CN107814996A - A kind of preparation method of crosslinkable polyethylene modified materials - Google Patents
A kind of preparation method of crosslinkable polyethylene modified materials Download PDFInfo
- Publication number
- CN107814996A CN107814996A CN201610825763.9A CN201610825763A CN107814996A CN 107814996 A CN107814996 A CN 107814996A CN 201610825763 A CN201610825763 A CN 201610825763A CN 107814996 A CN107814996 A CN 107814996A
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- China
- Prior art keywords
- polyethylene
- weight
- crosslinkable polyethylene
- preparation
- crosslinkable
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- -1 polyethylene Polymers 0.000 title claims abstract description 159
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 149
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 145
- 239000000463 material Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 238000004132 cross linking Methods 0.000 claims abstract description 38
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229920001903 high density polyethylene Polymers 0.000 claims description 63
- 239000004700 high-density polyethylene Substances 0.000 claims description 63
- 238000004898 kneading Methods 0.000 claims description 56
- 239000000155 melt Substances 0.000 claims description 41
- 229920001684 low density polyethylene Polymers 0.000 claims description 22
- 239000004702 low-density polyethylene Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 11
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229920002943 EPDM rubber Polymers 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 3
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 claims description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 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 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000012933 diacyl peroxide Substances 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 description 23
- 238000001035 drying Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 229920000092 linear low density polyethylene Polymers 0.000 description 17
- 239000004707 linear low-density polyethylene Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000005453 pelletization Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000012752 auxiliary agent Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 7
- 239000003245 coal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000010117 shenhua Substances 0.000 description 7
- 102100021792 Gamma-sarcoglycan Human genes 0.000 description 6
- 101000616435 Homo sapiens Gamma-sarcoglycan Proteins 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229920003020 cross-linked polyethylene Polymers 0.000 description 4
- 239000004703 cross-linked polyethylene Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 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 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- CQMDBLRKZWOZIW-UHFFFAOYSA-N 2-Methyl-2-phenyl-undecane Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1 CQMDBLRKZWOZIW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- DYONERTXTCKSOJ-UHFFFAOYSA-N [O].[N].CC1(NC(CCC1)(C)C)C Chemical compound [O].[N].CC1(NC(CCC1)(C)C)C DYONERTXTCKSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C08L2312/00—Crosslinking
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to crosslinkable polyethylene preparation field, discloses a kind of preparation method of crosslinkable polyethylene modified materials.Including：(1) it will be kneaded containing polyethylene a, crosslinking agent, crosslinking coagent, antioxidant, lubricant and the compound of cross-linked stable agent, crosslinkable polyethylene masterbatch be made；On the basis of the total amount of the crosslinkable polyethylene masterbatch, the total content of the crosslinking agent and crosslinking coagent is 12~27 weight %；(2) the crosslinkable polyethylene masterbatch, polyethylene b and toughening element are separately added into double screw extruder and carry out melt blending, obtain crosslinkable polyethylene modified materials；On the basis of the total amount of the crosslinkable polyethylene modified materials, the total content of the crosslinking agent and crosslinking coagent is 0.008~0.05 weight %.Can be so that reaction not be crosslinked in preparation process, obtained crosslinkable polyethylene modified materials are free of any gel.
Description
Technical field
The present invention relates to crosslinkable polyethylene preparation field, in particular it relates to a kind of system of crosslinkable polyethylene modified materials
Preparation Method.
Background technology
Crosslinkable polyethylene modified materials are to usually contain the combination of polyethylene, crosslinking agent and auxiliary agent, antioxidant, lubricant etc.
Thing, production application can be further processed in fields such as sheet extrusion, foaming, rotational moulding, thus more and more closed
Note.But during above-mentioned composition is prepared into crosslinkable polyethylene modified materials by mixing, due to said composition
In contain crosslinking agent and crosslinking coagent, heat, shearing and pressure in the presence of, easily crosslinked in composition and cause to obtain
Modified materials in contain gel, influence following process use.Therefore in the industrial production, how to ensure that said composition is mixed in extrusion
It is kneaded uniformly during refining as crosslinkable polyethylene modified materials, but does not crosslink effect in advance, what is obtained is cross-linking poly-
Ethylene modified material does not contain gel, does not influence follow-up process operation, is to be badly in need of research and the problem solved.
A kind of screw combinations for being used to produce high-performance polypropylene filled composite materials of CN203919665U, including mutually nibble
The two root architecture identical screw rods closed, two screw rods are equidirectional rotation, and the every screw rod includes splined shaft, fixed cover
The screwing element and kneading member being located on the splined shaft, the screwing element include the length direction point along the splined shaft
The multiple forward screw thread blocks and multiple reverse thread blocks of cloth, the engaged element include the length direction point of serious Sohu's splined shaft
The multiple positive kneading blocks and multiple reverse kneading blocks of cloth, it is characterised in that the forward screw thread block includes 56/56,72/
72nd, 96/96,56/56A, 112/56SK, 112/112SK, the reverse thread block include 56/28L, the positive kneading block
Include K60 °/5/56, K45 °/5/56, K60 °/4/56, K30 °/7/72, ZME16/32, the reversely kneading block includes
K45 °/5/36L, the screwing element and the kneading member are set gradually in the following order on the splined shaft：56/56A、
112/56SK、112/112SK、112/56SK、96/96、72/72、56/56、K30°/7/72、K45°/5/56、K60°/4/56、
56/56、56/56、K90°/5/56、K45°/5/36L、96/96、96/96、72/72、56/56、96/96、96/96、72/72、
56/56、56/56、K45°/5/56、K60°/4/56、K90°/5/56、56/56、56/56、ZME16/32、ZME16/32、56/
56、56/56、K45°/5/56、K45°/5/56、K45°/5/56、K45°/5/36L、56/56、56/56、K45°/5/56、K45°/
5/56、K90°/5/56、56/28L、96/96、96/96、96/96、72/72、72/72、56/56、56/56、56/56.The practicality
It is new to have disclosed the special kneading blocks of ZME, and the mode that other kneading blocks are engaged, composite is improved in polypropylene
Distribution and dispersion effect so that final products can possess excellent tensile strength and curved while good impact flexibility is kept
The mechanical performances such as Qu Qiangdu, and the yield of composite can be improved, saved the energy.The invention is mainly nibbled by zigzag
It is scattered to improve to close block, belongs to Strong shear combination, the processing for being not suitable for crosslinkable polyethylene modified materials is kneaded.
CN102529062B discloses a kind of screw rod for extrusion processing nylon without carrying out drying and processing to nylon
Combination, including extruding machine, it is characterised in that combined on extruding machine with two root architecture identical screw rods (1), screw rod (1) includes
The interior pore area of splined shaft (2), screwing element (3) and kneading member (4) with spline, screwing element (3) and kneading member (4)
There are the spline (5) corresponding with the spline on splined shaft (2), the forward and reverse screwing element (3) of multiple differences and multiple differences
Forward and reverse kneading member (4) is fixed；The steering of two screw rods (1) is identical, turns timing, and two screw rod (1) phases differ 90 °
Phase angle；Every screw rod is：(A) solid conveying section, (B) melt zone, (C) mixing section, (D) exhaust section and (E) homogenizing zone totally 5
Section.The invention provides nylon (polyamide PA) and removes drying and processing from before processing, energy-conservation it is low with cost be used for extrusion processing Buddhist nun
Screw combinations of the dragon without carrying out drying and processing to nylon.But mainly for the Combination Design of hygroscopic material, this screw rod
Combination makes the moisture in nylon (polyamide PA) fully be volatilized, and keeps the stable mechanical property of nylon.Can but be not suitable for
The processing of crosslinked polyethylene modified materials is kneaded.
CN105291402A discloses a kind of screw combinations for the processing of nano-powder master batch, including twin-screw extruder
Machine, and the machine barrel being arranged on the twin (double) screw extruder；Two parallel screw rods (6) are provided with the machine barrel, on every screw rod (6)
It is mounted on the helical member of multiple different sizes；The screw rod (6) is symmetrically laid in machine barrel, and steering is identical, the screw rod (6)
One end connecting screw bearing (7), and drive the screw rod (6) to rotate by the screw-bearing (7)；It is characterized in that：The screw rod (6)
Including the splined shaft (6-1) with spline, screwing element (6-2) and kneading member (6-3)；The screwing element (6-2) and kneading
The endoporus of element (6-3) carries the spline (6-4) corresponding with splined shaft (6-1) upper spline；The forward and reverse spiral shell of multiple differences
Texel part (6-2) and the forward and reverse kneading member (6-3) of multiple differences are arranged on splined shaft (6-1) in order, splined shaft
The both ends of (6-1) are fixed by the screwing element arranged (6-2) and kneading member (6-3), one end of the screw rod (6) be provided with
The screw head (6-5) that spline (6-4) notch matches, the other end of screw rod (6) are fixedly connected by screw-bearing (7)；Should
The external diameter of screw head (6-5) is less than the external diameter of the screw rod (6).But the processing for being not suitable for crosslinkable polyethylene modified materials is kneaded.
CN104448461A discloses a kind of preparation method of crosslinkable polyethylene, including (a) is used under purification condition
Gravimetric feeding manner adds antioxidant in screw extruder, and is plastified, filtered after being contacted with low density polyethylene (LDPE),
It is granulated again using underwater cutpellet mode, obtains polyethylene cleaning particle；(b) by the poly- second by the way of water particle conveying
Alkene cleaning particle dehydrates after being transported to the height that subsequent step can be made to carry out feeding by Gravitative Loads；(c) conducting oneself with dignity
Under effect, the polyethylene cleaning particle preheating after dehydrating；(d) under purification condition, using gravimetric feeding manner
Crosslinking agent is mixed with the polyethylene cleaning particle after preheating, infiltrated.
The content of the invention
During the invention aims to overcome prior art to prepare crosslinkable polyethylene material, exist and trigger crosslinking anti-too early
A kind of the defects of containing cross-linked structure in the crosslinkable polyethylene material that should cause to obtain, there is provided crosslinkable polyethylene modified materials
Preparation method.
To achieve these goals, the present invention provides a kind of preparation method of crosslinkable polyethylene modified materials, including：(1)
It will be kneaded, be made containing polyethylene a, crosslinking agent, crosslinking coagent, antioxidant, lubricant and the compound of cross-linked stable agent
Crosslinkable polyethylene masterbatch；On the basis of the total amount of the crosslinkable polyethylene masterbatch, the crosslinking agent and crosslinking coagent it is total
Content is 12~27 weight %；(2) the crosslinkable polyethylene masterbatch, polyethylene b and toughening element are separately added into twin-screw
Melt blending is carried out in extruder, obtains crosslinkable polyethylene modified materials；Using the total amount of the crosslinkable polyethylene modified materials as
Benchmark, the total content of the crosslinking agent and crosslinking coagent is 0.8~3 weight %.
Pass through above-mentioned technical proposal, prepared, first prepared cross-linking poly- containing crosslinking agent and various auxiliary agents etc. by substep
Ethene masterbatch, wherein crosslinking agent and crosslinking coagent content are high；Then again by crosslinkable polyethylene masterbatch and substantial amounts of polyethylene, increasing
Tough component extrusion carries out melt blending, reduces crosslinking agent and crosslinking coagent content, can be more beneficial for uniformly dividing for various auxiliary agents
Dissipate, and melt blending process is carried out under conditions of reaction is not crosslinked, so as to efficiently against cross-linking what is obtained
Cross-linked structure be present in PE modified material.
Further, in the double screw extruder for extrude melt blending, the screw rod used has specific screw rod
Combination, especially the melt zone part in screw rod, can using the screwing element and the permutation and combination method of kneading member especially set
So that the frictional heat of crosslinkable polyethylene masterbatch, polyethylene b, toughening element in extrusion is few, obtained cross-linking poly- second
Alkene modified materials are free of any gel.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the overall structural representation of screw rod；
Fig. 2 is the structural representation of screwing element；
Fig. 3 is the structural representation of kneading member.
Description of reference numerals
1st, screw rod 2, splined shaft 3, screwing element 4, kneading member
5th, spline A, solid conveying section B, melt zone C, mixing section
D, exhaust section E, homogenizing zone
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of crosslinkable polyethylene modified materials, including：(1) polyethylene a, crosslinking will be contained
Agent, crosslinking coagent, antioxidant, the compound of lubricant and cross-linked stable agent are kneaded, and crosslinkable polyethylene masterbatch is made；With
On the basis of the total amount of the crosslinkable polyethylene masterbatch, the total content of the crosslinking agent and crosslinking coagent is 12~27 weight %；
(2) the crosslinkable polyethylene masterbatch, polyethylene b and toughening element are separately added into double screw extruder and melt altogether
It is mixed, obtain crosslinkable polyethylene modified materials；On the basis of the total amount of the crosslinkable polyethylene modified materials, the crosslinking agent and friendship
The total content for joining auxiliary agent is 0.8~3 weight %.
In preparation method provided by the invention, step (1) is used to obtain cross-linking poly- containing the various auxiliary agents such as crosslinking agent
Ethene masterbatch, content concn of the various auxiliary agents in the crosslinkable polyethylene masterbatch are higher.The crosslinkable polyethylene is made
Melting temperature during masterbatch to be less than crosslinking agent and crosslinking coagent crosslinks the temperature of reaction, but polyethylene a can be melted
.Preferably, step (1) can be first by polyethylene a, crosslinking agent, crosslinking coagent, antioxidant, lubricant and cross-linked stable agent
It is uniformly the compound to be fully mixed in high-speed mixer, such as 3~5min；Then the compound is passed through into double spiral shells
Bar extruder realizes the mixing, carries out extruding pelletization and obtains crosslinkable polyethylene masterbatch.Wherein, each temperature of double screw extruder
The temperature of degree section can be preferably set to 130~145 DEG C, and the rotating speed of screw rod can be 60~350rpm.Routine can be selected
Double screw extruder, such as a diameter of 36~96mm of screw rod, draw ratio (spiro rod length and diameter ratio) are (36~48)：1.
During the extruding pelletization is realized and is kneaded, the temperature of double screw extruder does not have without rise or extruder electric current suddenly
Rise suddenly, it may be said that do not have cross-linking reaction during bright extruding pelletization.
In the case of, according to the invention it is preferred to, in step (1), the polyethylene a is selected from high density polyethylene (HDPE) and/or low close
Spend polyethylene.
Preferably, the density of the high density polyethylene (HDPE) is 0.94~0.965g/cm3, at 2.16 kg load 190 DEG C when
Melt index (MI) be 1~20g/10min.The high density polyethylene (HDPE) is known substance, can commercially available Shenhua packet header coal system
8007 (HDPE, melt index 8.2g/10min, density 0.963g/cm of oily Co., Ltd3)。
Preferably, the density of the low density polyethylene (LDPE) is 0.91~0.935g/cm3, at 2.16 kg load 190 DEG C when
Melt index be 1~20g/10min.The low density polyethylene (LDPE) is known substance, can commercially available Shenhua packet header coal liquifaction have
2426H (LDPE, melt index 2.1g/10min, density 0.924g/cm of limit company3)。
According to the present invention, the concentration of the summation for feeding intake to obtain the crosslinking agent and crosslinking coagent of each component in step (1)
Higher crosslinkable polyethylene masterbatch.It is described relative to the polyethylene a of 100 parts by weight in step (1) under preferable case
Crosslinking agent is 20~25 parts by weight, and the crosslinking coagent is 5~10 parts by weight, and the antioxidant is 2~15 parts by weight, the profit
Lubrication prescription is 5~15 parts by weight, and the cross-linked stable agent is 1~5 parts by weight.
In the present invention, the crosslinking agent can be selected from cumyl peroxide, benzoyl peroxide, hydrogen peroxide diisopropyl
Benzene, TBHP, 2,5- dimethyl -2,5- di-t-butyl hexane peroxides, 2,5- dimethyl -2,5- di-t-butyl mistakes
Aoxidize -3- alkynes, diacyl peroxide, di-tert-butyl peroxide, alkyl peroxide, dilauroyl peroxide, peroxide
Change at least one of MEK and cyclohexanone peroxide.
In the present invention, the crosslinking coagent can be selected from poly- 1,2- butadiene, diallyl p phthalate (DATP), two
Vinyl benzene (DVB), TAC (TAC), TAC (TAP) and triallyl isocyanate
At least one of (TAIC).Wherein the weight average molecular weight of poly 1,2-butadiene is 0.7 ten thousand~90,000.
In the present invention, the antioxidant can be conventional selection, preferably antioxidant 1010 and/or irgasfos 168.Institute
It is known substance to state antioxidant, can be commercially available by Chemical Reagent Co., Ltd., Sinopharm Group.
In the present invention, the lubricant can be conventional selection, preferably Tissuemat E, such as can commercially available Honeywell
The commodity of company obtain.
In the present invention, the cross-linked stable agent is free radical inhibitors, preferably phenols, quinones or arene nitro compound
Polymerization inhibitor, it is more preferably selected from phosphorous acid three (TEMPO) ester, (the 4- t-octyl benzene of 2,2- bis-
Base) at least one of -1- picryls hydrazine and NO free radical piperidine alcohols.
In preparation method provided by the invention, step (2) is used to dilute the crosslinkable polyethylene masterbatch, makes wherein to contain
Various auxiliary agents concentration, especially crosslinking agent and crosslinking coagent concentration, obtained crosslinkable polyethylene can be met and be modified
The composition requirement of material, it may be adapted in further processing use.
In the step (2) of the present invention, crosslinkable polyethylene masterbatch, polyethylene b, toughening element three parts material, preferably together
When from different charge door add double screw extruder.And crosslinkable polyethylene masterbatch, polyethylene b and toughening element are according to one
Certainty ratio relation is fed intake, female relative to the crosslinkable polyethylene of 100 parts by weight in step (2) under preferable case
Material, the polyethylene b is 500~1000 parts by weight, and the toughening element is 35~400 parts by weight.Can be the poly- second
Alkene b：The toughening element：The weight ratio of crosslinkable polyethylene master batch is (5~10)：(0.35~4)：1.
According to the present invention, step (2) can be used for diluting various auxiliary agents in the crosslinkable polyethylene masterbatch, especially hand over
Join the concentration of agent and crosslinking coagent, the polyethylene b can select identical polyethylene with the polyethylene a, can also basis
The polyethylene b and polyethylene a is needed to select different polyethylene.Preferably, the polyethylene b is selected from high density polyethylene (HDPE)
And/or low density polyethylene (LDPE)；It is preferred that the density of the high density polyethylene (HDPE) is 0.94~0.965g/cm3, in 2.16kg load
Melt index at lower 190 DEG C is 1~20g/10min；The density of the low density polyethylene (LDPE) is 0.91~0.935g/cm3,
Melt index when 2.16kg load is lower 190 DEG C is 1~20g/10min.The high density polyethylene (HDPE) is known substance, can be with business
Purchase 8007 (HDPE, melt index 8.2g/10min, density 0.963g/cm of packet header coal liquifaction Co., Ltd of Shenhua3).Institute
State low density polyethylene (LDPE) known substance, can commercially available packet header coal liquifaction Co., Ltd of Shenhua 2426H (LDPE, melt index
2.1g/10min, density 0.924g/cm3)。
According to the present invention, the toughening element can play a part of improving toughness of material, under preferable case, the toughness reinforcing
Component is selected from least one of LLDPE, ethylene-octene copolymer and ethylene propylene diene rubber.
Preferably, the density of the LLDPE is 0.91~0.935g/cm3, at 2.16 kg load 190
DEG C when melt index be 1~20g/10min.The LLDPE is known substance, can commercially available Shenhua packet header
7042 (LLDPE, melt index 2g/10min, density 0.92g/cm of coal liquifaction Co., Ltd3), the 8320 of Daqing petrochemical company
(LLDPE, melt index (MI) 20g/10min, density 0.926g/cm3)。
Preferably, in the ethylene-octene copolymer, the contents of octene based structures can be 20~30 weight %, described
The number-average molecular weight of ethylene-octene copolymer (POE) can be 7000~20000, and melt index (MI) is 2~7g/10min, density
For 0.75~0.95g/cm3.The ethylene-octene copolymer is known substance, can commercially available Dow Chemical
POE8200。
Preferably, the ethylene propylene diene rubber is the terpolymer of ethene, propylene and non-conjugated diene hydrocarbon, wherein non-common
Yoke alkadienes can be ethylidene norbornene (ENB) or dicyclopentadiene (DCPD).Ethylene, propylene in the ethylene propylene diene rubber
Than for 80：20 to 50：50, ENB contents are 0.5~10 weight %.(125 DEG C) of the Mooney viscosity of the ethylene propylene diene rubber is 20
~100.The ethylene propylene diene rubber is known substance, can commercially available Dow Chemical commodity.
In preparation method provided by the invention, further, the double screw extruder used in step (2) is preferably especially
The screw combinations of setting, the crosslinkable polyethylene masterbatch, polyethylene b, toughening element is set to be carried out in double screw extruder
During melt blending, the screw rod being subject to engages shear action stable and uniform, and caused frictional heat is few, so as to both complete
The molten homogeneous blending of material does not make crosslinking agent and crosslinking coagent crosslink reagentia again.
In the case of, according to the invention it is preferred to, in step (2), as shown in figure 1, the screw rod group in the double screw extruder
Conjunction includes intermeshing two root architectures identical screw rod 1；Screw rod 1 includes splined shaft 2, screwing element 3 and kneading member 4；It is more
The spline that the screwing element 3 of the individual positive and negative rotation of difference and the kneading member 4 of multiple Bu Tong positive and negative rotations are carried by respective endoporus
Groove 5 is sleeved on splined shaft 2.
According to the present invention, as shown in Fig. 2 screwing element 3 has the endoporus with spline 5.Under preferable case, screw thread member
The helical pitch of part 3 is 44~96mm, and the length of screwing element 3 is 44~96mm.In the present invention, screwing element can be represented with X/Y
For forward screw thread element, X/YL represents that screwing element is reverse-flight elements, and X/YA represents start screw threads element；Wherein X is represented
The helical pitch of screwing element, Y represent the length of screwing element.
According to the present invention, as shown in figure 3, kneading member 4 has the endoporus with spline 5, kneading member 4 can be by more
Block kneading block forms.Heterogeneous Permutation between polylith kneading block.The outer shape in the section of the vertical endoporus of kneading block is approximately oval
Shape.Under preferable case, the error angle of kneading member 4 is 30~60 °, and the length of kneading member 4 is 44~56mm, kneading member 4
Kneading block number be 4~6.In the present invention, positive kneading member can be represented with θ/n/m, represents reversely to pinch with θ/n/mL
Close element；Wherein, θ represents the error angle of kneading member, and n represents the number of kneading block, and m represents the length of whole kneading member.
In the case of, according to the invention it is preferred to, every screw rod 1 includes what is divided successively towards end from the driving end of screw rod 1
Solid conveying section A, melt zone B, mixing section C, exhaust section D and homogenizing zone E.
In the present invention, the solid conveying section A be used for convey from charge door material (such as crosslinkable polyethylene masterbatch,
Polyethylene b, toughening element) and prevent flash.In the solid conveying section, it is desirable to which this section has larger appearance material space to adapt to add
The adjustment of doses, prevent material is accumulated in spout from producing flash.The solid conveying section, can also be by pine in addition to conveying function
Degree of filling of the scattered granular material compacting or raising granular material in screw rod, to promote fusion plastification of the material at next section.
Therefore, driving end terminad descending change of the screw channel volume of the screwing element 3 of this section along screw rod 1, the spiral shell of screwing element 3
The descending gradual change of helical pitch of line.Preferably, heretofore described solid conveying section is using medium screw channel, large pitch, positive spiral shell
Line.Such as a kind of preferred embodiment, the arrangement of multiple screwing elements 3 of the solid conveying section is formed from the transmission of screw rod 1
End terminad is followed successively by 56/56A, and 96/96,96/96,72/72,72/72,56/56,44/44.
In the present invention, the melt zone B is used to pass through heat transfer and fricting shearing, material is fully melted and is homogenized.
In this section, material starts to melt after the solid conveying section A is by certain compression, and mixes.Make material melts
Thermal source has two kinds of sources, first, the external heat that barrel heat provides, another is the shear heat of screw rod.The shear heat of screw rod be according to
It is caused by high shear forces caused by the element of this section.Preferably, the melt zone B contains at least two groups of engaged sections, often
Section engaged section contains at least two kneading member 4；Contain at least one screwing element 3 between the engaged section；The melt zone contains
There is the screwing element 3 of at least one derotation.Compress and make by the backflow of the screwing element 3 of high shear and the derotation of kneading member 4
With plastic pellet fusion plastification can be made.
In the case of, according to the invention it is preferred to, the melt zone contains at least two groups of engaged sections, every section of engaged section and contained at least
1 kneading member 4；Contain at least one screwing element 3 between the engaged section；The melt zone contains at least one reverse spiral shell
Texel part or a reverse kneading member.
Preferably, when the engaged section that the melt zone contains be containing reverse kneading member when, close to positive kneading member
Number be no more than 1, can provide and effect is more suitably blended, and prevent to be crosslinked.
Preferably, when the engaged section that the melt zone contains is without reverse kneading member, the number of positive kneading member
Mesh is not less than 2, can provide and effect is more suitably blended, and prevent to be crosslinked.
In the present invention, forming a kind of preferred embodiment of the melt zone can be, form the multiple of the melt zone
The arrangement of screwing element 3 and kneading member 4 is followed successively by 45 °/5/56,45 °/5/ from the end of solid conveying section A to the screw rod 1
56,45 °/56/56,44/44,45 °/5/56,60 °/4/56,56/56,44/44,60 °/4/44,45 °/5/56L.
In the present invention, the mixing section C has distributivity and dispersed immixture, the material of melting is further refined
With it is uniform.Material is in molten condition after the melt zone, and the mixing in material between each component is melting since melting
During the sizes of various polymer occur further drastically to change, from primary millimetre-sized macroparticle to melting at the end of
Micron order.Due to the particle basic fusion plastification in the material that is come out from the melt zone, it is main to enter the mixing section
Based on scattered.It is spaced with kneading member 4 and screwing element 3 in the mixing section, moderate shear kneading disc is formed, to keep away
Exempt to shear superheating phenomenon.Such as a kind of preferred embodiment, form the multiple screwing elements 3 and kneading member 4 of the mixing section C
Arrangement be followed successively by 56/56,44/44,44/44,44/44,45 °/5/44,45 °/5/ from the end of melt zone B to the screw rod 1
44,45 °/5/44,56/56,56/56,44/44,44/44,45 °/5/44,45 °/5/56,56/56.
In the present invention, the exhaust section D is used to discharge the impurity such as steam, low molecular weight substance.In the exhaust section, thing
The flow performance of material is that the material of complete molten condition depressurizes suddenly after compression, and volatile material is rapid under vacuum
Volatilization, depart from melt.Preferably, the screwing element 3 of equal lead during the exhaust section can use, to form low degree of filling and thin
Melt zone, material is had the Free Surface that can be exposed, in favor of the discharge of gas.Such as a kind of preferred embodiment, composition
The arrangement of multiple screwing elements 3 of the exhaust section D is followed successively by 56/56,44/44 from the end of mixing section C to the screw rod 1,
44/44。
In the present invention, the homogenizing zone E is used to convey and be pressurized, and establishes certain pressure, makes to export in double screw extruder
Material at the die orifice of setting has certain consistency, is easy to material to discharge.The homogenizing zone E further mixes material simultaneously
Close, be finally reached the purpose of smooth extruding pelletization.Preferably, the homogenizing zone can by the helical pitch gradual change of screwing element 3 or
Screw channel gradual change is pressurized to realize.Such as a kind of preferred embodiment, form multiple screwing elements 3 of the homogenizing zone E and mediate
The arrangement of element 4 is followed successively by 45 °/5/44,60 °/4/44,64/64,64/64,44/ from the end of exhaust section D to the screw rod 1
44,44/44.
In the case of, according to the invention it is preferred to, the steering of two screw rods 1 is identical；During rotation, the phase difference of two screw rods 1
90 ° of phase angles.
In the case of, according to the invention it is preferred to, a diameter of 36~96mm of screw rod 1, draw ratio is (36~48)：1.It is a kind of excellent
Select embodiment, a diameter of 65mm of screw rod 1, draw ratio 36：1.
In the present invention, two screw rods 1 are placed in the machine barrel of double screw extruder.Heating is coated with the machine barrel
Area.From the driving end terminad of screw rod 1, the heating zone is equidistantly positioned as from the first heating zone to the 9th heating zone, such as Fig. 1
It is shown.
In the present invention, the melt blending of step (2) is realized, the temperature of the heating zone of double screw extruder can be with
It is arranged to 140~145 DEG C.It is preferred that a kind of embodiment, according to temperature of the heating zone from the first heating zone to the 9th heating zone
Degree is set as 140 DEG C, 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C.The rotating speed of screw rod 1 can be with
For 100~300rpm, rotating speed described in preferably a kind of embodiment is 200rpm.
In the present invention, the melt blending of step (2) is carried out, the melt temperature of extrudate can be higher than above-mentioned heating zone
Design temperature, but the method provided by the invention using crosslinkable polyethylene masterbatch still can ensure to finally give it is cross-linking
Cross-linked structure is not formed in PE modified material.
The melted melt that preparation method provided by the invention can also include extruding double screw extruder in step (2) passes through
Underwater pelletizer pelletizing, it is crosslinkable polyethylene modified materials that then 80~100 DEG C, which carry out 2~4h of drying,.
In the present invention, when carrying out the melt blending of step (2), it can observe by the extrudate of extruder extrusion
The gel content of form and final crosslinkable polyethylene modified materials come evaluate the present invention method effect.Wherein, can hand over
Joining the gel content of PE modified material can be measured by determining dimethylbenzene insolubles content method, judge crosslinkable polyethylene
Whether cross-linked structure is formed in modified materials.Under preferable case, the weight % of gel content 0 of the crosslinkable polyethylene modified materials.
In the present invention, when carrying out the melt blending of step (2), extruder electric current can reflect spiral shell in extrusion
The size of bar moment of torsion, whether reflection extrusion is difficult, directly proportional to the viscosity of extrudate., can be anti-when extruder electric current is big
It is big to reflect the viscosity of extrudate, extruder screw moment of torsion is big, illustrates that the material in extruder carries out extrusion and needs to consume more energy
Amount, the material small compared to extruder electric current under the same terms are more difficult to process.
The present invention will be described in detail by way of examples below.
In following examples, the gel content of crosslinkable polyethylene modified materials is by determining dimethylbenzene insolubles content method
Measure；
Material in following examples and comparative example,
HDPE (DMDA 8007, melt index (MI) 8.3g/10min, density 0.963g/cm3), Shenhua packet header coal liquifaction
Co., Ltd；
LLDPE (DMDA 7042, melt index (MI) 2g/10min, density 0.92g/cm3), Shenhua packet header coal liquifaction has
Limit company；
LLDPE (8320, melt index (MI) 20g/10min, density 0.926g/cm3), Daqing petrochemical company；
POE (8200, melt index (MI) 5g/10min, density 0.87g/cm3), Dow Chemical；
Crosslinking agent is di-t-butyl peroxide, J＆K Scientific；
Crosslinking coagent is Triallyl isocyanurate (TAIC) (technical grade), J＆K Scientific；
Cross-linked stable agent is phosphorous acid three (TEMPO) ester, J＆K Scientific；
Antioxidant 1010, irgasfos 168：Chemical Reagent Co., Ltd., Sinopharm Group；
Tissuemat E (A-C316A), Honeywell Inc..
Embodiment 1
(1) by 50kg high density polyethylene (HDPE)s powder (DMDA8007), 11.25kg di-t-butyl peroxide, 3.75kg's
Triallyl isocyanurate, 3kg antioxidant 1010,3kg irgasfos 168,2kg Tissuemat E (A-C316A),
2.5kg phosphorous acid three (TEMPO) ester is put into high-speed mixer and mixing 5 minutes, adds extrusion
Extrusion prepares crosslinkable polyethylene master batch at 145 DEG C of machine.
(2) by 500kg high density polyethylene (HDPE)s, 200kg LLDPEs (DMDA7042), the cross-linking poly- second of 50kg
Alkene masterbatch, it is put into three different weightless titles, by high density polyethylene (HDPE), LLDPE, crosslinkable polyethylene masterbatch
According to 10:4:65 type (screw diameter 65mm) equidirectional parallel double-screw extruder (Nanjing Rhea extruders are expected under 1 mass ratio
Tool equipment Co., Ltd, TSE65) in extruded, prepare crosslinkable polyethylene modified materials, the temperature of 9 sections of heating zones of extruder
Degree is respectively 140 DEG C, and 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, extruder rotating speed is
200rpm, the melt of double screw extruder is flowed out through underwater pelletizer pelletizing, 80 DEG C of feed bin of drying is drawn onto and carries out drying 2h, obtain
Crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；45 ° of (melt zone B)/
5/56,45 °/5/56,45 °/5/56,44/44,45 °/5/56,60 °/4/56,56/56,44/44,60 °/4/44,45 °/5/
56L；(mixing section C) 56/56,44/44,44/44,44/44,45 °/5/44,45 °/5/44,45 °/5/44,56/56,56/56,
44/44,44/44,45 °/5/44,45 °/5/56,56/56；(exhaust section D) 56/56,44/44,44/44；45 ° of (homogenizing zone E)/
5/44,60 °/4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Comparative example 1
First by 11.25kg di-t-butyl peroxide, 3.75kg Triallyl isocyanurate, 3kg antioxidant
1010,3kg irgasfos 168,2kg Tissuemat E (A-C316A), 2.5kg (2,2,6, the 6- tetramethyl piperidines of phosphorous acid three
NO free radical) ester adds high-speed mixer and mixing 5min and is used as assistant composition, be then added in weightless title -1；
High density polyethylene (HDPE) 550kg skies are delivered into weightless title -2, LLDPE (DMDA 7042) 200kg is empty
Deliver to weightless title -3；
By assistant composition, high density polyethylene (HDPE), LLDPE according to 0.51：11：4 mass ratioes, under expect
Extruded in 65 type equidirectional parallel double-screw extruders, prepare crosslinkable polyethylene master batch, the temperature of 9 sections of heating zones of extruder
Degree is respectively 140 DEG C, and 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, extruder rotating speed is
200rpm, the melt of double screw extruder is flowed out through underwater pelletizer pelletizing, 80 DEG C of feed bin of drying is drawn onto and carries out drying 2h, obtain
Crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；45 ° of (melt zone B)/
5/56,45 °/5/56,45 °/5/56,44/44,45 °/5/56,60 °/4/56,56/56,44/44,60 °/4/44,45 °/5/
56L；(mixing section C) 56/56,44/44,44/44,44/44,45 °/5/44,45 °/5/44,45 °/5/44,56/56,56/56,
44/44,44/44,45 °/5/44,45 °/5/56,56/56；(exhaust section D) 56/56,44/44,44/44；45 ° of (homogenizing zone E)/
5/44,60 °/4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Comparative example 2
(1) by 50kg high density polyethylene (HDPE)s powder (DMDA8007), 11.25kg di-t-butyl peroxide, 3.75kg's
Triallyl isocyanurate, 3kg antioxidant 1010,3kg irgasfos 168,2kg Tissuemat E (A-C316A),
2.5kg phosphorous acid three (TEMPO) ester is put into high-speed mixer and mixing 5 minutes, adds extrusion
Extrusion prepares crosslinkable polyethylene master batch at 145 DEG C of machine.
(2) by 500kg high density polyethylene (HDPE)s, 200kg LLDPEs (DMDA7042), the cross-linking poly- second of 50kg
Alkene masterbatch, it is put into three different weightless titles, by high density polyethylene (HDPE), LLDPE, crosslinkable polyethylene masterbatch
According to 10:4:65 type (screw diameter 65mm) equidirectional parallel double-screw extruder (Nanjing Rhea extruders are expected under 1 mass ratio
Tool equipment Co., Ltd, TSE65) in extruded, prepare crosslinkable polyethylene modified materials, the temperature of 9 sections of heating zones of extruder
Degree is respectively 140 DEG C, and 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, extruder rotating speed is
200rpm, the melt of double screw extruder is flowed out through underwater pelletizer pelletizing, 80 DEG C of feed bin of drying is drawn onto and carries out drying 2h, obtain
Crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；(melt zone B) 56/
56,60 °/5/56,56/56,44/44,45 °/5/56,60 °/4/56,56/56,44/44,60 °/4/44,45 °/5/56L；It is (mixed
Refine section C) 56/56,44/44,44/44,44/44,44/44,45 °/5/44,45 °/5/44,56/56,56/56,44/44,44/
44,45 °/5/44,45 °/5/56,56/56；(exhaust section D) 56/56,44/44,44/44；(homogenizing zone E) 45 °/5/44,60 °/
4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Embodiment 2
(1) by 50kg high density polyethylene (HDPE)s (DMDA 8007) powder, 10kg di-t-butyl peroxide, 5kg three allyls
Base isocyanuric acid ester, 2kg antioxidant 1010,2kg irgasfos 168,4.5kg Tissuemat E (A-C316A), 2kg Asia
Tricresyl phosphate (TEMPO) ester is put into high-speed mixer and mixing 5min, adds at 140 DEG C of extruder
Extrusion prepares crosslinkable polyethylene master batch.
(2) by high density polyethylene (HDPE) 500kg, LLDPE (8320) 100kg, crosslinkable polyethylene masterbatch
50kg, it is put into three different weightless titles, high density polyethylene (HDPE), LLDPE, crosslinkable polyethylene masterbatch is pressed
According to 10:2:Expect under 1 mass ratio and extruded in 65 type equidirectional parallel double-screw extruders, prepare crosslinkable polyethylene modification
Material, the temperature of 9 sections of heating zones of extruder are respectively 140 DEG C, 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, and 145
DEG C, 145 DEG C, extruder rotating speed is 200rpm, flows out the melt of double screw extruder through underwater pelletizer pelletizing, is drawn onto drying material
80 DEG C of storehouse carries out drying 2h, obtains crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；45 ° of (melt zone B)/
5/56,45 °/5/56,56/56,44/44,45 °/5/56,60 °/4/56,56/56,44/44,60 °/4/44,45 °/5/56L；
(mixing section C) 56/56,44/44,44/44,44/44,44/44,45 °/5/44,45 °/5/44,56/56；(exhaust section D) 56/
56,44/44,44/44,45 °/5/44,45 °/5/56,56/56,56/56,44/44,44/44；(homogenizing zone E) 45 °/5/44,
60 °/4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Comparative example 3
First by 10kg di-t-butyl peroxide, 5kg Triallyl isocyanurate, 2kg antioxidant 1010,2kg
Irgasfos 168,4.5kg Tissuemat E (A-C316A), (2,2,6,6- tetramethyl piperidine nitrogen oxygen are free for 2kg phosphorous acid three
Base) ester adds high-speed mixer and mixing 5min and is used as assistant composition, be then added in weightless title -1；
High density polyethylene (HDPE) 550kg skies are delivered into weightless title -2, LLDPE (8320) 100kg skies deliver to mistake
Claim -3 again；
By assistant composition, high density polyethylene (HDPE), LLDPE according to 0.51：11：Expect 65 under 2 mass ratioes
Extrusion is carried out in type equidirectional parallel double-screw extruder and prepares crosslinkable polyethylene master batch, the temperature of 9 sections of heating zones of extruder
Respectively 140 DEG C, 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, extruder rotating speed is
200rpm, the melt of double screw extruder is flowed out through underwater pelletizer pelletizing, 80 DEG C of feed bin of drying is drawn onto and carries out drying 2h, obtain
Crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；45 ° of (melt zone B)/
5/56,45 °/5/56,45 °/5/56,44/44,45 °/5/56,60 °/4/56,56/56,60 °/4/44,60 °/4/44,45 °/5/
56L；(mixing section C) 56/56,44/44,44/44,44/44,45 °/5/44,45 °/5/44,45 °/5/44,56/56,56/56,
44/44,44/44,45 °/5/44,45 °/5/56,56/56；(exhaust section D) 56/56,44/44,44/44；45 ° of (homogenizing zone E)/
5/44,60 °/4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Embodiment 3
(1) by 50kg high density polyethylene (HDPE)s powder (DMDA 8007), 11.25kg di-t-butyl peroxide, 3.75kg's
Triallyl isocyanurate, 3kg antioxidant 1010,3kg irgasfos 168,2.5kg Tissuemat E (A-C316A),
2kg phosphorous acid three (TEMPO) ester, high-speed mixer and mixing 5min is put into, adds extruder
Extrusion prepares crosslinkable polyethylene master batch at 135 DEG C.
(2) it is high density polyethylene (HDPE) 300kg, ethylene-octene copolymer (POE8200) 17.5kg, crosslinkable polyethylene is female
Expect 50kg, be put into three different weightless titles, high density polyethylene (HDPE), ethylene-octene copolymer, crosslinkable polyethylene masterbatch are pressed
According to 6:0.35:Expect under 1 mass ratio and extruded in 65 type equidirectional parallel double-screw extruders, prepare crosslinkable polyethylene and change
Property material, the temperature of 9 sections of heating zones of extruder is respectively 140 DEG C, 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C,
145 DEG C, 145 DEG C, extruder rotating speed is 200rpm, flows out the melt of double screw extruder through underwater pelletizer pelletizing, is drawn onto baking
80 DEG C of siccative storehouse carries out drying 2h, obtains crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；45 ° of (melt zone B)/
5/56,45 °/5/56,45 °/5/56,44/44,45 °/5/56,60 °/4/56,56/56,44/44,60 °/4/44,45 °/5/
56L；(mixing section C) 56/56,44/44,44/44,44/44,45 °/5/44,45 °/5/44,45 °/5/44,56/56,56/56,
44/44,44/44,45 °/5/44,45 °/5/56,56/56；(exhaust section D) 56/56,44/44,44/44；45 ° of (homogenizing zone E)/
5/44,60 °/4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Comparative example 4
First by 11.25kg di-t-butyl peroxide, 3.75kg Triallyl isocyanurates, 3kg antioxidant 1010s,
3kg irgasfos 168s, 2.5kg Tissuemat Es (A-C316A), 2kg phosphorous acid three (TEMPO)
Ester adds high-speed mixer and mixing 5min as assistant composition, is then added to weightless claim in 1；
High density polyethylene (HDPE) 350kg skies are delivered into weightless title 2, ethylene-octene copolymer (POE8200) 17.5kg adds to mistake
Claim 3 again；
By assistant composition, high density polyethylene (HDPE), ethylene-octene copolymer according to 0.51:7:Expect under 0.35 mass ratio
Extruded in 65 type equidirectional parallel double-screw extruders, prepare crosslinkable polyethylene master batch, the temperature of 9 sections of heating zones of extruder
Degree is respectively 140 DEG C, and 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, extruder rotating speed is
200rpm, the melt of double screw extruder is flowed out through underwater pelletizer pelletizing, 80 DEG C of feed bin of drying is drawn onto and carries out drying 2h, obtain
Crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；45 ° of (melt zone B)/
5/56,45 °/5/56,45 °/5/56,44/44,45 °/5/56,60 °/4/56,56/56,44/44,60 °/4/44,45 °/5/
56L；(mixing section C) 56/56,44/44,44/44,44/44,45 °/5/44,45 °/5/44,45 °/5/44,56/56,56/56,
44/44,44/44,45 °/5/44,45 °/5/56,56/56；(exhaust section D) 56/56,44/44,44/44；45 ° of (homogenizing zone E)/
5/44,60 °/4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Comparative example 5
(1) by 50kg high density polyethylene (HDPE)s powder (DMDA 8007), 11.25kg di-t-butyl peroxide, 3.75kg's
Triallyl isocyanurate, 3kg antioxidant 1010,3kg irgasfos 168,2.5kg Tissuemat E (A-C316A),
2kg phosphorous acid three (TEMPO) ester, high-speed mixer and mixing 5min is put into, adds extruder
Extrusion prepares crosslinkable polyethylene master batch at 135 DEG C.
(2) it is high density polyethylene (HDPE) 300kg, ethylene-octene copolymer (POE8200) 17.5kg, crosslinkable polyethylene is female
Expect 50kg, be put into three different weightless titles, high density polyethylene (HDPE), ethylene-octene copolymer, crosslinkable polyethylene masterbatch are pressed
According to 6:0.35:Expect under 1 mass ratio and extruded in 65 type equidirectional parallel double-screw extruders, prepare crosslinkable polyethylene and change
Property material, the temperature of 9 sections of heating zones of extruder is respectively 140 DEG C, 140 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C, 145 DEG C,
145 DEG C, 145 DEG C, extruder rotating speed is 200rpm, flows out the melt of double screw extruder through underwater pelletizer pelletizing, is drawn onto baking
80 DEG C of siccative storehouse carries out drying 2h, obtains crosslinkable polyethylene modified materials.
The screw combinations that double screw extruder uses in step (2) are followed successively by from screw drive end terminad：
(solid conveying section A) 56/56A, 96/96,96/96,72/72,72/72,56/56,44/44；45 ° of (melt zone B)/
5/56,45 °/5/56,45 °/5/56,44/44,45 °/5/56,60 °/4/56,56/56,60 °/4/44,60 °/4/44,45 °/5/
56L；(mixing section C) 56/56,44/44,44/44,44/44,45 DEG C/5/44,45 °/5/44,45 °/5/44,56/56,56/56,
44/44,44/44,45 °/5/44,45 °/5/56,56/56；(exhaust section D) 56/56,44/44,44/44；45 ° of (homogenizing zone E)/
5/44,60 °/4/44,64/64,64/64,44/44,44/44.
The melt temperature, extruder electric current, extrudate state of extruder are flowed out, obtained crosslinkable polyethylene modified materials
Gel content is shown in Table 1.
Table 1
Table 1 gives crosslinkable polyethylene masterbatch, polyethylene and toughening element and is being mounted with different shearing screw thread combinations
When being extruded in the double screw extruder of screw rod, melt temperature, extruder electric current, extrudate extrusion form and obtain can
The gel content of crosslinked polyethylene modified materials.
From the results shown in Table 1, embodiment 1-3 can ensure extrudate form as melting completely, that is, what is obtained can
Crosslinked polyethylene modified materials can be with melt well, and mixing can be uniform.Under the premise of herein, the melt of the extrudate in embodiment 1-3
Temperature is below comparative example, and the gel content of extrudate is 0 weight %, illustrates not crosslink in extrusion.Further
The current values of extruder are observed, when illustrating that embodiment realizes above-mentioned good melting, the viscosity of extrudate is little, and difficulty of processing is not
Greatly.
And in comparative example 1-4, extrudate form can not melt well, or even crosslinking, can not provide crosslinkable polyethylene
The good melting of modified materials, mixed effect can be poor.
The corresponding embodiment 1 of comparative example 1, but the charging process of various materials is directly to help polyethylene, crosslinking agent, crosslinking
Agent, antioxidant, lubricant, cross-linked stable agent etc. directly feed extrusion.The extrudate that cannot be melted completely is shown in table 1.It is right
Charging process in ratio 1 causes the material of different states of matters to carry out melt blending in an extruder, and master batch shape is not made in advance
Formula.It is liquid due to there is auxiliary agent, it is solid powder or particle to have material, causes batch mixing uneven and shear in extrusion to become
Weak, molten condition is bad.It additionally there are the loss of material.
The corresponding embodiment 1 of comparative example 2, although wherein master batch is first made, melt zone starts in the screw combinations used
Engaged section in be free of reverse kneading member, but comprise only a positive kneading member (60 °/5/56) and be different from embodiment 1
(containing three kneading members), therefore the screw combinations of melt zone are different, the melt blending effect as a result realized dies down, can not
Complete the complete melting of material.
Various material amounts correspond to embodiment 2 in comparative example 3, but the feeding method of various materials is directly charging,
And in comparative example 3 use different from embodiment 2 screw combinations, be Strong shear combination (60 °/4/44,60 °/4/44,45 °/
5/56L), melt temperature can be raised, crosslinked.
Material amount in comparative example 4 corresponds to embodiment 3, but feeding method is different, is formed without masterbatch, polyethylene
Blanking direct with various auxiliary agents adds extruder, can find white non-fusant in extrudate, i.e., elastomer is under this screw combinations
Shearing is weaker, it is impossible to effectively melts elastomeric shear.
Material amount and feeding method in comparative example 5 correspond to embodiment 3, but adjust screw thread combination, using cutting by force
Cut combination (60 °/4/44,60 °/4/44,45 °/5/56L), the extrudate rough surface of extrusion, and it is partial cross-linked.
Using the feeding method of the present invention in embodiment, by being first made crosslinkable polyethylene masterbatch, then with polyethylene, increase
Tough component melts blending, and the screw thread combination of adjustment melt zone is combined, the process for preparing crosslinkable polyethylene modified materials can be made
In, can have bigger processed safely section, shear heat is greatly reduced, and auxiliary agent volatilization is few, obtain gel content for 0,
There is no the crosslinkable polyethylene modified materials of cross-linked structure.It can be prepared using this crosslinkable polyethylene modified materials and be handed over high
The crosslinked polyethylene of connection degree.
Claims (10)
1. a kind of preparation method of crosslinkable polyethylene modified materials, including：
(1) will be mixed containing polyethylene a, crosslinking agent, crosslinking coagent, antioxidant, lubricant and the compound of cross-linked stable agent
Refining, is made crosslinkable polyethylene masterbatch；On the basis of the total amount of the crosslinkable polyethylene masterbatch, the crosslinking agent and crosslinking help
The total content of agent is 12~27 weight %；
(2) the crosslinkable polyethylene masterbatch, polyethylene b and toughening element are separately added into double screw extruder and melted
Blending, obtains crosslinkable polyethylene modified materials；On the basis of the total amount of the crosslinkable polyethylene modified materials, the crosslinking agent and
The total content of crosslinking coagent is 0.8~3 weight %.
2. preparation method according to claim 1, wherein, in step (1), relative to the polyethylene of 100 parts by weight
A, the crosslinking agent are 20~25 parts by weight, and the crosslinking coagent is 5~10 parts by weight, and the antioxidant is 2~15 parts by weight,
The lubricant is 5~15 parts by weight, and the cross-linked stable agent is 1~5 parts by weight.
3. preparation method according to claim 1 or 2, wherein, in step (1), the polyethylene a is selected from high-density polyethylene
Alkene and/or low density polyethylene (LDPE)；Preferably, the density of the high density polyethylene (HDPE) is 0.94~0.965g/cm3, in 2.16kg
Melt index when load is lower 190 DEG C is 1~20g/10min；The density of the low density polyethylene (LDPE) is 0.91~0.935g/
cm3, at 2.16 kg load 190 DEG C when melt index be 1~20g/10min.
4. preparation method according to claim 1, wherein, in step (2), relative to the described cross-linking of 100 parts by weight
Polyethylene master batch, the polyethylene b are 500~1000 parts by weight, and the toughening element is 35~400 parts by weight.
5. the preparation method according to claim 1 or 4, wherein, in step (2), the polyethylene b is selected from high-density polyethylene
Alkene and/or low density polyethylene (LDPE)；Preferably, the density of the high density polyethylene (HDPE) is 0.94~0.965g/cm3, in 2.16kg
Melt index when load is lower 190 DEG C is 1~20g/10min；The density of the low density polyethylene (LDPE) is 0.91~0.935g/
cm3, at 2.16 kg load 190 DEG C when melt index be 1~20g/10min.
6. according to the preparation method described in any one in claim 1-5, wherein, the toughening element is selected from linea low density
At least one of polyethylene, ethylene-octene copolymer and ethylene propylene diene rubber；The crosslinking agent is selected from peroxidating diisopropyl
Benzene, benzoyl peroxide, di-isopropylbenzene hydroperoxide, TBHP, 2,5- dimethyl -2,5- di-tert-butyl peroxides
Hexane, 2,5- dimethyl -2,5- di-tert-butyl peroxides -3- alkynes, diacyl peroxide, di-tert-butyl peroxide, alkane
At least one of base hydrogen peroxide, dilauroyl peroxide, methyl ethyl ketone peroxide and cyclohexanone peroxide；The crosslinking coagent
Selected from poly 1,2-butadiene, diallyl p phthalate, divinylbenzene, TAC, cyanuric acid triolefin
At least one of propyl ester and triallyl isocyanate；The cross-linked stable agent is selected from (the 2,2,6,6- tetramethyls of phosphorous acid three
Piperidine NO free radical) ester, at least one in 2,2- bis- (4- t-octyls phenyl) -1- picryls hydrazine and NO free radical piperidine alcohols
Kind.
7. preparation method according to claim 1, wherein, in step (2), the screw combinations in the double screw extruder
Including intermeshing two root architectures identical screw rod (1)；
Screw rod (1) includes splined shaft (2), screwing element (3) and kneading member (4)；
The screwing element (3) of multiple positive and negative rotations of difference and the kneading member (4) of multiple positive and negative rotations of difference pass through respective endoporus
The spline (5) carried is sleeved on splined shaft (2)；
Every screw rod (1) includes solid conveying section (A), the melt zone divided successively towards end from the driving end of screw rod (1)
(B), mixing section (C), exhaust section (D) and homogenizing zone (E).
8. preparation method according to claim 7, wherein, the helical pitch of screwing element (3) is 44~96mm, screwing element
(3) length is 44~96mm；The error angle of kneading member (4) is 30~60 °, and the length of kneading member (4) is 44~56mm,
The number of the kneading block of kneading member (4) is 4~6；
Preferably, the melt zone contains at least two groups of engaged sections, and every section of engaged section contains at least one kneading member (4)；
Contain at least one screwing element (3) between the engaged section；
The melt zone contains at least one reverse-flight elements or a reverse kneading member.
9. the preparation method according to claim 7 or 8, wherein, the steering of two screw rods (1) is identical；During rotation, two spiral shells
The phase of bar (1) differs 90 ° of phase angles；Preferably, a diameter of 36~96mm of screw rod (1), draw ratio (36~48)：1.
10. according to the preparation method described in any one in claim 1-9, wherein, the crosslinkable polyethylene modified materials
Gel content is 0 weight %.
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| WO2019148407A1 (en) * | 2018-02-01 | 2019-08-08 | Dow Global Technologies Llc | Masterbatch with semi-crystalline polyolefin carrier resin |
| CN110587949A (en) * | 2019-10-10 | 2019-12-20 | 安徽皖维皕盛新材料有限责任公司 | Method for improving output of PVB film extruder |
| CN112390995A (en) * | 2019-08-12 | 2021-02-23 | 国家能源投资集团有限责任公司 | Antistatic polyethylene composition, preparation method thereof and polyethylene product |
| CN113150419A (en) * | 2020-01-07 | 2021-07-23 | 国家能源投资集团有限责任公司 | Crosslinkable polyethylene composition, preparation method thereof and rotational molding product |
| CN113527796A (en) * | 2020-04-20 | 2021-10-22 | 国家能源投资集团有限责任公司 | High wear-resistant cross-linkable polyethylene composition, high wear-resistant cross-linked polyethylene material and preparation method thereof |
| CN115746344A (en) * | 2022-11-25 | 2023-03-07 | 神华(北京)新材料科技有限公司 | Ultra-high molecular weight polyethylene product and preparation method and application thereof |
| US11952470B2 (en) | 2018-02-01 | 2024-04-09 | Dow Global Technologies Llc | Masterbatch with semi-crystalline polyolefin carrier resin |
| CN118900760A (en) * | 2022-02-10 | 2024-11-05 | 道达尔能源一技术 | Process for treating an initial polyethylene-containing material to produce a polyethylene composition for injection molding |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001131331A (en) * | 1999-11-02 | 2001-05-15 | Toyota Central Res & Dev Lab Inc | Recycling method of cross-linked polyethylene resin |
| JP2001269980A (en) * | 2000-03-24 | 2001-10-02 | Okura Ind Co Ltd | Method for regenerating crosslinked polyethylene resin composition |
| CN102529062A (en) * | 2012-01-30 | 2012-07-04 | 天津戈瑞德新材料科技有限公司 | Screw rod assembly used for extrusion processing without dry processing to nylon |
-
2016
- 2016-09-14 CN CN201610825763.9A patent/CN107814996B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001131331A (en) * | 1999-11-02 | 2001-05-15 | Toyota Central Res & Dev Lab Inc | Recycling method of cross-linked polyethylene resin |
| JP2001269980A (en) * | 2000-03-24 | 2001-10-02 | Okura Ind Co Ltd | Method for regenerating crosslinked polyethylene resin composition |
| CN102529062A (en) * | 2012-01-30 | 2012-07-04 | 天津戈瑞德新材料科技有限公司 | Screw rod assembly used for extrusion processing without dry processing to nylon |
Non-Patent Citations (2)
| Title |
|---|
| 王加龙: "《过氧化物DC P母料的研制》", 《现代塑料加工应用》 * |
| 高福成: "《现代食品工程高新技术》", 31 May 1997 * |
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| WO2019148407A1 (en) * | 2018-02-01 | 2019-08-08 | Dow Global Technologies Llc | Masterbatch with semi-crystalline polyolefin carrier resin |
| US11952470B2 (en) | 2018-02-01 | 2024-04-09 | Dow Global Technologies Llc | Masterbatch with semi-crystalline polyolefin carrier resin |
| US12116463B2 (en) | 2018-02-01 | 2024-10-15 | Dow Global Technologies Llc | Masterbatch with semi-crystalline polyolefin carrier resin |
| CN112390995A (en) * | 2019-08-12 | 2021-02-23 | 国家能源投资集团有限责任公司 | Antistatic polyethylene composition, preparation method thereof and polyethylene product |
| CN112390995B (en) * | 2019-08-12 | 2022-06-07 | 国家能源投资集团有限责任公司 | Antistatic polyethylene composition and its preparation method and polyethylene product |
| CN110587949A (en) * | 2019-10-10 | 2019-12-20 | 安徽皖维皕盛新材料有限责任公司 | Method for improving output of PVB film extruder |
| CN110587949B (en) * | 2019-10-10 | 2022-03-08 | 安徽皖维皕盛新材料有限责任公司 | Method for improving output of PVB film extruder |
| CN113150419A (en) * | 2020-01-07 | 2021-07-23 | 国家能源投资集团有限责任公司 | Crosslinkable polyethylene composition, preparation method thereof and rotational molding product |
| CN113150419B (en) * | 2020-01-07 | 2022-12-27 | 国家能源投资集团有限责任公司 | Crosslinkable polyethylene composition, preparation method thereof and rotational molding product |
| CN113527796A (en) * | 2020-04-20 | 2021-10-22 | 国家能源投资集团有限责任公司 | High wear-resistant cross-linkable polyethylene composition, high wear-resistant cross-linked polyethylene material and preparation method thereof |
| CN118900760A (en) * | 2022-02-10 | 2024-11-05 | 道达尔能源一技术 | Process for treating an initial polyethylene-containing material to produce a polyethylene composition for injection molding |
| CN115746344A (en) * | 2022-11-25 | 2023-03-07 | 神华(北京)新材料科技有限公司 | Ultra-high molecular weight polyethylene product and preparation method and application thereof |
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