CN116285068A - High-elasticity toughened PE modified material and preparation method thereof - Google Patents
High-elasticity toughened PE modified material and preparation method thereof Download PDFInfo
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- CN116285068A CN116285068A CN202310425003.9A CN202310425003A CN116285068A CN 116285068 A CN116285068 A CN 116285068A CN 202310425003 A CN202310425003 A CN 202310425003A CN 116285068 A CN116285068 A CN 116285068A
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 115
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 115
- 239000004698 Polyethylene Substances 0.000 claims abstract description 77
- 229920000573 polyethylene Polymers 0.000 claims abstract description 66
- -1 compatilizer Substances 0.000 claims abstract description 41
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 34
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 34
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 33
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 33
- 239000000314 lubricant Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 21
- 238000010894 electron beam technology Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RLKFNDFGXOQHQN-UHFFFAOYSA-N 2-nonylphenol;phosphorous acid Chemical compound OP(O)O.CCCCCCCCCC1=CC=CC=C1O.CCCCCCCCCC1=CC=CC=C1O.CCCCCCCCCC1=CC=CC=C1O RLKFNDFGXOQHQN-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims description 2
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 claims description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 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 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 42
- 229910021389 graphene Inorganic materials 0.000 description 25
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 230000009471 action Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000002926 oxygen Chemical class 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- PZKRHHZKOQZHIO-UHFFFAOYSA-N [B].[B].[Mg] Chemical compound [B].[B].[Mg] PZKRHHZKOQZHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 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 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a PE modified material with high elasticity and toughness and a preparation method thereof. The PE modified material with high elastic toughness comprises low density polyethylene, modified low density polyethylene, high density polyethylene, compatilizer, antioxidant and lubricant. The invention also provides a preparation method of the composite. Compared with the prior art, the invention uses the low-density polyethylene, the modified low-density polyethylene, the high-density polyethylene, the compatilizer, the antioxidant and the lubricant as raw materials to interact, improves the strength, the toughness, the mechanical property, the flame retardant property and the like of the polyethylene, and has the advantages of simple processing technology, low cost, small environmental pollution and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PE modified material with high elasticity and toughness and a preparation method thereof.
Background
Polyethylene (PE) is thermoplastic resin obtained by polymerizing monomer ethylene, has good cold resistance, mechanical strength and dielectric property, and is widely applied to products such as cables, films, pipes, packages, containers, medical appliances and the like; although it has excellent electrical properties, mechanical properties and processability, it has some disadvantages such as low softening point, low strength, poor resistance to atmospheric aging, susceptibility to stress cracking, susceptibility to combustion, etc.
CN109438846a discloses a reinforced and toughened polyethylene composite material and a preparation method thereof, which solves the problem that the traditional polypropylene material is difficult to simultaneously meet the requirements of the air conditioner parts in multiple aspects of tensile strength, bending strength and elongation at break, and the technical points are as follows: the adhesive comprises the following raw materials in parts by weight: 50-70 parts of polypropylene, 10-25 parts of talcum powder, 10-15 parts of carbon black, 20-30 parts of silicon dioxide, 10-15 parts of calcium stearate, 10-15 parts of magnesium boride, 2-5 parts of dispersing agent, 1-3 parts of antioxidant and 5-10 parts of coupling agent. The invention also discloses a preparation method of the reinforced and toughened polyethylene composite material. The reinforced and toughened polyethylene composite material prepared by the invention has good mechanical property, high tensile strength and bending strength, can meet market demands, and has wide market prospect.
CN102002181a discloses a high-toughness high-strength polyethylene composite material and a preparation method thereof, the composite material comprises the following components in percentage by weight: 60-85% of polyethylene, 5-30% of phenolic resin, 0.4-3% of curing agent, 3-15% of compatilizer, 5-10% of toughening agent, 0.1-1% of antioxidant and 0.3-0.8% of lubricant; the phenolic resin is thermoplastic novolac resin. The preparation method comprises the following steps: (1) Weighing polyethylene, phenolic resin, curing agent, compatilizer, toughening agent, antioxidant and lubricant according to a proportion, and then placing the materials in a high-speed stirrer for stirring and mixing for 5 minutes; (2) Adding the prepared materials into a double-screw extruder for extrusion granulation, wherein the residence time of the materials in the screw extruder is 2-3 minutes, the screw temperature is 150-200 ℃, and the screw rotating speed is 300-400 rpm. The invention has the characteristics of high strength, high heat resistance and high toughness, and can replace the existing engineering plastics; however, there are all the toughness, mechanical properties still to be improved and flame retardant properties not improved.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a PE modified material with high elasticity and toughness and a preparation method thereof.
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight:
50-80 parts by weight of low-density polyethylene, 10-20 parts by weight of high-density polyethylene, 1-10 parts by weight of compatilizer, 0.5-3 parts by weight of antioxidant and 0.5-3 parts by weight of lubricant.
The antioxidant is one or more than two of pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, 3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2-ethylene-bis (4, 6-di-tert-butylphenol) and tri (nonylphenol) phosphite.
The lubricant is one or two of stearic acid and polyethylene wax.
Polyethylene is classified into low density polyethylene and high density polyethylene. The high-density polyethylene has large relative molecular weight, narrow distribution, linear and long molecular chain, small branching degree and large crystallinity, but the high-density polyethylene has poor mechanical property and is easy to deform, age and become brittle to limit the application of the high-density polyethylene because the molecular chain is flexible and has small intermolecular acting force. The molecular structure of the low-density polyethylene contains a plurality of long-chain branches, and the long-chain branches seriously affect the chemical stability, heat resistance, impact strength and tensile strength, and the product strength is low. The invention combines the low-density polyethylene and the high-density polyethylene, and overcomes the defects of the low-density polyethylene and the high-density polyethylene by interaction, thereby improving the performance of the low-density polyethylene and the high-density polyethylene.
On the basis, one half of the low-density polyethylene is modified, firstly, the low-density polyethylene is subjected to radiation treatment by adopting an electron beam, so that a series of oxygen-containing functional groups are introduced into a molecular chain of the low-density polyethylene, the surface activity of the molecular chain is improved, then, styrene is added, the modified low-density polyethylene is prepared under the action of benzoyl peroxide, and the polystyrene has certain toughness, so that the low-density polyethylene and the polystyrene are easy to yield and deform under stress after being mixed, and more impact energy is easy to absorb; meanwhile, the polystyrene and the polyethylene have good bonding interface, and the low-density polyethylene is crosslinked under the action of benzoyl peroxide to form a three-dimensional network structure, so that the impact resistance of the low-density polyethylene is improved, and further the toughness and other mechanical properties of the polyethylene are improved.
Further preferably, the PE modified material with high elastic toughness comprises the following raw materials in parts by weight: 25-40 parts by weight of low-density polyethylene, 25-40 parts by weight of modified low-density polyethylene, 10-20 parts by weight of high-density polyethylene, 1-10 parts by weight of compatilizer, 0.5-3 parts by weight of antioxidant and 0.5-3 parts by weight of lubricant.
The preparation method of the modified low-density polyethylene comprises the following steps:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene; wherein the dose rate of the electron beam is 5-10kGys -1 The total dose is 15-30kGy;
s2, adding 30-50 parts by weight of pretreated low-density polyethylene, 0.3-0.8 part by weight of sodium dodecyl benzene sulfonate and 10-20 parts by weight of styrene into 300-500 parts by weight of water, and uniformly mixing to obtain a suspension; heating the suspension to 60-80 ℃ for reaction for 30-60min, then introducing nitrogen, heating to 85-95 ℃ under nitrogen atmosphere, adding 0.1-0.5 part by weight of benzoyl peroxide and 10-20 parts by weight of styrene, keeping the temperature of 85-95 ℃ for reaction for 8-12h, centrifuging after the reaction is finished, taking out sediment, washing and drying to obtain the modified low-density polyethylene.
The compatilizer is one or a mixture of more than two of ethylene-propylene random copolymer, maleic anhydride grafted polyethylene and ethylene-methyl acrylate-glycidyl methacrylate copolymer; preferably, the compatibilizer is an ethylene-methyl acrylate-glycidyl methacrylate copolymer; further preferably, the compatibilizer is a modified ethylene methyl acrylate-glycidyl methacrylate copolymer.
The preparation method of the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer comprises the following steps:
(1) Adding graphene oxide into water for ultrasonic treatment for 30-60min, wherein the ultrasonic frequency is 15-25kHz, the ultrasonic power is 100-500W, and the bath ratio of the graphene oxide to the water is 1g: (20-30) mL, and obtaining pretreated graphene;
(2) Adding 1-5 parts by weight of pretreated graphene and 0.1-3 parts by weight of 3-chloropropyl trimethoxysilane into 30-100 parts by weight of water, uniformly mixing, heating to 70-90 ℃ for reacting for 5-10 hours, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain modified graphene;
(3) Adding 1-10 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into 50-100 parts by weight of toluene, uniformly mixing, heating to 70-90 ℃, reacting for 30-90min at 300-500r/min, then adding 10-30 parts by weight of mixed solvent, keeping 70-90 ℃ and reacting for 30-90min at 300-500r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out precipitate substances, centrifuging, taking precipitate, washing and drying to obtain the pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer; the mixed solvent is prepared by mixing sodium hydroxide and absolute ethyl alcohol according to a bath liquid ratio of 1g: (20-40) mL, and uniformly mixing to prepare the medicine;
(4) Uniformly mixing 5-10 parts by weight of pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer, 8-15 parts by weight of diphenyl chlorophosphate and 1-5 parts by weight of modified graphene, heating to 150-180 ℃ for reaction at 300-500r/min for 1-3h, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out a precipitate substance, centrifuging to obtain a precipitate, washing and drying to obtain the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer.
Although the mechanical properties are improved to a certain extent, the introduction of polystyrene is poor in compatibility due to the fact that the polystyrene is different from polypropylene in structure, delamination and cracking are easy to occur, and the ethylene-methyl acrylate-glycidyl methacrylate copolymer is introduced to enhance the interfacial viscosity. In order to further improve the compatibility, an ethylene-methyl acrylate-glycidyl methacrylate copolymer is pretreated by adopting a sodium hydroxide ethanol solution, diphenyl chlorophosphate and modified graphene are added for modification, and finally the obtained modified ethylene-methyl acrylate-glycidyl methacrylate copolymer contains phenyl, so that the introduction of the phenyl further improves the compatibility, and simultaneously, the impact resistance and the flame retardance of the polyethylene are improved. According to the invention, diphenyl chlorophosphate and modified graphene are introduced into an ethylene-methyl acrylate-glycidyl methacrylate copolymer main chain by a grafting method, so that the defects of poor compatibility of graphene and polyethylene and the like are effectively avoided, and the mechanical property and flame retardant property of the polyethylene are further improved. Graphene oxide and diphenyl chlorophosphate cannot effectively isolate air and heat from spreading, and simultaneously form a continuous and compact carbon layer to protect an unburned matrix; the graphene oxide and the diphenyl chlorophosphate act synergistically to improve the mechanical property and flame retardant property of the polyethylene.
The invention also discloses a preparation method of the PE modified material with high elastic toughness.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 1-10min at a rotating speed of 300-900r/min, then adding a compatilizer, an antioxidant and a lubricant, heating to 90-110 ℃ to react for 10-20min, stopping the reaction, taking out the mixed material, and cooling to room temperature for standby;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 45-85min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 1-5min, and then melting, extruding, vacuumizing, air cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210-220 ℃, second 220-235 ℃, third 235-245 ℃, fourth 245-255 ℃, fifth 245-255 ℃, sixth 245-255 ℃, seventh 245-255 ℃, eighth 235-245 ℃, ninth 235-245 ℃ and screw speed 100-500r/min.
The invention has the beneficial effects that:
1. the invention uses low density polyethylene, modified low density polyethylene, high density polyethylene, compatilizer, antioxidant and lubricant as raw materials, and improves the strength, toughness, mechanical property, flame retardant property and the like of polyethylene through interaction, and simultaneously has simple processing technology, low cost and little environmental pollution.
2. Compared with the prior art, the modified low-density polyethylene is introduced, one half of the low-density polyethylene is modified, the low-density polyethylene is firstly subjected to radiation treatment by adopting an electron beam, so that a series of oxygen-containing functional groups are introduced into a molecular chain of the low-density polyethylene, the surface activity of the low-density polyethylene is improved, then styrene is added, the modified low-density polyethylene is prepared under the action of benzoyl peroxide, and the polystyrene has certain toughness, so that the low-density polyethylene is easy to yield and deform after being mixed with the polystyrene, and more impact energy is easy to absorb; meanwhile, the polystyrene and the polyethylene have good bonding interface, and the low-density polyethylene is crosslinked under the action of benzoyl peroxide to form a three-dimensional network structure, so that the impact resistance of the low-density polyethylene is improved, and further the toughness and other mechanical properties of the polyethylene are improved.
3. Compared with the prior art, the ethylene-methyl acrylate-glycidyl methacrylate copolymer is pretreated by adopting the sodium hydroxide ethanol solution, then diphenyl chlorophosphate and modified graphene are added for modification, and finally the obtained modified ethylene-methyl acrylate-glycidyl methacrylate copolymer contains phenyl, so that the introduction of the phenyl further improves the compatibility, and simultaneously improves the shock resistance and flame retardance of the polyethylene. According to the invention, diphenyl chlorophosphate and modified graphene are introduced into an ethylene-methyl acrylate-glycidyl methacrylate copolymer main chain by a grafting method, so that the defects of poor compatibility of graphene and polyethylene and the like are effectively avoided, and the mechanical property and flame retardant property of the polyethylene are further limited. Graphene oxide and diphenyl chlorophosphate cannot effectively isolate air and heat from spreading, and simultaneously form a continuous and compact carbon layer to protect an unburned matrix; the graphene oxide and the diphenyl chlorophosphate act synergistically to improve the mechanical property and flame retardant property of the polyethylene.
Detailed Description
Parameters of specific chemicals in each example, sources:
low density polyethylene, brand: LDPE 1I60A, manufacturer: karta petrochemical.
High density polyethylene, brand: BE0400, manufacturer: korean LG chemistry.
Ethylene-methyl acrylate-glycidyl methacrylate copolymer, AX8900, commercially available from Dongguan Corp
Graphene oxide, sheet diameter: 10-20 μm, oxygen content: 40-45% of carbon-oxygen molar ratio: 1.3-1.5, purchased from Nanjing Biotechnology Inc.
Example 1
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight: 80 parts by weight of low density polyethylene, 20 parts by weight of high density polyethylene, 1 part by weight of antioxidant and 1 part by weight of lubricant.
The antioxidant is prepared by mixing pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and tris (nonylphenol) phosphite according to a mass ratio of 1:1.
The lubricant is stearic acid.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 5min at a rotating speed of 450r/min, then adding an antioxidant and a lubricant, heating to 110 ℃ for reacting for 20min, stopping the reaction, taking out the mixed materials, and cooling to room temperature for later use;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 50min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 5min, and then melting, extruding, vacuumizing, air-cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210 ℃, second 220 ℃, third 235 ℃, fourth 245 ℃, fifth 245 ℃, sixth 245 ℃, seventh 245 ℃, eighth 245 ℃, ninth 235 ℃ and screw rotation speed 300r/min.
Example 2
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight: 40 parts by weight of low density polyethylene, 40 parts by weight of modified low density polyethylene, 20 parts by weight of high density polyethylene, 1 part by weight of antioxidant and 1 part by weight of lubricant.
The antioxidant is prepared by mixing pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and tris (nonylphenol) phosphite according to a mass ratio of 1:1.
The lubricant is stearic acid.
The preparation method of the modified low-density polyethylene comprises the following steps:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene; wherein the dose rate of the electron beam is 7kGys -1 The total dose was 15kGy;
s2, adding 40 parts by weight of pretreated low-density polyethylene, 0.5 part by weight of sodium dodecyl benzene sulfonate and 15 parts by weight of styrene into 350 parts by weight of water, and uniformly mixing to obtain a suspension; heating the suspension to 75 ℃ for reaction for 60min, then introducing nitrogen, heating to 95 ℃ under nitrogen atmosphere, adding 0.4 part by weight of benzoyl peroxide and 5 parts by weight of styrene, keeping the temperature of 95 ℃ for reaction for 10h, centrifuging to obtain precipitate, washing and drying to obtain the modified low-density polyethylene.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 5min at a rotating speed of 450r/min, adding an antioxidant and a lubricant, heating to 110 ℃ to react for 20min, stopping the reaction, taking out the mixed materials, and cooling to room temperature for later use;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 50min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 5min, and then melting, extruding, vacuumizing, air-cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210 ℃, second 220 ℃, third 235 ℃, fourth 245 ℃, fifth 245 ℃, sixth 245 ℃, seventh 245 ℃, eighth 245 ℃, ninth 235 ℃ and screw rotation speed 300r/min.
Example 3
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight:
40 parts by weight of low density polyethylene, 40 parts by weight of modified low density polyethylene, 20 parts by weight of high density polyethylene, 8 parts by weight of compatilizer, 1 part by weight of antioxidant and 1 part by weight of lubricant.
The antioxidant is prepared by mixing pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and tris (nonylphenol) phosphite according to a mass ratio of 1:1.
The lubricant is stearic acid.
The compatilizer is ethylene-methyl acrylate-glycidyl methacrylate copolymer.
The preparation method of the modified low-density polyethylene comprises the following steps:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene; wherein the dose rate of the electron beam is 7kGys -1 The total dose was 15kGy;
s2, adding 40 parts by weight of pretreated low-density polyethylene, 0.5 part by weight of sodium dodecyl benzene sulfonate and 15 parts by weight of styrene into 350 parts by weight of water, and uniformly mixing to obtain a suspension; heating the suspension to 75 ℃ for reaction for 60min, then introducing nitrogen, heating to 95 ℃ under nitrogen atmosphere, adding 0.4 part by weight of benzoyl peroxide and 5 parts by weight of styrene, keeping the temperature of 95 ℃ for reaction for 10h, centrifuging to obtain precipitate, washing and drying to obtain the modified low-density polyethylene.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 5min at a rotating speed of 450r/min, adding a compatilizer, an antioxidant and a lubricant, heating to 110 ℃ for reacting for 20min, stopping the reaction, taking out the mixed materials, and cooling to room temperature for later use;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 50min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 5min, and then melting, extruding, vacuumizing, air-cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210 ℃, second 220 ℃, third 235 ℃, fourth 245 ℃, fifth 245 ℃, sixth 245 ℃, seventh 245 ℃, eighth 245 ℃, ninth 235 ℃ and screw rotation speed 300r/min.
Example 4
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight: 40 parts by weight of low density polyethylene, 40 parts by weight of modified low density polyethylene, 20 parts by weight of high density polyethylene, 8 parts by weight of compatilizer, 1 part by weight of antioxidant and 1 part by weight of lubricant.
The antioxidant is prepared by mixing pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and tris (nonylphenol) phosphite according to a mass ratio of 1:1.
The lubricant is stearic acid.
The preparation method of the modified low-density polyethylene comprises the following steps:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene; wherein the dose rate of the electron beam is 7kGys -1 The total dose was 15kGy;
s2, adding 40 parts by weight of pretreated low-density polyethylene, 0.5 part by weight of sodium dodecyl benzene sulfonate and 15 parts by weight of styrene into 350 parts by weight of water, and uniformly mixing to obtain a suspension; heating the suspension to 75 ℃ for reaction for 60min, then introducing nitrogen, heating to 95 ℃ under nitrogen atmosphere, adding 0.4 part by weight of benzoyl peroxide and 5 parts by weight of styrene, keeping the temperature of 95 ℃ for reaction for 10h, centrifuging to obtain precipitate, washing and drying to obtain the modified low-density polyethylene.
The compatilizer is a modified ethylene-methyl acrylate-glycidyl methacrylate copolymer; the preparation method of the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer comprises the following steps:
(1) Adding graphene oxide into water for ultrasonic treatment for 60min, wherein the ultrasonic frequency is 18kHz, the ultrasonic power is 300W, and the bath ratio of the graphene oxide to the water is 1g:20mL, to obtain pretreated graphene;
(2) Adding 5 parts by weight of pretreated graphene and 2 parts by weight of 3-chloropropyl trimethoxysilane into 100 parts by weight of water, uniformly mixing, heating to 70 ℃ for reaction for 10 hours, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain modified graphene;
(3) Adding 10 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into 100 parts by weight of toluene, uniformly mixing, heating to 80 ℃, reacting for 60min at 500r/min, then adding 30 parts by weight of mixed solvent, keeping 80 ℃, reacting for 60min at 500r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out precipitate substances, centrifuging, taking precipitate, washing and drying to obtain the pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer; the mixed solvent is prepared by mixing sodium hydroxide and absolute ethyl alcohol according to a bath liquid ratio of 1g:30mL of the mixture is uniformly mixed to prepare the medicine;
(4) Uniformly mixing 10 parts by weight of pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer, 15 parts by weight of diphenyl chlorophosphate and 5 parts by weight of modified graphene, heating to 160 ℃, reacting for 3 hours at 300r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out a precipitate substance, centrifuging, taking out the precipitate, washing and drying to obtain the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 5min at a rotating speed of 450r/min, adding a compatilizer, an antioxidant and a lubricant, heating to 110 ℃ for reacting for 20min, stopping the reaction, taking out the mixed materials, and cooling to room temperature for later use;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 50min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 5min, and then melting, extruding, vacuumizing, air-cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210 ℃, second 220 ℃, third 235 ℃, fourth 245 ℃, fifth 245 ℃, sixth 245 ℃, seventh 245 ℃, eighth 245 ℃, ninth 235 ℃ and screw rotation speed 300r/min.
Example 5
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight: 40 parts by weight of low density polyethylene, 40 parts by weight of modified low density polyethylene, 20 parts by weight of high density polyethylene, 8 parts by weight of compatilizer, 1 part by weight of antioxidant and 1 part by weight of lubricant.
The antioxidant is prepared by mixing pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and tris (nonylphenol) phosphite according to a mass ratio of 1:1.
The lubricant is stearic acid.
The preparation method of the modified low-density polyethylene comprises the following steps:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene; wherein the dose rate of the electron beam is 7kGys -1 The total dose was 15kGy;
s2, adding 40 parts by weight of pretreated low-density polyethylene, 0.5 part by weight of sodium dodecyl benzene sulfonate and 15 parts by weight of styrene into 350 parts by weight of water, and uniformly mixing to obtain a suspension; heating the suspension to 75 ℃ for reaction for 60min, then introducing nitrogen, heating to 95 ℃ under nitrogen atmosphere, adding 0.4 part by weight of benzoyl peroxide and 5 parts by weight of styrene, keeping the temperature of 95 ℃ for reaction for 10h, centrifuging to obtain precipitate, washing and drying to obtain the modified low-density polyethylene.
The compatilizer is a modified ethylene-methyl acrylate-glycidyl methacrylate copolymer; the preparation method of the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer comprises the following steps:
(1) Adding 10 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into 100 parts by weight of toluene, uniformly mixing, heating to 80 ℃, reacting for 60min at 500r/min, then adding 30 parts by weight of mixed solvent, keeping 80 ℃, reacting for 60min at 500r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out precipitate substances, centrifuging, taking precipitate, washing and drying to obtain the pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer; the mixed solvent is prepared by mixing sodium hydroxide and absolute ethyl alcohol according to a bath liquid ratio of 1g:30mL of the mixture is uniformly mixed to prepare the medicine;
(2) Uniformly mixing 10 parts by weight of pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer and 20 parts by weight of diphenyl chlorophosphate, heating to 160 ℃, reacting for 3 hours at 300r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out precipitate substances, centrifuging, taking out precipitate, washing and drying to obtain the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 5min at a rotating speed of 450r/min, adding a compatilizer, an antioxidant and a lubricant, heating to 110 ℃ for reacting for 20min, stopping the reaction, taking out the mixed materials, and cooling to room temperature for later use;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 50min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 5min, and then melting, extruding, vacuumizing, air-cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210 ℃, second 220 ℃, third 235 ℃, fourth 245 ℃, fifth 245 ℃, sixth 245 ℃, seventh 245 ℃, eighth 245 ℃, ninth 235 ℃ and screw rotation speed 300r/min.
Example 6
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight: 40 parts by weight of low density polyethylene, 40 parts by weight of modified low density polyethylene, 20 parts by weight of high density polyethylene, 8 parts by weight of compatilizer, 1 part by weight of antioxidant and 1 part by weight of lubricant.
The antioxidant is prepared by mixing pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and tris (nonylphenol) phosphite according to a mass ratio of 1:1.
The lubricant is stearic acid.
The preparation method of the modified low-density polyethylene comprises the following steps:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene; wherein the dose rate of the electron beam is 7kGys -1 The total dose was 15kGy;
s2, adding 40 parts by weight of pretreated low-density polyethylene, 0.5 part by weight of sodium dodecyl benzene sulfonate and 15 parts by weight of styrene into 350 parts by weight of water, and uniformly mixing to obtain a suspension; heating the suspension to 75 ℃ for reaction for 60min, then introducing nitrogen, heating to 95 ℃ under nitrogen atmosphere, adding 0.4 part by weight of benzoyl peroxide and 5 parts by weight of styrene, keeping the temperature of 95 ℃ for reaction for 10h, centrifuging to obtain precipitate, washing and drying to obtain the modified low-density polyethylene.
The compatilizer is a modified ethylene-methyl acrylate-glycidyl methacrylate copolymer; the preparation method of the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer comprises the following steps:
(1) Adding graphene oxide into water for ultrasonic treatment for 60min, wherein the ultrasonic frequency is 18kHz, the ultrasonic power is 300W, and the bath ratio of the graphene oxide to the water is 1g:20mL, to obtain pretreated graphene;
(2) Adding 5 parts by weight of pretreated graphene and 2 parts by weight of 3-chloropropyl trimethoxysilane into 100 parts by weight of water, uniformly mixing, heating to 70 ℃ for reaction for 10 hours, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain modified graphene;
(3) Adding 10 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer into 100 parts by weight of toluene, uniformly mixing, heating to 80 ℃, reacting for 60min at 500r/min, then adding 30 parts by weight of mixed solvent, keeping 80 ℃, reacting for 60min at 500r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out precipitate substances, centrifuging, taking precipitate, washing and drying to obtain the pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer; the mixed solvent is prepared by mixing sodium hydroxide and absolute ethyl alcohol according to a bath liquid ratio of 1g:30mL of the mixture is uniformly mixed to prepare the medicine;
(4) Uniformly mixing 10 parts by weight of the pretreated ethylene-methyl acrylate-glycidyl methacrylate copolymer and 20 parts by weight of the modified graphene, heating to 160 ℃, reacting for 3 hours at 300r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out a precipitate substance, centrifuging, taking the precipitate, washing and drying to obtain the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 5min at a rotating speed of 450r/min, adding a compatilizer, an antioxidant and a lubricant, heating to 110 ℃ for reacting for 20min, stopping the reaction, taking out the mixed materials, and cooling to room temperature for later use;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 50min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 5min, and then melting, extruding, vacuumizing, air-cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210 ℃, second 220 ℃, third 235 ℃, fourth 245 ℃, fifth 245 ℃, sixth 245 ℃, seventh 245 ℃, eighth 245 ℃, ninth 235 ℃ and screw rotation speed 300r/min.
Example 7
A PE modified material with high elasticity and toughness comprises the following raw materials in parts by weight: 40 parts by weight of low density polyethylene, 40 parts by weight of modified low density polyethylene, 20 parts by weight of high density polyethylene, 8 parts by weight of compatilizer, 1 part by weight of antioxidant and 1 part by weight of lubricant.
The antioxidant is prepared by mixing pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and tris (nonylphenol) phosphite according to a mass ratio of 1:1.
The lubricant is stearic acid.
The preparation method of the modified low-density polyethylene comprises the following steps:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene; wherein the dose rate of the electron beam is 7kGys -1 The total dose was 15kGy;
s2, adding 40 parts by weight of pretreated low-density polyethylene, 0.5 part by weight of sodium dodecyl benzene sulfonate and 15 parts by weight of styrene into 350 parts by weight of water, and uniformly mixing to obtain a suspension; heating the suspension to 75 ℃ for reaction for 60min, then introducing nitrogen, heating to 95 ℃ under nitrogen atmosphere, adding 0.4 part by weight of benzoyl peroxide and 5 parts by weight of styrene, keeping the temperature of 95 ℃ for reaction for 10h, centrifuging to obtain precipitate, washing and drying to obtain the modified low-density polyethylene.
The compatilizer is a modified ethylene-methyl acrylate-glycidyl methacrylate copolymer; the preparation method of the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer comprises the following steps: uniformly mixing 10 parts by weight of ethylene-methyl acrylate-glycidyl methacrylate copolymer, 15 parts by weight of diphenyl chlorophosphate and 5 parts by weight of graphene oxide, heating to 160 ℃, reacting for 3 hours at 300r/min, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out a precipitate substance, centrifuging, taking out the precipitate, washing and drying to obtain the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer.
A preparation method of a PE modified material with high elasticity and toughness comprises the following steps:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 5min at a rotating speed of 450r/min, adding a compatilizer, an antioxidant and a lubricant, heating to 110 ℃ for reacting for 20min, stopping the reaction, taking out the mixed materials, and cooling to room temperature for later use;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 50min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 5min, and then melting, extruding, vacuumizing, air-cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
Wherein the processing temperature of each section of the double-screw extruder is as follows: first 210 ℃, second 220 ℃, third 235 ℃, fourth 245 ℃, fifth 245 ℃, sixth 245 ℃, seventh 245 ℃, eighth 245 ℃, ninth 235 ℃ and screw rotation speed 300r/min.
Test example 1
Tensile strength and elongation at break: determination of tensile Properties of plastics section 2, see GB/T1040.2-2006: test conditions for molding and extrusion of plastics the tensile properties were tested. Test conditions: preparing dumbbell type sample bars obtained by injection molding of PE modified materials with high elastic toughness into 1A type sample bars, and performing stretching loading speed in a room temperature environment: each group of samples was tested 5 times at 2mm/min and averaged.
Impact strength: the notched impact strength test of the cantilever beam is carried out by referring to GB/T1843-2008 "determination of impact strength of Plastic cantilever beam", the notch type is A type, each group of samples is tested 5 times, and the average value is obtained.
Flexural strength: flexural strength testing was performed with reference to GB/T9341-2008 determination of flexural Properties of plastics. Test conditions: the dumbbell-shaped sample bars obtained by injection molding are manufactured to be 80mm long, 10mm wide and 4mm thick, and are performed in a room temperature environment, and the tensile loading speed is high: 2mm/min, span 64mm, 5 times per group of samples, and average.
TABLE 1 test results of mechanical Properties of high elastic toughened PE modified materials
| Tensile Strength/MPa | Impact strength/(kJ/m) 2 ) | Flexural Strength/MPa | |
| Example 1 | 19.4 | 52.9 | 39.6 |
| Example 2 | 24.3 | 58.7 | 42.2 |
| Example 3 | 26.2 | 59.5 | 44.1 |
| Example 4 | 38.8 | 73.6 | 62.5 |
| Example 5 | 36.4 | 70.1 | 59.3 |
| Example 6 | 33.5 | 68.4 | 56.5 |
| Example 7 | 27.6 | 61.3 | 49.4 |
As can be seen from table 1, the toughness and mechanical properties of example 2 are significantly better than those of example 1, as a possible reason for the comparison of example 1 and example 2 is: in the invention, the low-density polyethylene and the high-density polyethylene are used in combination in the embodiment 1, and the defects of the low-density polyethylene and the high-density polyethylene are overcome by interaction, so that the performance of the low-density polyethylene and the high-density polyethylene is improved; on the basis of the embodiment 1, modifying one half of the low-density polyethylene, firstly adopting electron beams to radiate the low-density polyethylene, leading a series of oxygen-containing functional groups into the molecular chain of the low-density polyethylene, improving the surface activity of the low-density polyethylene, then adding styrene, preparing the modified low-density polyethylene under the action of benzoyl peroxide, wherein the polystyrene has certain toughness, leading the low-density polyethylene to be easy to yield and deform after being mixed with the polystyrene, and being easy to absorb more impact energy; meanwhile, the polystyrene and the polyethylene have good bonding interface, and the low-density polyethylene is crosslinked under the action of benzoyl peroxide to form a three-dimensional network structure, so that the impact resistance of the low-density polyethylene is improved, and further the toughness and other mechanical properties of the polyethylene are improved.
As can be seen from a comparison of example 2 and example 3, example 3 has a tensile strength of 26.2MPa and an impact strength of 59.5kJ/m 2 The bending strength of 44.1MPa is significantly better than the corresponding performance in example 2, probably due to: the polystyrene is introduced, and has poor compatibility with polypropylene, so that layering and cracking are easy to occur, and the ethylene-methyl acrylate-glycidyl methacrylate copolymer is introduced to strengthen the interfaceViscosity.
As can be seen from the comparison of the example 3 and the example 4, the toughness and the mechanical properties of the example 4 are obviously superior to those of the example 3, and the possible reasons are that the ethylene-methyl acrylate-glycidyl methacrylate copolymer is pretreated by adopting a sodium hydroxide ethanol solution, then diphenyl chlorophosphate and modified graphene are added for modification, and the finally obtained modified ethylene-methyl acrylate-glycidyl methacrylate copolymer contains phenyl groups, so that the introduction of the phenyl groups further improves the compatibility, and meanwhile, the impact resistance and the flame retardance of the polyethylene are improved.
As can be seen from the comparison of examples 4-6, the toughness and mechanical properties of example 4 are significantly better than those of examples 5-6, possibly due to the following: according to the invention, diphenyl chlorophosphate and modified graphene are introduced into an ethylene-methyl acrylate-glycidyl methacrylate copolymer main chain by a grafting method, so that the defects of poor compatibility of graphene and polyethylene and the like are effectively avoided, and the mechanical property and flame retardant property of the polyethylene are further improved. The graphene oxide and the diphenyl chlorophosphate have the same interaction, so that the toughness and mechanical property of the polyethylene are improved.
Test example 2
Vertical combustion performance test:
the vertical combustion performance test was performed with reference to the vertical combustion test in GB/T2408-2008 "determination of Plastic Combustion Performance horizontal method and vertical method".
Table 2 test results of flame retardant properties of high elastic toughened PE modified materials
| Vertical combustion/(UL 94.1.6 mm) | |
| Example 4 | V-0 |
| Example 5 | V-0 |
| Example 6 | V-0 |
| Example 7 | V-1 |
As is clear from Table 2, in example 4, the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer is prepared by modifying the ethylene-methyl acrylate-glycidyl methacrylate copolymer with diphenyl chlorophosphate and modified graphene, and the diphenyl chlorophosphate and the modified graphene are introduced into the main chain of the ethylene-methyl acrylate-glycidyl methacrylate copolymer by a grafting method, so that the defects of poor compatibility of the graphene and the polyethylene and the like are effectively avoided, and the mechanical property and the flame retardant property of the polyethylene are further improved. Graphene oxide and diphenyl chlorophosphate cannot effectively isolate air and heat from spreading, and simultaneously form a continuous and compact carbon layer to protect an unburned matrix; the graphene oxide and the diphenyl chlorophosphate act synergistically to improve the mechanical property and flame retardant property of the polyethylene.
Claims (9)
1. The PE modified material with high elastic toughness is characterized by comprising the following raw materials: low density polyethylene, modified low density polyethylene, high density polyethylene, compatilizer, antioxidant and lubricant.
2. The high elastic toughened PE modified material as claimed in claim 1, wherein said modified low density polyethylene is prepared by a process comprising the steps of:
s1, pre-radiating the low-density polyethylene by adopting an electron beam to obtain pre-treated low-density polyethylene;
s2, adding the pretreated low-density polyethylene, sodium dodecyl benzene sulfonate and styrene into water, and uniformly mixing to obtain a suspension; and heating the suspension for reaction, introducing nitrogen, heating for reaction under the nitrogen atmosphere, adding benzoyl peroxide and styrene, keeping the heating for reaction, centrifuging after the reaction is finished, taking out precipitate, washing and drying to obtain the modified low-density polyethylene.
3. The high elastic toughened PE modified material of claim 2 wherein: the dose rate of the electron beam in the step S1 is 5-10kGys -1 The total dose is 15-30kGy.
4. The high elastic toughening PE modified material according to claim 1, wherein the antioxidant is one or a mixture of more than two of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, 3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2-ethylene-bis (4, 6-di-tert-butylphenol), tris (nonylphenol) phosphite.
5. The high elastic toughening PE modified material according to claim 1, wherein the lubricant is one or a mixture of two of stearic acid and polyethylene wax.
6. The high elastic toughening PE modified material according to claim 1, wherein the compatibilizer is one or a mixture of more than two of an ethylene-propylene random copolymer, a maleic anhydride grafted polyethylene, an ethylene-methyl acrylate-glycidyl methacrylate copolymer, and a modified ethylene-methyl acrylate-glycidyl methacrylate copolymer.
7. The high elastic toughening PE modified material according to claim 6, wherein the preparation method of the modified ethylene-methyl acrylate-glycidyl methacrylate copolymer comprises the following steps: adding ethylene-methyl acrylate-glycidyl methacrylate copolymer into toluene, uniformly mixing, heating for reaction, then adding mixed solvent, keeping heating for reaction, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol to separate out precipitate substances, centrifuging, taking precipitate, washing and drying to obtain modified ethylene-methyl acrylate-glycidyl methacrylate copolymer; the mixed solvent is prepared by mixing sodium hydroxide and absolute ethyl alcohol according to a bath liquid ratio of 1g: (20-40) mL, and mixing uniformly.
8. A method of preparing a high elastic toughened PE modified material as claimed in any of claims 1 to 7 comprising the steps of:
step 1, adding low-density polyethylene, modified low-density polyethylene and high-density polyethylene into a high-speed mixer, stirring for 1-10min at a rotating speed of 300-900r/min, then adding a compatilizer, an antioxidant and a lubricant, heating to 90-110 ℃ to react for 10-20min, stopping the reaction, taking out the mixed material, and cooling to room temperature for standby;
step 2, feeding the cooled mixture in the step 1 into a kneader for kneading for 45-85min;
and 3, feeding the kneaded mixture in the step 2 into a double-screw extruder, preheating for 1-5min, and then melting, extruding, vacuumizing, air cooling, granulating and drying to obtain the high-elasticity toughened PE modified material.
9. The method of claim 8, wherein the twin screw extruder processing temperatures of the stages: first 210-220 ℃, second 220-235 ℃, third 235-245 ℃, fourth 245-255 ℃, fifth 245-255 ℃, sixth 245-255 ℃, seventh 245-255 ℃, eighth 235-245 ℃, ninth 235-245 ℃ and screw speed 100-500r/min.
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