CN114736443A - Crosslinkable polyethylene composition and application thereof, crosslinked polyethylene and preparation method and application thereof - Google Patents
Crosslinkable polyethylene composition and application thereof, crosslinked polyethylene and preparation method and application thereof Download PDFInfo
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- CN114736443A CN114736443A CN202110020292.5A CN202110020292A CN114736443A CN 114736443 A CN114736443 A CN 114736443A CN 202110020292 A CN202110020292 A CN 202110020292A CN 114736443 A CN114736443 A CN 114736443A
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- -1 polyethylene Polymers 0.000 title claims abstract description 70
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 69
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 55
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 59
- 238000004132 cross linking Methods 0.000 claims abstract description 30
- 150000002978 peroxides Chemical class 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- IGJPWUZGPMLVDT-UHFFFAOYSA-N tris(ethenyl)-tris(ethenyl)silyloxysilane Chemical compound C=C[Si](C=C)(C=C)O[Si](C=C)(C=C)C=C IGJPWUZGPMLVDT-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- BKPKTOIGWIYKJZ-UHFFFAOYSA-N [bis(ethenyl)-methylsilyl]oxy-bis(ethenyl)-methylsilane Chemical compound C=C[Si](C=C)(C)O[Si](C)(C=C)C=C BKPKTOIGWIYKJZ-UHFFFAOYSA-N 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- SPCHDFGQKLHKIZ-UHFFFAOYSA-N ethenyl-(ethenyl-methoxy-methylsilyl)oxy-methoxy-methylsilane Chemical compound CO[Si](C)(C=C)O[Si](C)(OC)C=C SPCHDFGQKLHKIZ-UHFFFAOYSA-N 0.000 claims description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 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 1
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 229910007266 Si2O Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- KGLJCWSSVJJHRY-UHFFFAOYSA-N ethenyl-[ethenyl(dimethoxy)silyl]oxy-dimethoxysilane Chemical compound CO[Si](OC)(C=C)O[Si](OC)(OC)C=C KGLJCWSSVJJHRY-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000004717 peroxide crosslinked polyethylene Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000008883 yougui Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention relates to the field of polyolefin, and discloses a crosslinkable polyethylene composition and application thereof, crosslinked polyethylene and a preparation method and application thereof. The composition comprises polyethylene, a peroxide crosslinking agent and a co-crosslinking agent; the peroxide crosslinking agent is used in an amount of 0.05 to 2 parts by weight relative to 100 parts by weight of polyethylene; the dosage of the auxiliary crosslinking agent is 0.05-2 parts by weight; the assistant crosslinking agent has a structure shown as formula I, Rn 1R2 (6‑n)Si2O is shown as formula I; wherein, in the formula I, R1Is alkenyl of C2-C5, R2Is methyl, ethyl, methoxy or ethoxy, and n is an integer of 1 to 6. The composition is prepared byHas high-temperature creep resistance, crosslinking degree and notch impact performance at minus 20 ℃, and obviously reduces the odor of a crosslinked polyethylene product prepared from the composition.
Description
Technical Field
The invention relates to the field of polyolefin, and particularly relates to a crosslinkable polyethylene composition and application thereof, crosslinked polyethylene and a preparation method and application thereof.
Background
Compared with non-crosslinked polyethylene, crosslinked polyethylene has excellent mechanical properties, environmental cracking resistance and high-temperature creep resistance, which are mainly attributed to the fact that linear thermoplastic polyethylene macromolecular chains are converted into reticular thermosetting macromolecular materials after being crosslinked. In addition to the properties of crosslinked polyethylene products, which are related to the structure and forming process of polyethylene, the degree of crosslinking is a major factor affecting the properties of crosslinked polyethylene products. The higher the crosslinking degree of the crosslinked polyethylene, the more perfect the crosslinking network, and the better the environmental stress cracking resistance, high temperature creep resistance and other properties of the product.
Crosslinked polyethylene articles are typically subjected to low and high temperature service environments during service, which have a significant impact on the article properties during service. The sample is embrittled under the application of low-temperature environment, and the impact property of the sample is poor; and the sample is softened due to the temperature rise in the process of using the sample in a high-temperature environment, so that obvious creep deformation can occur. It is therefore important to improve the impact properties of the samples at low temperatures and to reduce the creep deformation rate of the samples at high temperatures. At present, the temperature is mostly above minus 20 ℃ in most northern China and in south China in winter, so the impact property at the low temperature of minus 20 ℃ is an important index for representing the impact resistance of a sample.
In the preparation process of the crosslinked polyethylene, in the process of preparing a high crosslinking sample, a method mainly adopted for improving the crosslinking degree of the sample is to add more crosslinking agents or add a small amount of auxiliary crosslinking agents, wherein the addition of the auxiliary crosslinking agents has high efficiency and small dosage, so the application is wide. At present, the crosslinking aids such as (methyl) acrylate, organic allyl, maleimide and the like are widely used.
CN104334630A discloses a crosslinked polyethylene composition with improved processability comprising: 100 parts by weight of polyethylene, 0.03 to 5 parts by weight of a crosslinking agent, 0.03 to 5 parts by weight of a crosslinking accelerator, and 0.01 to 1.5 parts by weight of a radical inhibitor. The cross-linking agent is a peroxide cross-linking agent; the crosslinking accelerator is an organic substance containing maleimide groups, (methyl) acrylate groups and/or allyl groups, and/or a polymer with the vinyl content higher than 50%; the free radical inhibitor is an organic antioxidant, hydroquinone, and/or substituted hydroquinone.
CN106336568A discloses a crosslinked polyethylene composition, wherein the mass fraction of trichlorobenzene dissolved precipitate at 90 ℃ of the crosslinked polyethylene is 50-85%; the gel content of the crosslinked polyethylene is 20 to 70% by weight based on the total amount of the crosslinked polyethylene. The compositions likewise comprise customary crosslinking aids based on acrylate and/or allyl groups.
CN106977804A discloses a peroxide crosslinked polyethylene and a production process thereof, which comprises the following components in percentage by weight: polyethylene: 77.5 to 97.8 percent; porous adsorption material: 1 to 10 percent; a compatilizer: 0.5 to 5 percent; antioxidant: 0.3 to 0.5 percent; auxiliary crosslinking agent: 0.1-3%; lubricant: 0.2-1%; a crosslinking agent: 0.1 to 3 percent. The melt processability of crosslinked polyethylene is improved mainly by porous inorganic particles. The composition also uses conventional co-crosslinking agents of acrylate and/or allyl type (e.g., poly (triallyl isocyanurate), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, cumene hydroperoxide).
In the prior art, acrylate group and/or allyl group compounds are used as an auxiliary crosslinking agent for crosslinkable polyethylene, however, the auxiliary crosslinking agent has high irritation, so that the prepared crosslinked polyethylene product has a large odor, and the high-temperature creep resistance, crosslinking degree and minus 20 ℃ notch impact performance of the prepared crosslinked polyethylene cannot meet actual requirements.
Disclosure of Invention
The invention aims to overcome the problems of strong odor, low high-temperature creep resistance, low crosslinking degree and low-20 ℃ notch impact performance of crosslinked polyethylene prepared by the prior art, and provides a crosslinkable polyethylene composition and application thereof, crosslinked polyethylene and a preparation method and application thereof.
In order to achieve the above objects, in one aspect, the present invention provides a crosslinkable polyethylene composition, characterized in that the composition comprises polyethylene, a peroxide crosslinking agent, and an auxiliary crosslinking agent;
the peroxide crosslinking agent is used in an amount of 0.05 to 2 parts by weight relative to 100 parts by weight of polyethylene; the usage of the auxiliary crosslinking agent is 0.05-2 parts by weight;
the assistant crosslinking agent has a structure shown in a formula I,
Rn 1R2 (6-n)Si2o is shown as formula I;
wherein, in the formula I, R1Is alkenyl of C2-C5, R2Is methyl, ethyl, methoxy or ethoxy, and n is an integer of 1 to 8.
The second aspect of the present invention provides a method for preparing crosslinked polyethylene, characterized in that the method comprises the steps of:
s1, mixing the crosslinkable polyethylene composition, and carrying out melt extrusion processing by a double-screw extruder to obtain a crosslinkable polyethylene composition A;
s2, carrying out hot press molding on the crosslinkable polyethylene composition A, and cooling to room temperature to obtain crosslinked polyethylene;
wherein the crosslinkable polyethylene composition is the crosslinkable polyethylene composition described above.
In a third aspect, the present invention provides a crosslinked polyethylene obtainable by the above process.
The fourth aspect of the present invention provides an application of the crosslinkable polyethylene composition and crosslinked polyethylene in low temperature resistant plates, low temperature resistant sheets, low temperature resistant pipes and low temperature resistant drums.
Through the technical scheme, the crosslinkable polyethylene composition and the application thereof, the crosslinked polyethylene and the preparation method and the application thereof provided by the invention have the following beneficial technical effects:
the crosslinkable polyethylene composition provided by the invention comprises a peroxide crosslinking agent and an auxiliary crosslinking agent shown in a formula I, and the peroxide crosslinking agent and the auxiliary crosslinking agent can be matched with each other, so that the crosslinking degree, the high-temperature creep resistance and the notch impact strength at 20 ℃ below zero of the crosslinkable polyethylene composition are obviously improved; meanwhile, the auxiliary crosslinking agent represented by formula I has no pungent odor, so that the composition comprising the auxiliary crosslinking agent has a low odor.
Furthermore, the crosslinked polyethylene product prepared from the crosslinkable polyethylene composition provided by the invention has excellent mechanical property, environmental cracking resistance, high temperature creep resistance, and notched impact strength at minus 20 ℃, has low odor, and can be applied to the fields of refrigerator lining plates, concentrated sulfuric acid tanks and the like.
Drawings
Fig. 1 is a graph of the composite viscosity versus time for the crosslinkable polyethylene compositions provided in examples 1-2 and comparative examples 1, 3-4.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides in a first aspect a crosslinkable polyethylene composition, characterized in that the composition comprises polyethylene, a peroxide crosslinking agent and a co-crosslinking agent;
the peroxide crosslinking agent is used in an amount of 0.05 to 2 parts by weight relative to 100 parts by weight of polyethylene; the dosage of the auxiliary crosslinking agent is 0.05-2 parts by weight;
the auxiliary crosslinking agent has a structure shown in a formula I,
Rn 1R2 (6-n)Si2o is shown as formula I;
wherein, in the formula I, R1Is alkenyl of C2-C5, R2Is methyl, ethyl, methoxy or ethoxy, and n is an integer of 1 to 6.
In the invention, the crosslinkable polyethylene composition adopts peroxide as a crosslinking agent and is matched with the auxiliary crosslinking agent shown in the formula I, so that the high-temperature creep resistance, the crosslinking degree and the notch impact property at 20 ℃ below zero of the composition can be obviously improved, and the odor of a crosslinked polyethylene product prepared from the composition is obviously reduced.
Further, when the peroxide crosslinking agent and the co-crosslinking agent in the crosslinkable polyethylene composition satisfy the above-mentioned amount ranges, the composition thus obtained has a high crosslinking degree and is excellent in high-temperature creep resistance and-20 ℃ notched impact resistance, while having a low odor.
To further improve the overall properties of the crosslinkable polyethylene composition, the peroxide crosslinking agent is preferably used in an amount of 0.2 to 1.2 parts by weight, relative to 100 parts by weight of polyethylene; the amount of the auxiliary crosslinking agent is 0.2-1.5 parts by weight.
Further, the inventors have found that, when in formula I, R1Is alkenyl of C2-C4, R2When the crosslinking assistant agent is methyl, methoxy or ethoxy, and n is an integer of 2-6, the crosslinking degree, the high temperature creep resistance and the minus 20 ℃ notch impact performance of the crosslinkable polyethylene composition containing the crosslinking assistant agent shown in the formula I are further improvedAnd the odor of the composition is further reduced.
Further, in formula I, R1Is vinyl, R2Is methyl or methoxy, and n is an integer of 2 to 4.
According to the invention, the co-crosslinking agent is selected from at least one of tetramethyldivinyldisiloxane, 1, 3-dimethoxy-1, 3-dimethyl-1, 3-divinyldisiloxane, 1,3, 3-tetramethyl-1, 3-divinyldisiloxane, 1, 3-dimethyl-1, 1,3, 3-tetravinyldisiloxane and hexavinyldisiloxane.
According to the present invention, the peroxide crosslinking agent is at least one selected from the group consisting of 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, di-tert-butylperoxydicumyl, dicumyl peroxide and tert-butylcumyl peroxide.
According to the invention, the polyethylene is selected from at least one of high density polyethylene, linear low density polyethylene and low density polyethylene.
According to the invention, the polyethylene has a melt index at 190 ℃ and under a load of 2.16kg of from 2 to 50g/10min, preferably from 3 to 30g/10 min.
According to the invention, the composition also comprises an antioxidant; the antioxidant is used in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, relative to 100 parts by weight of polyethylene.
According to the invention, the antioxidant is at least one selected from antioxidant 168, 1010, DSTP and antioxidant 264
The second aspect of the present invention provides a method for preparing crosslinked polyethylene, characterized in that the method comprises the steps of:
s1, mixing the crosslinkable polyethylene composition, and performing melt extrusion processing by a double-screw extruder to obtain a crosslinkable polyethylene composition A;
s2, carrying out hot press molding on the crosslinkable polyethylene composition A, and cooling to room temperature to obtain crosslinked polyethylene;
wherein the crosslinkable polyethylene composition is the crosslinkable polyethylene composition described above.
According to the present invention, in step (1), the melt extrusion conditions include: the extrusion temperature is 80-150 ℃, preferably 110-140 ℃; the rotating speed is 10-200r/min, preferably 50-120 r/min.
According to the present invention, in the step (2), the conditions of the hot press molding include: the hot pressing temperature is 160-220 ℃, and preferably 180-200 ℃; the pressure is 10-200bar, preferably 80-150 bar; the hot pressing time is 3-20min, preferably 5-10 min.
According to the invention, in step (2), the cooling rate is 1-50 ℃/min, preferably 5-20 ℃/min.
In the present invention, the thickness of the crosslinked polyethylene is 1 to 100mm, preferably 2 to 30 mm.
In one embodiment of the present invention, the preparation method of the crosslinked polyethylene comprises the following steps:
1. firstly weighing the peroxide crosslinking agent, the crosslinking assistant, the optional antioxidant and the polyethylene particles according to the weight ratio, and then preliminarily mixing the components by adopting a high-speed mixer.
2. And adding the mixture into a double-screw extruder for melt extrusion processing to obtain the crosslinkable polyethylene composition A.
3. And (2) carrying out hot pressing on the composition A at 200 ℃ under the pressure of 100bar for 10min to prepare a sample with the thickness of 4mm, and then cooling the sample to room temperature at the speed of 10 ℃/min to obtain the crosslinked polyethylene.
In a third aspect, the invention provides a crosslinked polyethylene obtainable by the above process.
According to the invention, the notched impact strength of the crosslinked polyethylene at-20 ℃ is from 40 to 90kJ/m2Preferably 45-85kJ/m2。
According to the invention, the crosslinked polyethylene has a degree of crosslinking of from 30 to 97%, preferably from 60 to 97%.
In the invention, the crosslinking degree of the crosslinked polyethylene is characterized by the gel content of the crosslinked polyethylene.
According to the invention, the cross-linked polyethylene has a high-temperature creep deformation rate of 1 to 100%, preferably 30 to 90%, at 200 ℃.
The invention provides a use of the crosslinkable polyethylene composition or the crosslinked polyethylene in low temperature resistant plates, low temperature resistant sheets, low temperature resistant pipes and low temperature resistant barrels.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the crosslinking degree is characterized by adopting gel content, and the crosslinking degree is tested according to ASTM D2765-2011 by a specific test method: taking dimethylbenzene as a solvent, putting about 0.3g of a sample in a 150-micron copper net, wrapping the sample into a small sample bag, putting the small sample bag in a 160-DEG C solvent for extraction for 24 hours, taking out the sample bag, and putting the sample bag in an 80-DEG C oven for drying until the weight is constant;
the notched impact strength of the cantilever beam is according to ISO 180:2000, and the testing temperature is-20 ℃;
high temperature creep resistance: testing according to GB/T2951.11-2008, wherein the temperature is 200 ℃, the load is 0.2MPa, the thermal extension time is 15min, the recovery time is 5min, and the high-temperature creep resistance is represented by the elongation under the load;
the compound viscosity is tested by adopting rotational rheology, and the specific steps are that a sample is subjected to film pressing at 130 ℃ and 100bar to form a wafer with the thickness of 1.5 mm; then changing the complex viscosity change (complex viscocity) of the sample in the cross-linking process of the sample tested by a rotational rheometer, wherein the temperature is 150 → 200 ℃, the heating rate is 10 ℃/min, and the temperature is kept for 5min after the temperature reaches 200 ℃;
polyethylene is designated HDPE2911, melt index 20g/10min (190 ℃, 2.16kg), density 0.955g/cm3Purchased from compliant petrochemical companies;
antioxidant: antioxidant 168, available from carbofuran technologies, inc;
a crosslinking agent: 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane available from Arkema under the designation Luperox 101;
auxiliary crosslinking agent 1: TAIC, available from Sigma-aldrich;
auxiliary crosslinking agent 2: hexavinyldisiloxane, formula I wherein R1 is vinyl and n is 6, available from shanghai petrochemical company, ltd;
auxiliary crosslinking agent 3: cycloorganosiloxane, brand tetramethyltetravinylcyclotetrasiloxane, available from Sigma-aldrich.
Auxiliary crosslinking agent 4: 1, 3-dimethyl-1, 1,3, 3-tetraene disiloxane, formula I, wherein R1 is vinyl, n is 4, R2 is methyl, available from bailing technologies ltd, beijing;
auxiliary crosslinking agent 5: 1, 3-divinyl-1, 1,3, 3-tetramethoxydisiloxane, formula I, wherein R1 is vinyl, n is 2, and R2 is methoxy, was purchased from Shanghai Yougui New Material science and technology Co.
Examples and comparative examples
The formulation of the crosslinkable polyethylene composition is shown in table 1.
The preparation method of the crosslinked polyethylene comprises the following steps:
1. firstly weighing the peroxide crosslinking agent, the crosslinking assistant, the optional antioxidant and the polyethylene particles according to the weight ratio, and then preliminarily mixing the components by using a high-speed mixer.
2. And adding the mixture into a double-screw extruder for melt extrusion processing to obtain the crosslinkable polyethylene composition A.
3. And (2) carrying out hot pressing on the composition A at 200 ℃ under the pressure of 100bar for 10min to prepare a sample with the thickness of 4mm, and then cooling the sample to room temperature at the speed of 10 ℃/min to obtain the crosslinked polyethylene. The change in the complex viscosity of the crosslinkable polyethylene composition over time is shown in fig. 1.
TABLE 1
Note: x sample fracture
As can be seen from Table 1, the crosslinked polyethylenes provided in examples 1-5 of the present invention all have a high degree of crosslinking and a notched impact strength at-20 ℃ and are also superior in high temperature creep resistance compared to comparative examples 1-4.
Specifically, in example 1, after 0.5phr of the auxiliary crosslinking agent shown in formula I is adopted, the crosslinking degree of the prepared crosslinked polyethylene is 72.4%, the notch impact strength at 20 ℃ below zero reaches 48.3J/mm, and the elongation of a high-temperature creep sample is 80.1%.
In comparative example 1, however, when only 0.3phr of the crosslinking agent was added, the crosslinked polyethylene article obtained had a degree of crosslinking of 32.5%, a notched impact strength at-20 ℃ of 18.2J/mm, and a high-temperature creep sample fractured. Similarly, in comparative example 3, after 0.5phr of TAIC, the crosslinked polyethylene product obtained has 65.4% crosslinking degree, 38.5J/mm notch impact strength at minus 20 ℃ and 190.8% deformation rate of high temperature creep sample.
As can be seen from fig. 1, the complex viscosity of examples 1 and 2 is significantly higher than that of comparative examples 1,3 and 4, indicating that the viscosity of examples 1-2 is higher during high temperature creep at 200 ℃ to facilitate reduction of high temperature creep, and the data of table 1 also confirm that the high temperature creep resistance of examples 1 and 2 is superior to that of comparative examples 1,3 and 4.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A crosslinkable polyethylene composition, characterized in that the composition comprises polyethylene, a peroxide crosslinking agent and a co-crosslinking agent;
the peroxide crosslinking agent is used in an amount of 0.05 to 2 parts by weight relative to 100 parts by weight of polyethylene; the dosage of the auxiliary crosslinking agent is 0.05-2 parts by weight;
the auxiliary crosslinking agent has a structure shown in a formula I,
Rn 1R2 (6-n)Si2o is shown as formula I;
wherein, in the formula I, R1Is alkenyl of C2-C5, R2Is methyl, ethyl or methoxyOr ethoxy, n is an integer from 1 to 6.
2. The crosslinkable polyethylene composition according to claim 1, wherein the peroxide crosslinking agent is used in an amount of 0.2 to 1.2 parts by weight, relative to 100 parts by weight of polyethylene; the usage of the auxiliary crosslinking agent is 0.2-1.5 weight parts.
3. The crosslinkable polyethylene composition according to claim 1 or 2, wherein in formula I, R1Is alkenyl of C2-C4, R2Is methyl, methoxy or ethoxy, and n is an integer of 2 to 6;
preferably, in formula I, R1Is vinyl, R2Is methyl or methoxy, and n is an integer of 2 to 4.
4. The crosslinkable polyethylene composition according to any one of claims 1-3, wherein said co-crosslinking agent is selected from at least one of tetramethyldivinyldisiloxane, 1, 3-dimethoxy-1, 3-dimethyl-1, 3-divinyldisiloxane, 1,3, 3-tetramethyl-1, 3-divinyldisiloxane, 1, 3-dimethyl-1, 1,3, 3-tetravinyldisiloxane and hexavinyldisiloxane.
5. The crosslinkable polyethylene composition according to any one of claims 1-4, wherein said peroxide crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, di-tert-butylperoxydicumyl peroxide, dicumyl peroxide and tert-butylcumyl peroxide.
6. The crosslinkable polyethylene composition according to any one of claims 1-5, wherein said polyethylene is selected from at least one of high density polyethylene, linear low density polyethylene and low density polyethylene;
preferably, the polyethylene has a melt index at 190 ℃ and under a load of 2.16kg of from 2 to 50g/10min, preferably from 3 to 30g/10 min.
7. The crosslinkable polyethylene composition according to any one of claims 1-6, further comprising an antioxidant; the antioxidant is used in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, relative to 100 parts by weight of polyethylene;
preferably, the antioxidant is at least one selected from antioxidant 168, antioxidant 1010, antioxidant DSTP and antioxidant 264.
8. A process for the preparation of crosslinked polyethylene, characterized in that it comprises the following steps:
s1, mixing the crosslinkable polyethylene composition, and performing melt extrusion processing by a double-screw extruder to obtain a crosslinkable polyethylene composition A;
s2, carrying out hot press molding on the crosslinkable polyethylene composition A, and cooling to room temperature to obtain crosslinked polyethylene;
wherein the crosslinkable polyethylene composition is the crosslinkable polyethylene composition of any one of claims 1-7.
9. The production method according to claim 8, wherein in the step (1), the conditions of the melt extrusion include: the extrusion temperature is 80-150 ℃, preferably 110-140 ℃; the rotating speed is 10-200r/min, preferably 50-120 r/min;
in the step (2), the conditions of the hot press molding include: the hot pressing temperature is 160-220 ℃, and preferably 180-200 ℃; the pressure is 10-200bar, preferably 80-150 bar; the hot pressing time is 3-20min, preferably 5-10 min;
in the step (2), the cooling rate is 1-50 ℃/min, preferably 5-20 ℃/min.
10. Crosslinked polyethylene obtainable by the process according to claim 8 or 9.
11. The crosslinked polyethylene according to claim 10, wherein the crosslinked polyethylene has a notched impact strength at-20 ℃ of from 40 to 90kJ/m2Preferably 45-85kJ/m2；
Preferably, the crosslinked polyethylene has a degree of crosslinking of from 30 to 97%, preferably from 60 to 97%;
preferably, the crosslinked polyethylene has a high temperature creep deformation rate of 1 to 100%, preferably 30 to 90%, at 200 ℃.
12. Use of the crosslinkable polyethylene composition according to any one of claims 1-7 or the crosslinked polyethylene according to claim 10 or 11 in low temperature resistant sheets, low temperature resistant pipes and low temperature resistant tubs.
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