CN116063769A - Polyethylene composition, preparation method and application thereof, and polyolefin microporous breathable film - Google Patents
Polyethylene composition, preparation method and application thereof, and polyolefin microporous breathable film Download PDFInfo
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- CN116063769A CN116063769A CN202111272418.4A CN202111272418A CN116063769A CN 116063769 A CN116063769 A CN 116063769A CN 202111272418 A CN202111272418 A CN 202111272418A CN 116063769 A CN116063769 A CN 116063769A
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- Prior art keywords
- polyethylene
- maleic anhydride
- polyethylene composition
- weight
- composition according
- Prior art date
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- -1 Polyethylene Polymers 0.000 title claims abstract description 179
- 239000000203 mixture Substances 0.000 title claims abstract description 167
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 156
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 156
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 229920001577 copolymer Polymers 0.000 claims abstract description 59
- 239000004005 microsphere Substances 0.000 claims abstract description 54
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000009826 distribution Methods 0.000 claims abstract description 31
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 229920001684 low density polyethylene Polymers 0.000 claims description 21
- 239000004702 low-density polyethylene Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 18
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 16
- 239000008116 calcium stearate Substances 0.000 claims description 16
- 235000013539 calcium stearate Nutrition 0.000 claims description 16
- 238000007334 copolymerization reaction Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000003361 porogen Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 239000012456 homogeneous solution Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000012429 reaction media Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 229940117955 isoamyl acetate Drugs 0.000 claims description 3
- 229920001179 medium density polyethylene Polymers 0.000 claims description 3
- 239000004701 medium-density polyethylene Substances 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229920000034 Plastomer Polymers 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- YTXCAJNHPVBVDJ-UHFFFAOYSA-N octadecyl propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC YTXCAJNHPVBVDJ-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000004043 trisaccharides Chemical class 0.000 claims 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 19
- 230000002776 aggregation Effects 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005469 granulation Methods 0.000 description 11
- 230000003179 granulation Effects 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005266 casting Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- 150000005691 triesters Chemical class 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- 150000001336 alkenes Chemical class 0.000 description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention relates to the field of polyolefin compositions, and discloses a polyethylene composition, a preparation method and application thereof. The composition comprises polyethylene, a pore-forming agent and an antioxidant; based on 100 parts by weight of polyethylene, the dosage of the pore-forming agent is 35-110 parts by weight, and the dosage of the antioxidant composite auxiliary agent is 0.1-2 parts by weight; the pore-forming agent is maleic anhydride copolymer microspheres, and the average particle size of the maleic anhydride copolymer microspheres is 500-1600nm. The composition contains organic Kong Jima maleic anhydride copolymer microspheres, the copolymer microspheres have uniform particle size distribution, the dispersibility in a polyethylene blend matrix is good without agglomeration phenomenon under the condition of not using a coupling agent or a dispersing agent, and the defects of uneven pore size distribution, poor dispersibility, poor compatibility and the like caused by an inorganic pore-forming agent can be avoided. The composition can be applied to a breathable film to improve the breathable uniformity of the product.
Description
Technical Field
The invention relates to the field of polyolefin compositions, in particular to a polyethylene composition, a preparation method and application thereof, and a polyolefin microporous breathable film.
Background
The breathable film is also called as a 'water-blocking breathable microporous film', and has the characteristics of ventilation and water impermeability. A composite material is prepared from thermoplastic plastics as matrix, and solid particles (such as calcium carbonate, barium sulfate, titanium oxide and talc powder) through blowing, rolling or casting to obtain film, and uniaxial or biaxial stretching under proper conditions to obtain microporous film. The microporous breathable film can allow gases such as water vapor, air and the like to pass through, can block liquid, can be widely applied to medical articles such as medical protective clothing, wound nursing bandages, dressings and the like, sanitary articles such as baby diapers, adult nursing products and the like, and the fields such as food packaging, daily products and the like, and is a new material which is rapidly developed in the last twenty years.
In theory, thermoplastics could be the matrix resin for the breathable film material, but polyethylene breathable films have the greatest ratio from the point of view of the overall market value of microporous breathable films. Polyethylene has the advantages of rich raw material sources, easy processing and forming, good film forming effect, comfortable and soft hand feeling and the like, and is widely used for matrix resins of breathable film materials.
The hygiene industry is the largest end market for polyethylene breathable films, and therefore the safety and comfort of the breathable film must be considered, and therefore, considerable quality requirements are placed on the porogens used in the preparation of the polyethylene breathable films. Inorganic filler, especially calcium carbonate, is the preferred material for pore-forming agent due to its abundant resources, low cost and good comprehensive properties. However, the inorganic pore-forming agent has the advantages of hydrophilic and oleophobic surface, extremely strong polarity, poor compatibility with a polymer matrix and difficult uniform dispersion in the matrix. Meanwhile, the dispersion uniformity of the pore-forming agent in the matrix can influence the mechanical property, the surface flatness, the pore diameter uniformity of micropores, the porosity and other parameters of the breathable film. In the traditional production process, the inorganic filler is pretreated by adopting a surfactant, so that the compatibility of the inorganic filler and a matrix is improved, and meanwhile, the dispersing problem of the inorganic filler is solved by adding a coupling agent and a dispersing agent.
CN102336940a discloses a composition of a breathable film with low air permeability and a preparation method thereof, and the composition comprises a polyolefin resin mixture, an air permeability regulator, surface modified micron-sized inorganic particles, an antioxidant, a lubricant and a coupling agent, and has the advantages that the micron-sized inorganic filler can improve the mechanical property of the breathable film, and meanwhile, the surface of the inorganic particles is coupled and modified to increase the compatibility with the polyolefin resin, but the disadvantage that the micron-sized inorganic particles cannot be uniformly dispersed in matrix resin, thereby affecting the air permeability uniformity of the film.
The CN1176986C discloses a preparation method of a special resin for polyolefin high-air-permeability casting film, which is prepared by taking polyolefin resin (three compounds of LDPE, LLDPE and copolymerized PP) and superfine mineral filler (calcium carbonate, talcum powder and the like with the particle size of 3-10 mu m) as main raw materials, adding a Ti-Al composite coupling agent, a POE modifier and an OPE dispersing agent, and carrying out coupling treatment, compatibilization dispersion, banburying and extrusion granulation. The special resin is prepared through casting and stretching processes, so that uniform and fine pores are generated between mineral filler particles and polyolefin in the film, and the polyolefin high-permeability casting film is formed after cooling and crystallization. The method can not effectively form holes and control the aperture, and an internal mixer is used, so that the process is complicated.
CN101747548A discloses a composite and a method for preparing a high strength polyolefin breathable film, the components comprising: polyolefin resin, micron-sized and nano-sized inorganic filler, antioxidant, processing aid and coupling agent. Wherein the nano inorganic filler can improve the mechanical property of the polyolefin breathable film, reduce the thickness of the breathable film, and can prepare the breathable film with high strength and high air permeability by adjusting the process conditions; however, the poor compatibility of the nano inorganic filler and the polyolefin resin can cause non-uniformity of ventilation of the material, thereby affecting the use of the breathable film.
At present, the following problems exist with inorganic porogens used in the market for producing breathable films: (1) easy agglomeration; (2) The pore diameter uniformity of the breathable film is poor due to the large particle size and the non-uniformity of the particle size distribution, and even a large number of pinhole defects occur; (3) The surface modification effect of the filler particles is poor, and the compatibility with a matrix is poor, so that the strength of the film is affected; (4) The filler particles have poor dispersibility and migrate to the surface of the breathable film, so that the breathable film has color differences or color spots.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a polyethylene composition, a preparation method and application thereof and a polyolefin microporous breathable film. The composition contains organic Kong Jima maleic anhydride copolymer microspheres, the copolymer microspheres have uniform particle size distribution, the dispersibility in a polyethylene matrix is good without using a coupling agent or a dispersing agent, the agglomeration phenomenon does not occur, and the defects of uneven pore size distribution, poor dispersibility, poor compatibility and the like caused by an inorganic pore-forming agent can be avoided. The composition can be applied to a breathable film to improve the breathable uniformity of the product.
In order to achieve the above object, the present invention provides, in a first aspect, a polyethylene composition characterized in that the composition comprises polyethylene, a porogen and an antioxidant;
based on 100 parts by weight of polyethylene, the dosage of the pore-forming agent is 35-110 parts by weight, and the dosage of the antioxidant composite auxiliary agent is 0.1-2 parts by weight;
the pore-forming agent is maleic anhydride copolymer microspheres, and the average particle size of the maleic anhydride copolymer microspheres is 500-1600nm.
In a second aspect, the invention provides the use of the above polyethylene composition in a polyolefin microporous breathable film.
A third aspect of the present invention provides a process for producing the above polyethylene composition, characterized in that the process comprises:
(1) Mixing polyethylene, a pore-forming agent and an antioxidant composite auxiliary agent to obtain a mixture;
(2) And carrying out melt blending extrusion, granulating and drying on the mixture in a double-screw extruder to obtain the polyethylene composition.
According to a fourth aspect of the present invention, there is provided a microporous breathable film of polyolefin, characterized in that said microporous breathable film is produced from the above polyethylene composition.
Through the technical scheme, the polyethylene composition, the preparation method and the application thereof and the polyolefin microporous breathable film provided by the invention have the following beneficial effects:
The composition provided by the invention is added with the maleic anhydride copolymer microsphere as the pore-forming agent, the copolymer microsphere has uniform particle size distribution, and the uniform dispersion of the pore-forming agent in the polyethylene blend matrix and the uniform pore size of micropores can be realized under the condition that a coupling agent and a dispersing agent are not used; the method can solve the problems of small adjustable range of physical properties and air permeability of the air permeable membrane in the prior art, and has the advantages of wide adaptability, simple operation and stable product performance.
The polyethylene composition provided by the invention can be widely applied to the fields of disposable medical and health products, water-blocking and moisture-permeable materials and the like.
Drawings
FIG. 1 is a SEM photograph of a cross-section of a sample of the polyethylene composition prepared in example 1;
FIG. 2 is a SEM photograph of a cross-section of a sample of the polyethylene composition prepared in example 2;
FIG. 3 is a SEM photograph of a cross-section of a sample of the polyethylene composition prepared in example 4;
FIG. 4 is a SEM photograph of a cross-section of a polyethylene composition-sheet prepared in example 5;
FIG. 5 is an SEM photograph of a cross-section of a sample of the polyethylene composition prepared in comparative example 1;
FIG. 6 is an SEM photograph of a cross-section of a sample of the polyethylene composition prepared in comparative example 2;
FIG. 7 is an SEM photograph of a cross-section of a polyethylene composition-sheet prepared in comparative example 3.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a polyethylene composition, which is characterized in that the composition comprises polyethylene, a pore-forming agent and an antioxidant;
based on 100 parts by weight of polyethylene, the dosage of the pore-forming agent is 35-110 parts by weight, and the dosage of the antioxidant composite auxiliary agent is 0.1-2 parts by weight;
the pore-forming agent is maleic anhydride copolymer microspheres, and the average particle size of the maleic anhydride copolymer microspheres is 500-1600nm.
The composition provided by the invention is added with the maleic anhydride copolymer microsphere as the pore-forming agent, the copolymer microsphere has uniform particle size distribution, and the uniform dispersion of the pore-forming agent in the polyethylene blend matrix and the uniform pore size of micropores can be realized under the condition that a coupling agent and a dispersing agent are not used; the method can solve the problems of small adjustable range of physical properties and air permeability of the air permeable membrane in the prior art, and has the advantages of wide adaptability, simple operation and stable product performance.
Further, based on 100 parts by weight of polyethylene, the dosage of the pore-forming agent is 50-100 parts by weight, and the dosage of the antioxidant composite auxiliary agent is 0.1-1.5 parts by weight.
According to the invention, the average particle diameter of the maleic anhydride copolymer microspheres is 600-1300nm, preferably 600-1200nm.
According to the invention, the polyethylene has a melting enthalpy of DeltaH mPE The polyethylene composition has a melting enthalpy of DeltaH m composition ；
Wherein DeltaH mPE And DeltaH m composition The difference is 10-45J/g.
In the present invention, when the difference between the melting enthalpy of the polyethylene and the melting enthalpy of the polyethylene composition satisfies the above range, it can be shown that the maleic anhydride copolymer microspheres are uniformly distributed in the polyethylene composition, and a phenomenon that the melting enthalpy of the composition is greatly reduced due to the agglomeration of the maleic anhydride copolymer microspheres does not occur, thereby enabling the breathable film prepared from the composition to have both excellent physical properties and breathability.
In the present invention, the enthalpy of fusion of the polyethylene and the polyethylene composition is measured by differential scanning calorimetry.
Further, ΔH mPE And DeltaH m composition The difference is 20-45J/g.
According to the invention, the maleic anhydride copolymer microsphere copolymer comprises structural units A from maleic anhydride and structural units B from comonomer, wherein the molar content of the structural units A is 48-55% and the molar content of the structural units B is 45-52% based on the total molar amount of the structural units in the copolymer.
According to the invention, the comonomer is selected from at least one of styrene, alpha-methylstyrene, vinyl acetate, mixed carbon four and mixed carbon five.
In the present invention, the mixed carbon four refers to a generic term of hydrocarbon compounds (mainly including butene) with four carbon atoms, and generally, the mixed carbon four includes a certain amount of alkane (such as n-butane) and other impurities which may exist in addition to butene (such as trans-2-butene, cis-2-butene, n-butene and isobutene) with various structures. In the present invention, the content of the olefin in the mixed carbon four is in the range of 60 to 75 wt%.
In the present invention, the mixed carbon five refers to a generic term for hydrocarbon compounds having five carbon atoms (mainly including pentene), and generally, in addition to pentenes (such as diene (isoprene, cyclopentadiene, 1, 4-pentadiene, piperylene) and mono-olefins (1-pentene, 2-pentene, cyclopentene, 2-methyl-1-butene, 2-methyl-2-butene)) having various structures, a certain amount of alkane (such as n-pentane, isopentane, cyclopentane, 2-methylbutane), alkyne (such as butyne-2, 3-pentene-1 alkyne) and other impurities which may be present are included in the carbon five. In the invention, the content of olefin in the mixed carbon five is 55-65 wt%.
According to the invention, the molar content of the structural units A is from 48 to 53%, preferably from 49 to 51%, and the molar content of the structural units B is from 47 to 52%, preferably from 49 to 51%, based on the total molar amount of the structural units in the copolymer.
In one embodiment of the invention, the Kong Jima maleic anhydride copolymer microsphere is prepared according to the following steps:
(1) Dissolving maleic anhydride, comonomer and initiator in a reaction medium in an inert atmosphere to form a homogeneous solution;
(2) Carrying out polymerization reaction on the homogeneous solution to obtain copolymer emulsion suspension, and carrying out solid-liquid separation to obtain the maleic anhydride copolymer microsphere;
wherein the amount of the maleic anhydride is 50-90wt% and the amount of the comonomer is 10-50wt% based on the total weight of the maleic anhydride and the comonomer;
the reaction medium is a mixture of a compound shown in the formula (1) and alkane;
wherein R is 1 And R is 2 Each independently is an alkyl group having 1 to 6 carbon atoms;
the comonomer is selected from at least one of styrene, alpha-methyl styrene and vinyl acetate.
In the invention, the maleic anhydride monomer and the comonomer are copolymerized according to a specific proportion, so that the prepared maleic anhydride copolymer is microsphere with excellent uniformity, and the copolymer has the characteristics of clean surface, good dispersibility in a medium and no aggregation.
Further, in order to obtain maleic anhydride copolymer microspheres with uniform particles and excellent morphology, the inventors have studied the amounts of maleic anhydride and comonomer in the polymerization process, and have shown that when the amount of maleic anhydride is 50-60wt% and the amount of comonomer is 40-50wt% based on the total weight of the polymerized monomers, the prepared maleic anhydride copolymer microspheres have uniform particles, excellent particle morphology, clean particle surfaces and excellent comprehensive properties.
According to the invention, the total mass concentration of maleic anhydride and comonomer is 5 to 25 wt.%, preferably 5 to 20 wt.%, based on the total weight of the homogeneous solution.
According to the invention, the mass concentration of the initiator is 0.01 to 5 wt.%, preferably 1 to 4 wt.%, based on the total weight of the homogeneous solution.
According to the invention, in formula (1), R 1 And R is 2 Each independently is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
According to the invention, the alkane is an alkane having 6 to 12 carbon atoms.
In the invention, a mixture of a compound shown in the formula (1) and alkane is selected as a reaction medium, the mixture can be matched with the specific dosage of maleic anhydride and comonomer, the self-stabilization precipitation polymerization reaction of the maleic anhydride and the comonomer I can be realized, any stabilizer and auxiliary stabilizer are not required to be added in a polymerization reaction system, the self-stabilization dispersion effect is realized, and the obtained polymer microsphere has clean surface and no pollution.
Further, the alkane is selected from at least one of hexane, heptane and octane, more preferably hexane.
According to the invention, the alkane is used in an amount of 50 to 90vol%, preferably 60 to 80vol%, based on the total volume of the reaction medium.
In the present invention, the polymerization reaction is carried out in an inert atmosphere, which may be provided by inert gases conventional in the art, such as nitrogen.
According to the invention, the polymerization conditions include: the polymerization temperature is 61-100 ℃, preferably 70-90 ℃; the polymerization time is 1 to 24 hours, preferably 2 to 12 hours.
In one embodiment of the present invention, the Kong Jima maleic anhydride copolymer microsphere is prepared according to the following steps:
in the presence of inert atmosphere, an initiator and an organic solvent, carrying out copolymerization reaction on maleic anhydride and a comonomer to prepare the maleic anhydride copolymer microsphere;
the comonomer is selected from mixed carbon four and/or mixed carbon five.
In the present invention, the copolymerization reaction may be a one-step reaction using a precipitation polymerization method.
According to the invention, the weight ratio of maleic anhydride to comonomer is 1 (0.2-3); preferably 1 (0.8-3).
According to the invention, the initiator is used in an amount of 0.05 to 20mol%, based on the total amount of maleic anhydride.
According to the present invention, the organic solvent is at least one selected from the group consisting of isoamyl acetate, butyl acetate, isopropyl acetate and ethyl acetate. Preferably, the concentration of maleic anhydride is from 5 to 25wt%, based on the total weight of the organic solvent; preferably 10 to 20wt%.
According to the invention, the conditions of the copolymerization reaction are: the copolymerization reaction temperature is 50-100 ℃, preferably 70-90 ℃; the copolymerization pressure is 0.2-2MPa, preferably 0.5-1MPa; the copolymerization time is 5 to 10 hours, preferably 6 to 9 hours.
According to the invention, the initiator is an organic peroxide and/or an azo compound.
According to the present invention, the organic peroxide is at least one selected from dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
According to the invention, the azo compound is selected from azobisisobutyronitrile and/or azobisisoheptonitrile.
In the present invention, a water bath and/or an oil bath is used to provide the heat required for the polymerization of the present invention.
In the present invention, the solid-liquid separation may be a solid-liquid separation means conventional in the art, such as centrifugal separation or flash separation.
In the invention, when centrifugal separation is adopted, the centrifugal rotating speed is 1500-5000rad/min, and the centrifugal time is 5-60min.
In the invention, when flash separation is adopted, the flash separation can be carried out in a flash separator, the flash evaporation temperature is 10-40 ℃, and the flash evaporation pressure is 0MPa.
According to the invention, the polyethylenes are linear low density polyethylenes and low density polyethylenes.
According to the invention, the linear low density polyethylene is used in an amount of 60 to 99 parts by weight, preferably 70 to 95 parts by weight, based on 100 parts by weight of polyethylene; the low density polyethylene is used in an amount of 1 to 40 parts by weight, preferably 5 to 30 parts by weight.
According to the invention, the linear low density polyethylene is a copolymer of ethylene and an alpha-olefin; preferably, the alpha-olefin is selected from at least one of butene, hexene and octene.
In the invention, the linear low density polyethylene is prepared by Ziegler Natta catalyst and/or metallocene catalyst.
According to the invention, the linear low density polyethylene has a density of 0.905g/cm 3 -0.935g/cm 3 。
According to the invention, the linear low density polyethylene has a melt flow rate of 0.5g/10min to 10g/10min, preferably 2g/10min to 6g/10min, at 190℃and under a load of 2.16 kg.
According to the invention, the linear low density polyethylene has a molecular weight distribution of 2 to 12, preferably 2 to 10.
According to the invention, the density of the low density polyethylene is 0.913g/cm 3 -0.934g/cm 3 。
According to the invention, the melt flow rate of the low density polyethylene at 190℃and 2.16kg load is from 0.1g/10min to 12g/10min, preferably from 2g/10min to 9g/10min.
According to the invention, the molecular weight distribution of the low density polyethylene is 5 to 11, preferably 6 to 10.
According to the present invention, the polyethylene composition further comprises at least one selected from the group consisting of: medium Density Polyethylene (MDPE), high Density Polyethylene (HDPE), ultra low density polyethylene (VLDPE), ultra high molecular weight polyethylene (hmwppe), polypropylene, propylene-based copolymers, ethylene-vinyl acetate copolymers, ethylene methyl acrylate copolymers, polyolefin plastomers, polyolefin elastomers and polybutenes.
According to the invention, the antioxidant composite auxiliary comprises an antioxidant and an acid absorber.
According to the invention, the weight ratio of the antioxidant to the acid absorber is 1-6:1, a step of; preferably 2-5:1.
according to the present invention, the antioxidant is at least one selected from the group consisting of pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], phenyl tris (2, 4-di-t-butyl) phosphite, stearyl propionate and alkylated polyphenols.
According to the present invention, the acid absorbing agent is a stearate, preferably at least one selected from the group consisting of calcium stearate, zinc stearate and sodium stearate.
According to the invention, the antioxidant compound auxiliary is a mixture of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), phosphoric triester of (2, 4-di-tert-butylphenyl) phosphite and calcium stearate, wherein the weight ratio of the pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), the phosphoric triester of (2, 4-di-tert-butylphenyl) phosphite to the calcium stearate is (1-3): 1, preferably (1-2): 1.
According to the present invention, the polyethylene composition does not contain a coupling agent and a dispersing agent.
In a second aspect, the invention provides the use of the above polyethylene composition in a polyolefin microporous breathable film.
According to the invention, the polyethylene composition is used for preparing the polyolefin microporous breathable film, so that the physical properties and the air permeability of the breathable film can be obviously improved, and the polyethylene composition can be further used in the fields of disposable medical and health products, water-blocking and moisture-permeable materials and the like.
A third aspect of the present invention provides a process for producing the above polyethylene composition, characterized in that the process comprises:
(1) Mixing polyethylene, a pore-forming agent and an antioxidant composite auxiliary agent to obtain a mixture;
(2) And carrying out melt blending extrusion, granulating and drying on the mixture in a double-screw extruder to obtain the polyethylene composition.
According to the invention, the rotating speed of the double-screw extruder is 150-400r/min; preferably 180-350r/min.
According to the invention, the temperatures of the feeding section, melting section, homogenizing section and die of the twin-screw extruder are 150-180deg.C, 165-200deg.C, 180-215 deg.C, 175-210 deg.C, respectively.
Preferably, the temperatures of the feeding section, melting section, homogenizing section and die of the twin-screw extruder are 160-175 ℃, 175-190 ℃, 190-210 ℃, 180-205 ℃, respectively.
According to a fourth aspect of the present invention, there is provided a microporous breathable film of polyolefin, characterized in that said microporous breathable film is produced from the above polyethylene composition.
In the invention, the polyolefin microporous breathable film prepared from the polyethylene composition not only maintains the excellent physical properties of the polyethylene composition, but also has high air permeability, and can be used in the fields of disposable medical and health products, water-blocking and moisture-permeable materials and the like.
In the present invention, the method for producing the polyolefin microporous breathable film is not particularly limited, and can be produced by selecting an appropriate method according to need, for example: and adding the polyethylene composition into an extrusion casting machine for melting and casting the sheet, wherein the extrusion temperature is 210-240 ℃, and the cooling roller temperature is 20-60 ℃, so as to prepare the polyethylene casting film. The cast film is uniaxially stretched by 2-5 times to obtain the polyethylene microporous breathable film with the average thickness of 25-35 mu m, and the heat setting temperature is 70-120 ℃.
The present invention will be described in detail by examples. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The relevant data in the invention and the embodiment thereof are obtained according to the following test method:
1. the content of each structural unit in the maleic anhydride copolymer microsphere adopts 1 H NMR was tested by 1 The content of each structural unit is measured according to the proportion of the peak area corresponding to the characteristic hydrogen in the corresponding structural unit in H NMR;
2. polymerization yield of maleic anhydride copolymer (Cp): cp=mp×100%/Mm
Wherein Mp is the mass of the resulting polymer; mm is the total mass of the monomers added;
3. copolymer microsphere particle size test method: performing vacuum metal spraying on the copolymer microsphere powder, performing morphology observation on Hitachi S4800 type field emission scanning electron microscope of Hitachi, selecting 500 microspheres from an electron microscope photograph, measuring the diameters of the microspheres, and calculating the average particle diameter of the microspheres by using a mathematical average method;
4. conversion efficiency of mixed carbon four: the polymer after the reaction was weighed, and the conversion efficiency (%) = [ (4×mass of the polymer actually obtained)/(11×mass of carbon four actually used) ]×100%;
5. Morphology of cross section of polyethylene composition sample and dispersion of porogen: soaking a sample in liquid nitrogen for 15 minutes, performing brittle fracture, performing metal spraying treatment on the section, and characterizing the section of the material by using a Hitachi S4800 type field emission scanning electron microscope of Hitachi, so as to obtain a microscopic morphology photo;
6. melt flow rate MFR: measured at 190℃under a load of 2.16kg according to the method specified in GB/T3682-2000;
7. density: the measurement was carried out according to the method specified in GB/T1033.2-2010 and using a density gradient column method;
8. tensile properties: the measurement was carried out according to the method specified in GB/T1040.3-2006 and using a universal tensile machine.
9、T C Tm and Δhm: the melting process and crystallization process of the material were analyzed using a differential scanning calorimeter. The specific operation is as follows: under the protection of nitrogen, 5-10mg of sample is measured by adopting a three-section temperature-raising and lowering measuring method from 20 ℃ to 200 ℃, the melting and crystallization process of the material is reflected by the change of heat flow, and the crystallization temperature T is calculated according to GB/T19466.3-2004 C Melting temperature Tm and melting enthalpy DeltaHm.
10. Water Vapor Transmission Rate (WVTR): the measurement was carried out according to the method specified in GB/T12704-1991.
The raw materials used in the examples and comparative examples are all commercially available.
Preparation example 1
Preparation of porogens
302.5g of maleic anhydride, 51.3g of azobisisobutyronitrile, 299.9g of styrene, 1.462L of acetone and 4.614L of hexane (the amount of hexane is 75.9 vol%) are added into a 20L reaction kettle, after the materials are uniformly mixed, nitrogen is introduced for 20 minutes, the temperature of the reaction kettle is raised to 70 ℃, the reaction is carried out for 6 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at a rotating speed of 2000rad/min, and thus the 1 542g of the pore-forming agent maleic anhydride styrene copolymer microsphere A is obtained, and the corresponding polymerization yield is 90%. In the polymerized monomer, the amount of maleic anhydride was 50.2wt%, the amount of styrene was 49.8wt%, the mass concentration of maleic anhydride and comonomer in the homogeneous solution was 12.4wt%, and the mass concentration of initiator was 1.06wt%.
Subjecting the polymer microspheres to 1 H NMR measurement revealed that the molar content of the structural unit A derived from maleic anhydride was 49.5% and the molar content of the structural unit B derived from styrene was 50.5% based on the total molar amount of the structural units in the polymer.
The average particle diameter of the Kong Jima maleic anhydride copolymer microsphere A1 was about 1000nm.
Preparation example 2
The mass percentage of each component in the mixed carbon four is as follows: 1, 3-butadiene, 0.06%; trans-2-butene, 12.67%; isobutane, 37.09%; isobutene, 19.48%; cis 2-butene, 27.79%; 1-butene, 1.02%; other 1.89%. Carrying out free radical copolymerization reaction on 13.5kg of mixed carbon four-way reactor with the composition and 200L of organic reaction liquid containing 10kg of maleic anhydride, 4kg of dibenzoyl peroxide and 100L of isoamyl acetate, wherein the copolymerization reaction pressure is 1MPa, the copolymerization reaction temperature is 80 ℃, and the copolymerization reaction time is 6h; the weight ratio of maleic anhydride to the mixed carbon number is 1:1.35. the concentration of maleic anhydride in the organic solvent was 10.2wt%.
Introducing the copolymerization reaction product into a flash separator for gas-liquid separation at 30 ℃ and 0MPa, and continuously carrying out liquid-solid separation on the obtained liquid-solid mixture in a centrifugal separator at 4000rad/min and centrifugal separation for 20min to obtain a solid product, wherein the liquid returns to the reaction kettle. The solid product was washed with hexane, and the filter cake obtained by suction filtration through a sand core funnel was dried in vacuo at 90℃for 8 hours to give 20.5kg of maleic anhydride-mixed carbon tetrapolymer A2.
1H NMR measurement was conducted on the resulting Kong Jima maleic anhydride-mixed carbon tetrapolymer A2 to determine that the molar content of the structural unit A derived from maleic anhydride was 49mol% based on the total molar amount of each structural unit in the polymer; the molar content of the structural unit B derived from the mixed C4 was 51mol%, and the conversion efficiency of the mixed C four was 55wt% as calculated by the gravimetric method.
The average particle size of the maleic anhydride-mixed carbon tetrapolymer microspheres was about 1200nm.
Preparation example 3
Preparation of porogens
376.4g of maleic anhydride, 48.8g of azobisisobutyronitrile, 256.6g of styrene, 1.165L of acetone and 4.614L of hexane (the dosage of hexane is 79.8 vol%) are added into a 20L reaction kettle, after the materials are uniformly mixed, nitrogen is introduced for 20 minutes, the temperature of the reaction kettle is raised to 70 ℃, the reaction is carried out for 8 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and the porous agent maleic anhydride styrene copolymer microsphere A3493g is obtained, and the corresponding polymerization yield is 78%. In the polymerized monomer, the amount of maleic anhydride was 59.5wt%, the amount of styrene was 40.5wt%, the mass concentration of maleic anhydride and comonomer in the homogeneous solution was 13.6wt%, and the mass concentration of initiator was 1.1wt%.
Subjecting the polymer microspheres to 1 H NMR measurement revealed that the molar content of the structural unit A derived from maleic anhydride was 48% and the molar content of the structural unit B derived from styrene was 52% based on the total molar amount of the structural units in the polymer.
The average particle diameter of the Kong Jima maleic anhydride copolymer microsphere A3 was about 1200nm.
Preparation example 4
Preparation of porogens
262.6g of maleic anhydride, 51.3g of azobisisobutyronitrile, 235.1g of styrene, 1.253L of acetone and 4.614L of hexane (the using amount of hexane is 78.6 vol%) are added into a 20L reaction kettle, after the materials are uniformly mixed, nitrogen is introduced for 20min, the temperature of the reaction kettle is raised to 70 ℃, the reaction is carried out for 5h, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20min by a centrifugal machine at a rotating speed of 2000rad/min, so as to obtain Kong Jima maleic anhydride copolymer microspheres A4438g, and the corresponding polymerization yield is 88%. In the polymerized monomer, the amount of maleic anhydride was 52.8wt%, the amount of styrene was 47.2wt%, the mass concentration of maleic anhydride and comonomer in the homogeneous solution was 10.9wt%, and the mass concentration of initiator was 1.1wt%.
The polymer microspheres were subjected to 1H NMR measurement to determine that the molar content of the structural unit A derived from maleic anhydride was 49% and the molar content of the structural unit B derived from styrene was 51% based on the total molar amount of the structural units in the polymer.
The average particle diameter of the Kong Jima maleic anhydride copolymer microsphere A4 was about 700nm.
Preparation example 5
124.6g maleic anhydride, 51.3g azobisisobutyronitrile, 129.9g styrene, 2.307L acetone and 2.645L hexane (53.4 vol%) are added into a 20L reaction kettle, after the materials are uniformly mixed, nitrogen is introduced for 20min, the temperature of the reaction kettle is raised to 70 ℃, the reaction is carried out for 4h, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20min by a centrifugal machine at a rotating speed of 2000rad/min, and Kong Jima maleic anhydride copolymer microspheres A5 191g are obtained, and the corresponding polymer yield is 75%. In the polymerized monomer, the amount of maleic anhydride was 49.0wt%, the amount of styrene was 51.0wt%, the mass concentration of maleic anhydride and comonomer in the homogeneous solution was 6.6wt%, and the mass concentration of initiator was 1.3wt%.
Subjecting the polymer microspheres to 1 H NMR measurement revealed that the molar content of the structural unit A derived from maleic anhydride was 47% and the molar content of the structural unit B derived from styrene was 53% based on the total molar amount of the structural units in the polymer.
The average particle size of the Kong Jima maleic anhydride copolymer microsphere A5 was about 460nm.
Example 1
Preparation of polyethylene composition
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 70 parts of pore-forming agent A1 and 1 part of antioxidant compound auxiliary agent are mixed in a high-speed stirrer, wherein the antioxidant compound auxiliary agent is tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) The weight ratio of pentaerythritol ester, (2, 4-di-tert-butylphenyl) phosphite triester to calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1. The polyethylene composition was melted at 200℃and tabletted, the plaques were 120-160 μm thick. Fig. 1 is an SEM photograph of a cross section of a sample of a polyethylene composition, and it can be seen from fig. 1 that the porogen has a uniform particle size and is uniformly distributed in the polyethylene matrix.
Example 2
Preparation of polyethylene composition
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 100 parts of pore-forming agent A1 and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the weight ratio of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, (2, 4-di-tert-butylphenyl) phosphite triester and calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. Drying the prepared polyethylene composition and drying the prepared polyethylene composition. The properties of the polyethylene composition are shown in Table 1. The polyethylene composition was melted at 200℃and tabletted, the plaques were 120-160 μm thick. Fig. 2 is an SEM photograph of a cross section of a sample of the polyethylene composition, and it can be seen from fig. 2 that the porogen has a uniform particle size and is uniformly distributed in the polyethylene matrix.
Example 3
Preparation of polyethylene composition
75 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 25 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 85 parts of pore-forming agent A2 and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the weight ratio of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, (2, 4-di-tert-butylphenyl) phosphite triester and calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1.
Example 4
Preparation of polyethylene composition
75 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 25 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 100 parts of pore-forming agent A3 and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the weight ratio of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, (2, 4-di-tert-butylphenyl) phosphite triester and calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. Drying the prepared polyethylene composition and drying the prepared polyethylene composition. The properties of the polyethylene composition are shown in Table 1. The polyethylene composition was melted at 200℃and tabletted, the plaques were 120-160 μm thick. Fig. 3 is an SEM photograph of a cross section of a sample of the polyethylene composition, and it can be seen from fig. 3 that the porogen has a uniform particle size and is uniformly distributed in the polyethylene matrix.
Example 5
Preparation of polyethylene composition
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 45 parts of pore-forming agent A4 and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the weight ratio of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, (2, 4-di-tert-butylphenyl) phosphite triester and calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1. The polyethylene composition was melted at 200℃and tabletted, the plaques were 120-160 μm thick. Fig. 4 is an SEM photograph of a cross section of a sample of the polyethylene composition, and it can be seen from fig. 4 that the porogen has a uniform particle size and is uniformly distributed in the polyethylene matrix.
Comparative example 1
Preparation of polyethylene composition
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 25 parts of pore-forming agent A1 and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the weight ratio of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, (2, 4-di-tert-butylphenyl) phosphite triester and calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1. The polyethylene composition was melted at 200℃and tabletted, the plaques were 120-160 μm thick. Fig. 5 is an SEM photograph of a cross section of a sample of the polyethylene composition, and it can be seen from fig. 5 that the porogen has a uniform particle size, but a small number and a non-uniform distribution.
Comparative example 2
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 Molecular weight distribution of 7.2), 100 parts of nano CaCO 3 Powder (10000 meshes of Shanghai river chemical industry Co., ltd.) and 1 part of antioxidant compound auxiliary agent are mixed in a high-speed mixer, wherein the weight ratio of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), phosphoric triester (2, 4-di-tert-butylphenyl) phosphite and calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1. The polyethylene composition was melted at 200℃and tabletted, the plaques were 120-160 μm thick. Fig. 6 is an SEM photograph of a cross-section of a sample of the polyethylene composition, showing significant agglomeration of porogens.
Comparative example 3
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 Molecular weight distribution of 7.2), 100 parts of nano BaSO 4 Powder (Sa Ha Liben Blanc FixeMicro, organic coating, d50=0.7 mu m) and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the weight ratio of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, (2, 4-di-tert-butylphenyl) phosphite triester to calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition of the invention. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1. The polyethylene composition was melted at 200℃and tabletted, the plaques were 120-160 μm thick. Fig. 7 is an SEM photograph of a cross-section of a sample of the polyethylene composition, and it can be seen that significant agglomeration of porogens occurs.
Comparative example 4
Preparation of polyethylene composition
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 140 parts of pore-forming agent A1 and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the antioxidant compound auxiliary agent is pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and the weight ratio of the (2, 4-di-tert-butylphenyl) phosphite triester to the calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1.
Comparative example 5
Preparation of polyethylene composition
90 parts of a linear low density polyethylene (MFR 3.5g/10min, density 0.917 g/cm) 3 Molecular weight distribution of 4) and 10 parts of a low density polyethylene (MFR 7.5g/10min, density 0.919g/cm 3 The molecular weight distribution is 7.2), 70 parts of pore-forming agent A5 and 1 part of antioxidant compound auxiliary agent are blended in a high-speed stirrer, wherein the antioxidant compound auxiliary agent is pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and the weight ratio of the (2, 4-di-tert-butylphenyl) phosphite triester to the calcium stearate is 2:2:1.
After being evenly mixed, the mixture is added into a double-screw extruder for melt blending, extrusion granulation, the rotating speed of a screw is 200r/min, and the temperatures of a feeding section, a melting section, a homogenizing section and a die head are respectively as follows: 170 ℃, 180 ℃, 200 ℃ and 190 ℃ to obtain the polyethylene composition. The resulting polyethylene composition was dried. The properties of the polyethylene composition are shown in Table 1.
TABLE 1
As can be seen from Table 1, the polyethylene composition provided by the invention has a Melt Flow Rate (MFR) meeting the casting process requirements, and ΔH mPE And DeltaH m composition When the difference meets the range of the invention, the maleic anhydride copolymer microspheres in the composition are uniformly distributed in the composition, so that the composition has better mechanical property and can meet the requirement of stretching multiplying power of the breathable film.
Test case
The polyethylene compositions of examples and comparative examples were fed into an extrusion casting machine to melt and cast a cast sheet, the extrusion temperature was 210 to 240℃and the chill roll temperature was 20 to 60℃to prepare polyethylene cast films. The cast film was uniaxially stretched 3 times to obtain a polyethylene microporous breathable film having an average thickness of 30 μm, and the heat setting temperature was 85 ℃. The properties of the polyethylene microporous breathable film are shown in table 2.
TABLE 2
As can be seen from Table 2, the organic pore-forming agent and the polyolefin matrix resin with uniform particles are reasonably selected, so that the uniformity of the dispersion of the pore-forming agent in the matrix resin is obviously improved under the condition of not using a coupling agent and a dispersing agent, and the prepared breathable film has high breathability. The polyethylene breathable film prepared by the embodiment of the invention has high breathability and can be widely applied to the fields of disposable medical and health products, water-blocking and moisture-permeable materials and the like.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (22)
1. A polyethylene composition, characterized in that the composition comprises polyethylene, a porogen and an antioxidant;
based on 100 parts by weight of polyethylene, the dosage of the pore-forming agent is 35-110 parts by weight, and the dosage of the antioxidant composite auxiliary agent is 0.1-2 parts by weight;
the pore-forming agent is maleic anhydride copolymer microspheres, and the average particle size of the maleic anhydride copolymer microspheres is 500-1600nm.
2. The polyethylene composition according to claim 1, wherein the pore-forming agent is used in an amount of 50 to 100 parts by weight and the antioxidant complex aid is used in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of polyethylene;
preferably, the average particle diameter of the maleic anhydride copolymer microsphere is 600-1300nm.
3. The polyethylene composition according to claim 1 or 2, wherein the polyethylene has a melting enthalpy Δh mPE The polyethylene composition has a melting enthalpy of DeltaH m composition ；
Wherein DeltaH mPE And DeltaH m composition The difference is 10 to 45J/g, preferably 20 to 45J/g.
4. A polyethylene composition according to any one of claims 1-3, wherein the maleic anhydride copolymer microsphere copolymer comprises structural units a from maleic anhydride and structural units B from comonomer, the molar content of structural units a being 48-55% and the molar content of structural units B being 45-52% based on the total molar amount of structural units in the copolymer;
preferably, the comonomer is selected from at least one of styrene, alpha-methylstyrene, vinyl acetate, mixed carbon four and mixed carbon five;
preferably, the molar content of the structural unit A is from 49 to 51% and the molar content of the structural unit B is from 49 to 51%, based on the total molar amount of the structural units in the copolymer.
5. The polyethylene composition according to any one of claims 1-4, wherein said microspheres of maleic anhydride copolymer of Kong Jima are prepared by:
(1) Dissolving maleic anhydride, comonomer and initiator in a reaction medium in an inert atmosphere to form a homogeneous solution;
(2) Carrying out polymerization reaction on the homogeneous solution to obtain copolymer emulsion suspension, and carrying out solid-liquid separation to obtain the maleic anhydride copolymer microsphere;
wherein the amount of the maleic anhydride is 50-90wt% and the amount of the comonomer is 10-50wt% based on the total weight of the maleic anhydride and the comonomer;
the reaction medium is a mixture of a compound shown in the formula (1) and alkane;
wherein R is 1 And R is 2 Each independently is an alkyl group having 1 to 6 carbon atoms.
6. The polyethylene composition according to claim 5, wherein the comonomer is selected from at least one of styrene, alpha-methylstyrene and vinyl acetate;
preferably, the mass concentration of the polymerized monomer is 5-25wt%, preferably 5-20wt%, based on the total weight of the homogeneous solution;
preferably, the mass concentration of the initiator is 0.01-5wt%, preferably 1-4wt%, based on the total weight of the homogeneous solution;
preferably, the maleic anhydride is used in an amount of 50 to 60wt% and the comonomer is used in an amount of 40 to 50wt% based on the total weight of maleic anhydride and comonomer.
7. The polyethylene composition according to claim 5 or 6, wherein in formula (1), R 1 And R is 2 Each independently is methyl or ethyl;
preferably, the alkane is an alkane having 6 to 12 carbon atoms;
preferably, the alkane is used in an amount of 50 to 90vol%, preferably 60 to 80vol%, based on the total volume of the reaction medium.
8. The polyethylene composition according to any one of claims 5-7, wherein the polymerization conditions comprise: the polymerization temperature is 61-100 ℃, preferably 70-90 ℃; the polymerization time is 1 to 24 hours, preferably 2 to 12 hours.
9. The polyethylene composition according to any one of claims 1 to 4, wherein the method for preparing microspheres of the maleic anhydride copolymer of Kong Jima comprises the steps of:
and (3) carrying out copolymerization reaction on maleic anhydride and a comonomer in the presence of an inert atmosphere, an initiator and an organic solvent to obtain the maleic anhydride copolymer microsphere.
10. The polyethylene composition according to claim 9, wherein the comonomer is selected from mixed carbon four and/or mixed carbon five;
preferably, the weight ratio of maleic anhydride to comonomer is 1 (0.2-3); preferably 1 (0.8-3);
preferably, the initiator is used in an amount of 0.05 to 20 mole% based on the total amount of maleic anhydride;
Preferably, the organic solvent is selected from at least one of isoamyl acetate, butyl acetate, isopropyl acetate and ethyl acetate;
preferably, the concentration of maleic anhydride is from 5 to 25wt%, based on the total weight of the organic solvent; preferably 10 to 20wt%.
11. The polyethylene composition according to claim 9 or 10, wherein the conditions of the copolymerization reaction comprise: the copolymerization reaction temperature is 50-100 ℃, preferably 70-90 ℃; the copolymerization pressure is 0.2-2MPa, preferably 0.5-1MPa; the copolymerization time is 5 to 10 hours, preferably 6 to 9 hours.
12. The polyethylene composition according to any one of claims 1-11, wherein the polyethylene is a linear low density polyethylene and a low density polyethylene;
preferably, the linear low density polyethylene is used in an amount of 60 to 99 parts by weight, preferably 70 to 95 parts by weight, based on 100 parts by weight of polyethylene; the low density polyethylene is used in an amount of 1 to 40 parts by weight, preferably 5 to 30 parts by weight.
13. The polyethylene composition according to claim 12, wherein the linear low density polyethylene is a copolymer of ethylene and an α -olefin; preferably, the alpha-olefin is selected from at least one of butene, hexene and octene;
Preferably, the linear low density polyethylene has a density of 0.905g/cm 3 -0.935g/cm 3 ；
Preferably, the linear low density polyethylene has a melt flow rate of 0.5g/10min to 10g/10min, preferably 2g/10min to 6g/10min, at 190℃and under a load of 2.16 kg;
preferably, the linear low density polyethylene has a molecular weight distribution of from 2 to 12, preferably from 2 to 10.
14. The polyethylene composition according to claim 12 or 13, wherein the low density polyethylene has a density of 0.913g/cm 3 -0.934g/cm 3 ；
Preferably, the low density polyethylene has a melt flow rate of 0.1g/10min to 12g/10min, preferably 2g/10min to 9g/10min, at 190℃and under a load of 2.16 kg;
preferably, the low density polyethylene has a molecular weight distribution of 5 to 11, preferably 6 to 10.
15. The polyethylene composition according to any one of claims 12-14, wherein the polyethylene composition further comprises at least one member selected from the group consisting of: medium density polyethylene, high density polyethylene, ultra low density polyethylene, ultra high molecular weight polyethylene, polypropylene, propylene-based copolymers, ethylene-vinyl acetate copolymers, ethylene methyl acrylate copolymers, polyolefin plastomers, polyolefin elastomers and polybutenes.
16. The polyethylene composition of any of claims 1-15, wherein the antioxidant co-agent comprises an antioxidant and an acid absorber;
preferably, the weight ratio of the antioxidant to the acid absorber is 1-6:1;
preferably, the antioxidant is selected from at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], phenyl tri (2, 4-di-tert-butyl) phosphite, stearyl propionate and alkylated polyphenols;
preferably, the acid absorber is a stearate, preferably at least one selected from the group consisting of calcium stearate, zinc stearate and sodium stearate.
17. The polyethylene composition according to claim 16, wherein the antioxidant co-agent is a mixture of pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), trisaccharide (2, 4-di-tert-butylphenyl) phosphite and calcium stearate, wherein the weight ratio of pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), trisaccharide (2, 4-di-tert-butylphenyl) phosphite to calcium stearate is (1-3): (1-3): 1.
18. The polyethylene composition according to any one of claims 1-17, wherein the polyethylene composition is free of coupling agents and dispersants.
19. Use of the polyethylene composition according to any one of claims 1 to 18 in a polyolefin microporous breathable film.
20. A process for preparing a polyethylene composition according to any one of claims 1 to 18, comprising:
(1) Mixing polyethylene, a pore-forming agent and an antioxidant composite auxiliary agent to obtain a mixture;
(2) And carrying out melt blending extrusion, granulating and drying on the mixture in a double-screw extruder to obtain the polyethylene composition.
21. The production method according to claim 20, wherein the twin-screw extruder has a rotation speed of 150 to 400r/min.
Preferably, the temperatures of the feeding section, melting section, homogenizing section and die of the twin-screw extruder are 150-180deg.C, 165-200deg.C, 180-215 deg.C, 175-210 deg.C, respectively.
22. A polyolefin microporous breathable film prepared from the polyethylene composition of any of claims 1-17.
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| CN202111272418.4A CN116063769B (en) | 2021-10-29 | 2021-10-29 | Polyethylene composition, preparation method and application thereof, and polyolefin microporous breathable film |
| CA3236535A CA3236535A1 (en) | 2021-10-29 | 2022-10-28 | Polyethylene composition and use thereof, and polyolefin microporous breathable film prepared therefrom |
| EP22886129.0A EP4424766A1 (en) | 2021-10-29 | 2022-10-28 | Polyethylene composition and use thereof, and polyolefin microporous breathable film prepared therefrom |
| KR1020247018145A KR20240091240A (en) | 2021-10-29 | 2022-10-28 | Polyethylene composition and uses thereof, polyolefin microporous breathable film made therefrom |
| PCT/CN2022/128276 WO2023072254A1 (en) | 2021-10-29 | 2022-10-28 | Polyethylene composition and use thereof, and polyolefin microporous breathable film prepared therefrom |
| AU2022374330A AU2022374330A1 (en) | 2021-10-29 | 2022-10-28 | Polyethylene composition and use thereof, and polyolefin microporous breathable film prepared therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040253442A1 (en) * | 2003-06-11 | 2004-12-16 | Ervin Mubarekyan | Method of forming a nanoporous film and compositions useful in such methods |
| CN110982171A (en) * | 2019-11-26 | 2020-04-10 | 金旸（厦门）新材料科技有限公司 | Low-density toughened polypropylene open-cell micro-foaming material |
| CN111849055A (en) * | 2019-04-25 | 2020-10-30 | 中国石油化工股份有限公司 | Polyethylene resin composition, polyethylene resin pellet, polyethylene expanded bead, method for producing same, and molded article |
| CN112708021A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere as well as preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040253442A1 (en) * | 2003-06-11 | 2004-12-16 | Ervin Mubarekyan | Method of forming a nanoporous film and compositions useful in such methods |
| CN111849055A (en) * | 2019-04-25 | 2020-10-30 | 中国石油化工股份有限公司 | Polyethylene resin composition, polyethylene resin pellet, polyethylene expanded bead, method for producing same, and molded article |
| CN112708021A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Maleic anhydride/N-phenylmaleimide/alpha-methylstyrene copolymer microsphere as well as preparation method and application thereof |
| CN110982171A (en) * | 2019-11-26 | 2020-04-10 | 金旸（厦门）新材料科技有限公司 | Low-density toughened polypropylene open-cell micro-foaming material |
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