacturer: exxon Mobil;
A first metallocene polyethylene (mPE 1-2), a sequence ratio of 40-50 methylene sequences of 25%, a branching degree of 4.0, 1-hexene as comonomer, 2.5% as comonomer mass ratio, manufacturer: exxon Mobil;
First metallocene polyethylene (mPE 1-3), a sequence ratio of 40-50 in methylene sequence length of 15%, a branching degree of 3.0, 1-hexene as comonomer, 2.5% as comonomer mass ratio, manufacturer: exxon Mobil;
A second metallocene polyethylene (mPE 2-1), a sequence ratio of 40-50 methylene sequences length of 30%, a branching degree of 4.3, a comonomer of 1-octene, a comonomer mass ratio of 2.7%, manufacturer: daqing petrochemical institute;
A second metallocene polyethylene (mPE 2-2), a sequence ratio of 40-50 methylene sequences length of 35%, a branching degree of 5.0, a comonomer of 1-octene, a comonomer mass ratio of 3.2%, manufacturer: daqing petrochemical institute;
Low density polyethylene: a density of 0.92g/cm 2, a melt mass flow rate MFR of 1.85g/10min at 190℃under a load of 2.16kg test; the manufacturing factory: qilu petrochemical industry;
Compounding an antioxidant 1: the mass ratio of the hindered phenol 3114 to the hindered phenol 300 to the barium sulfate is 3:1:30, a mixture of two or more of the following; self-making;
And (2) compounding an antioxidant 2: the mass ratio of the hindered phenol 1330 to the hindered phenol 1076 to the barium sulfate is 2:2:20, a mixture of two or more of the following; self-making;
and (3) compounding an antioxidant 3: the mass ratio of the hindered phenol 1010 to the hindered phenol 1024 to the barium sulfate is 1:3:10, a mixture of two or more of the following; self-making;
And (3) compounding an antioxidant 4: the mass ratio of the hindered phenol 3114 to the barium sulfate is 1:10, a mixture of two or more of the following; self-making;
and (3) compounding an antioxidant 5: the mass ratio of the hindered phenol 300 to the barium sulfate is 1:30, a mixture of two or more of the following; self-making;
And (3) compounding an antioxidant 6: the mass ratio of the hindered phenol 3114 to the hindered phenol 300 is 3:1, a mixture of two or more of the above-mentioned materials; self-making;
light stabilizers: hindered amine 944, commercially available;
ultraviolet light absorber: UV-531, commercially available;
And (3) a lubricant: calcium stearate, commercially available.
Examples 1 to 6
The preparation method of the metallocene polyethylene ultrathin film in the embodiments 1-6 comprises the following steps:
(1) The raw materials are added into a high-speed mixer according to a proportion and mixed uniformly, the rotating speed of the mixer is 1500r/min, the mixing time is 10min, and then the mixture is added into a double-screw extruder for extrusion granulation and drying, so that master batch is obtained; the conditions of extrusion granulation are as follows: the twin screw extruder temperature was set at 150℃and the screw speed at 400rpm.
(2) Adding the master batch into a blow molding machine, and preparing the metallocene polyethylene ultrathin film through a film blowing process; the film blowing process comprises the following steps: the temperature of the feeding section is 100 ℃, the temperature of the melting section is 150 ℃, the temperature of the homogenizing section is 180 ℃, the temperature of the machine head is 160 ℃, the temperature of the die is 160 ℃, the blowing ratio is 2.1, and the draft ratio is 2.
Table 1 examples 1-6 raw material ratios (in parts by weight)
。
Comparative examples 1 to 8
The preparation method of the metallocene polyethylene ultra-thin films described in comparative examples 1 to 8 was the same as that in examples 1 to 6, except that the composition and the ratio of each component in comparative examples 1 to 8 were different from those in example 1, and the specific composition ratios are shown in Table 2. Wherein, the comparison of comparative example 1 and example 1 differs in that no second metallocene polyethylene was added; comparative example 2 differs from example 1 in that no first metallocene polyethylene was added; comparative example 3 differs from example 1 in that the addition amounts of the first metallocene polyethylene and the second metallocene polyethylene are lower; comparative example 4 differs from example 1 in that the ratio of the first metallocene polyethylene and the second metallocene polyethylene is different; comparative example 5 differs from example 1 in that a first metallocene polyethylene of a different property is used; comparative examples 6-8 differ from example 1 in the use of a different compounded antioxidant.
Table 2 comparative examples 1 to 8 raw material ratios (in parts by weight)
。
Performance test:
The metallocene polyethylene ultra-thin films prepared in examples 1 to 6 and comparative examples 1 to 8 were subjected to performance test according to the corresponding national standard test method, and specific test standards and methods are as follows:
Film thickness: measured using a micrometer outside micrometer, manufacturer: the Guilin gauge blade has responsibility limited company. The specific method comprises the following steps: the film was cut into a 20cm x 20cm sample, 50 layers were laid up on top of each other, the film thickness of the 50 layers was measured at 3 different positions, the average value was taken, and then the average value was divided by the number of film layers (50 layers), to obtain the average film thickness of each layer of film.
Tensile strength and elongation at break: the film samples in examples and comparative examples were cut into long bars (150 mm. Times.10 mm) with a cutter, and the tensile properties were tested according to GB1040.3-2006 standard, the tensile speed was 500 mm.min -1, and the results of the tensile strength and elongation at break test were arithmetically averaged for three samples of each group. The greater the tensile strength, the less likely the film will break; the greater the elongation at break, the better the flexibility of the film.
Hernia lamp aging: detection is carried out according to GB/T16422.
Natural insolation experiment: the detection is carried out according to GB 3681283.
Film blowing conditions: the stability of the bubble during film blowing was observed by naked eyes.
Abrasion resistance: the force to scratch the film was measured using an Elikesen scratch tester (ISO 4586-2/DINEN 438-2) at a Tip of 0.5 mm.
TABLE 3 Properties of the metallocene polyethylene ultra-films prepared in examples 1-6 and comparative examples 1-8
。
As can be seen from the data in Table 3, the metallocene polyethylene ultra-thin films prepared in examples 1 to 6 have a lower film thickness, which can be as low as 0.0027mm at the minimum, and are excellent in abrasion resistance, initial tensile strength and elongation at break before aging, and retention of tensile strength and retention of elongation at break after aging. In addition, the film blowing conditions are observed, and the film bubble is stable in the film blowing process of the embodiments 1-6, so that the processing stability of the film blowing method is good. From comparative examples 1,2 and example 1, comparative example 1 was free of the addition of the second metallocene polyethylene, comparative example 2 was free of the addition of the first metallocene polyethylene, the scratch resistance and the aging resistance of the film were significantly inferior to those of example 1, and the film processing stability was poor; as is clear from comparative example 3 and example 1, the addition amounts of the first metallocene polyethylene and the second metallocene polyethylene in comparative example 3 are low, the scratch resistance and aging resistance of the film are both inferior to those of example 1, and the film processing stability is poor; as is clear from comparative example 4 and example 1, the proportions of the first metallocene polyethylene and the second metallocene polyethylene in comparative example 4 are different, the scratch resistance and the aging resistance of the obtained film are significantly reduced, and the film processing stability is poor; from comparative example 5 and example 1, it is known that comparative example 5 uses the first metallocene polyethylene having different properties, the scratch resistance and aging resistance of the obtained film are significantly reduced, and the film processing stability is poor; as is clear from comparative examples 6 to 8 and example 1, the films used in comparative examples 6 to 8 have poor aging resistance due to the use of different compound antioxidants.
Therefore, the invention carries out compounding in different proportions by selecting metallocene polyethylene with different structural characteristics and utilizing the difference of the precipitation speeds of different antioxidants in the resin, and the components are synergistic, so that the crystallization behavior of the polyethylene is effectively regulated, the comprehensive performance of the film is obviously improved, the film thickness of the film is lower, and meanwhile, the film has good scratch resistance, ageing resistance and processing stability.
Claims (8)
1. The metallocene polyethylene ultrathin film is characterized by comprising the following components in parts by weight:
30-60 parts of first metallocene polyethylene;
20-30 parts of a second metallocene polyethylene;
10-20 parts of low-density polyethylene;
4-5 parts of compound antioxidant;
4-5 parts of light stabilizer;
2-3 parts of other auxiliary agents;
Wherein the sequence proportion of the methylene sequence length of 40-50 in the first metallocene polyethylene is 20-25%, and the branching degree is 3.2-4.0 branched chains per 1000 carbons; the sequence proportion of the methylene sequence length of 40-50 in the second metallocene polyethylene is 30-35%, and the branching degree is 4.3-5.0 branches/1000 carbons;
The mass ratio of the first metallocene polyethylene to the second metallocene polyethylene is 1.5-2:1, a step of;
the thickness of the metallocene polyethylene ultrathin film is 0.0027-0.0030mm.
2. The metallocene polyethylene ultrathin film according to claim 1, wherein the density of the low-density polyethylene is 0.92-0.93g/cm 2, and the melt mass flow rate MFR under the test condition of 190 ℃ and 2.16kg load is 1.85-1.90g/10min.
3. The metallocene polyethylene ultrathin film according to claim 1, wherein the first metallocene polyethylene is a copolymer of ethylene and 1-hexene, and the mass content of the 1-hexene is 2.0-2.5%; the second metallocene polyethylene is a copolymer of ethylene and 1-octene, and the mass content of the 1-octene is 2.7-3.2%.
4. The metallocene polyethylene ultrathin film according to claim 1, wherein the compound antioxidant is formed by compounding a first hindered phenol, a second hindered phenol and barium sulfate, and the mass ratio of the first hindered phenol to the second hindered phenol to the barium sulfate is 1-3:1-3:10-30 parts of a base; wherein the first hindered phenol comprises at least one of hindered phenol 3114, hindered phenol 1330, and hindered phenol 1010, and the second hindered phenol comprises at least one of hindered phenol 300, hindered phenol 1076, and hindered phenol 1024.
5. The metallocene polyethylene ultrathin film according to claim 1, wherein the light stabilizer comprises at least one of hindered amine compounds; the other auxiliary agent comprises one or more of an ultraviolet absorbent and a lubricant.
6. A process for the preparation of a metallocene polyethylene ultrathin film according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) The raw materials are added into a high-speed mixer according to a proportion to be mixed uniformly, then added into a double-screw extruder to be extruded, granulated and dried, and master batch is obtained;
(2) And adding the master batch into a blow molding machine, and preparing the metallocene polyethylene ultrathin film through a film blowing process.
7. The method for preparing a metallocene polyethylene ultra-thin film according to claim 6, wherein in the step (2), the film blowing process is as follows: the temperature of the feeding section is 90-130 ℃, the temperature of the melting section is 150-170 ℃, the temperature of the homogenizing section is 180-190 ℃, the temperature of the machine head is 160-170 ℃, the temperature of the die is 160-170 ℃, the blowing ratio is 2-2.5, and the draft ratio is 2-3.
8. Use of the metallocene polyethylene ultrathin film according to any one of claims 1-5 or the metallocene polyethylene ultrathin film prepared by the preparation method according to any one of claims 6-7 in flooring materials.
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