CN104271342A - 用于管材的丙烯基三元共聚物 - Google Patents
用于管材的丙烯基三元共聚物 Download PDFInfo
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- CN104271342A CN104271342A CN201280056469.6A CN201280056469A CN104271342A CN 104271342 A CN104271342 A CN 104271342A CN 201280056469 A CN201280056469 A CN 201280056469A CN 104271342 A CN104271342 A CN 104271342A
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- hexene
- terpolymer
- ethylene
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- 229920001897 terpolymer Polymers 0.000 title claims abstract description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 3
- -1 propylene, ethylene Chemical group 0.000 abstract description 17
- 239000000155 melt Substances 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000009863 impact test Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical group COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 1
- IJBYVSUZCRXTOD-UHFFFAOYSA-N 1-methoxy-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(OC)=CC=C2 IJBYVSUZCRXTOD-UHFFFAOYSA-N 0.000 description 1
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 1
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GJTGYNPBJNRYKI-UHFFFAOYSA-N hex-1-ene;prop-1-ene Chemical compound CC=C.CCCCC=C GJTGYNPBJNRYKI-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229920005621 immiscible polymer blend Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 150000004291 polyenes Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a general shape other than plane
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
- F16L9/127—Rigid pipes of plastics with or without reinforcement the walls consisting of a single layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
一种含有丙烯、乙烯和1-己烯的三元共聚物,其中:(i)1-己烯衍生单元的含量范围为1wt%到2.6wt%;(ii)乙烯衍生单元的含量高于0.7wt%,并满足下列关系式(1):C2<C6-0.2 (1)其中,C2是乙烯衍生单元的含量wt%,且C6为1-己烯衍生单元的含量wt%;(iii)熔体流动速率(MFR)(ISO1133230℃,2.16kg)范围为0.5到3.9g/10min;(iv)熔融温度范围为130℃到138℃;优选为132℃到136℃。
Description
本发明涉及一种丙烯/乙烯/1-己烯三元共聚物,特别适合用于生产管材,特别是小直径管材。
丙烯/乙烯/1-己烯三元共聚物用于生产管材已经是业内已知的。例如,WO2006/002778涉及一种包含丙烯/乙烯和α-烯烃的三元共聚物的管材系统,其中乙烯含量为0到9mol%,优选为1到7mol%,且1-己烯含量范围为0.2到5%wt。
当需要小直径管材时,使管材具有有限的壁厚是很重要的。这允许得到含有较少材料的管材,最重要的是由于内径较大,改善管材进料效率。然而,当壁厚变小时,管材可能会变脆,因而有必要使用具有高耐冲击性,特别是在低温下具有高耐冲击性的材料。
申请人发现,可以从这些范围中选择具有改善的性能,特别是用于小直径管材的改善的抗冲击性的组合物。
因此,本发明的目的是一种含有丙烯、乙烯和1-己烯的三元共聚物,其中
(i)1-己烯衍生单元的含量范围为1wt%到3.2wt%;优选为1.5wt%到3.0wt%;更优选为1.5wt%到2.8wt%;甚至更优选为1.8wt%到2.6wt%;诸如,1.8-2.4wt%;
(ii)乙烯衍生单元的含量高于1.4wt%,优选为高于1.5wt%,甚至更优选为高于1.6wt%并满足下列关系式(1):
C2<C6-0.2 (1)
其中,C2是乙烯衍生单元的含量wt%,且C6为1-己烯衍生单元的含量wt%;优选地是,关系式(1)是C2<C6-0.3;更优选为C2<C6-0.5;
(iii)熔体流动速率(MFR)(ISO1133230℃,5kg)范围为0.1到3.9g/10min;优选为0.5到1.9g/10min;
(iv)熔融温度范围为130℃到138℃;优选为132℃到136℃。
本发明的三元共聚物具有立构规整性的全同立构型的丙烯序列,通过二甲苯可萃取物的低值,这是清楚的,该值低于10%wt:优选为低于8%wt;更优选为低于7%wt
优选地,本发明的三元共聚物具有多分散指数(PI),其范围为2.0到7.0,优选为3.0到6.5,更优选为3.5到6.0。
结晶温度范围优选为70℃到100℃,优选为80℃到97℃;更优选为85℃到97℃。
利用本发明的三元共聚物,可以得到管材,特别是即使在压力下也适合使用的具有特别小的壁厚的小直径管材。所述管材给出了这样的结果:在0℃下的冲击试验(ISO9854)中,每10个管材中有0个破裂。
优选地,根据本发明的管材显示在95℃下测量的液压阻力(ISO方法1167-1)和超过500小时的4.8MPa的压力;更优选为超过550小时;甚至更优选为超过580小时,甚至更优选为超过600小时。
因此,本发明的另一个目的是一种包含本发明的三元共聚物的管材。
如本文所用,术语“管材”也包括管材配件、阀门和通常是,例如,热水管道系统必需的所有零件。定义还包括单层和多层管材,其中,例如层体中的一或多者是金属层且可包括粘合层。
这种制品可以通过本领域中公知的各种工业生产方法,诸如,举例而言,模塑、压制等来制造。
在本发明的另一个实施例中,本发明的三元共聚物还包含相对于100重量份的所述多相聚丙烯组合物,量从0.5变化到60重量份的无机填料剂。这种填料剂的典型例子是碳酸钙、硫酸钡、二氧化钛和滑石。滑石和碳酸钙是优选的。一些填料剂也可能具有成核效果,诸如,滑石,这也是一种成核剂。成核剂的量通常为0.2到5wt%,相对于聚合物的量而言。
本发明的三元共聚物还适用于提供具有除了具有光滑的内表面和外表面的那些以外的任何构型的壁的聚丙烯管材。例子有具有夹心状管壁的管材、具有带有沿纵向延伸的腔室的中空壁构造的管材、具有带有螺旋腔室的中空壁构造的管材、具有光滑内表面和紧凑的或中空的、螺旋形,或环状带肋外表面的管材,与各管材端部的构型无关。
根据本发明的制品、压力管和相关配件以公知的方式生产,例如,举例而言,通过(共)压制或模塑。
可以利用不同类型的聚烯烃挤压机来压制制品,例如,单螺杆或双螺杆挤压机。
本发明的另一个实施例是一种方法,其中所述多相聚合物组合物被模塑成所述制品。
当管材是多层时,至少一层由上述三元共聚物制成。其他层优选地由R-CH=CH2烯烃的非晶或结晶性聚合物(诸如,均聚物和共聚物或三元共聚物)制成,其中R是氢原子或C1-C6烷基。特别优选的是以下聚合物:
1)全同立构型或主要是全同立构型的丙烯均聚物;
2)具有乙烯和/或C4-C8α-烯烃的丙烯的无规共聚物和三元共聚物,诸如,1-丁烯、1-己烯、1-辛烯、4-甲基-1-戊烯,其中,按质量算,总共聚单体含量范围为0.05%到20%,或具有全同立构型或主要是全同立构型的丙烯均聚物的所述聚合物的混合物;
3)多相聚合物共混物,其包含(a)丙烯均聚物和/或项(2)的共聚物和三元共聚物之一,和弹性部分(b),弹性部分(b)包含具有丙烯和/或C4-C8α-烯烃的乙烯的共聚物和三元共聚物,任选地含有少量二烯,同为聚合物(2)(a)公开;以及
4)非晶聚合物,诸如,举例而言,含氟聚合物、聚二氟乙烯(PVDF)。
在多层管材中,管材各层可能具有相同的或不同的厚度。
本发明中使用的三元共聚物可以通过一个或多个聚合步骤中的聚合反应来制备。这种聚合反应可以在齐格勒-纳塔催化剂存在情况下进行。所述催化剂的一个重要组分是固体催化剂组分,其包含具有至少一个钛-卤键的钛化合物,和电子供体化合物,这两者均以活性形式负载在卤化镁上。另一重要组分(助催化剂)是有机铝化合物,诸如,烷基铝化合物。
可任选地加入外部供体。
通常用于本发明方法的催化剂能够产生二甲苯不溶性的值在环境温度下大于90%,优选为大于95%的聚丙烯。
具有上文提到的特性的催化剂在专利文献中是众所周知的;特别有利的是美国专利4,399,054和欧洲专利45977中描述的催化剂。其他例子可以在美国专利4,472,524中找到。
所述催化剂中使用的固体催化剂组分包含,作为电子供体(内部供体),选自醚、酮、内酯、含N、P和/或S原子的化合物,以及单和二羧酸酯组成的基团的化合物。
特别合适的电子供体化合物是下式的邻苯二甲酸酯和1,3-二醚酯:
其中RI和RII是相同的或不同的,且是C1-C18烷基、C3-C18环烷基或C7-C18芳烃基;RIII和RIV是相同的或不同的,且是C1-C4烷基;或为1,3-二醚,其中位置2上的碳原子属于由5、6或7个碳原子或者5-n或6-n’个碳原子组成的环状或多环结构,且n个氮原子和n’个杂原子分别选自N、0、S和Si组成的基团,其中n是1或2,且n’是1、2或3,所述结构含有两个或三个不饱和键(环多烯结构),并且可选地与其它环状结构缩合,或被选自直链或支链烷基;环烷基、芳基、芳烷基、烷芳基和卤素组成的基团的一个或多个取代基取代,或者与其它环状结构缩合并被上文提到的也可键合到缩合环状结构的取代基中的一或多者;上文提到的烷基、环烷基、芳基、芳烷基或烷芳基和任选地含有一个或多个杂原子作为碳原子或氢原子或两者的取代物的缩合环状结构中的一或多者取代。
这种类型的醚在公开的欧洲专利申请361493和728769中描述。
所述二醚的代表性例子是2-甲基-2-异丙基-1,3-二甲氧基丙烷、2,2-二异丁基-1,3-二甲氧基丙烷、2-异丙基-2-环戊基-1,3-二甲氧基丙烷、2-异丙基-2-异戊基-1,3-二甲氧基丙烷、9,9-双(甲氧基甲基)芴。
其他合适的电子供体化合物是邻苯二甲酸酯,诸如,二异丁基、二辛基、二苯基和苄酯。
上文提到的催化剂组分的制备是根据各种方法执行的。
例如,MgCl2·nROH加合物(特别是球形颗粒形式),其中n通常为1到3,且ROH是乙醇、丁醇或异丁醇,与含有电子供体化合物的过量的TiCl4发生反应。反应温度通常为80到120℃。然后将固体分离,并再次与TiCl4发生反应,在电子供体化合物存在或不存在的情况下,然后将其用烃的等分试样分离并洗涤,直至所有氯离子消失为止。
在固体催化剂组分中,以Ti表示的钛化合物通常存在的量为0.5到10%,按重量计算。相对于二卤化镁,保持固定在固体催化剂组分上的电子供体化合物的量一般为5到20mol%。
可用于制备固体催化剂组分的钛化合物是钛的卤化物和卤醇化物。四氯化钛是优选的化合物。
上述反应导致活性形式的卤化镁形成。其它反应是文献中已知的,这会导致活性形式的卤化镁形成,起始物除了卤化物以外,还有镁化合物,诸如,羧酸镁。
用作助催化剂的烷基铝化合物包含三烷基铝,诸如,三乙基铝、三异丁基铝、铝-三正丁基,和含有通过0或N原子,或者SO4或SO3基团彼此键合的两个或更多个A]原子的直链或环状烷基铝化合物。
烷基铝化合物一般用量是这样的,即Al/Ti比为1到1000。
可用作外部供体的电子供体化合物包括芳族酸酯,诸如,苯甲酸烷基酯,且特别是含有至少一个Si-OR键的硅化合物,其中R是烃基。
硅化合物的例子是(叔丁基)2Si(OCH3)2、(环己基)(甲基)Si(OCH3)2,(环戊基)2Si(OCH3)2和(苯基)2Si(OCH3)2以及(1,1,2-三甲基丙基)Si(OCH3)3。
也可有利地使用具有上述公式的1,3-二醚。如果内部供体是这些二醚之一,则外部供体可以省略。
特别地,即使先前所述催化剂组分的许多其他组合可以允许根据本发明得到丙烯聚合物组合物,三元共聚物优选通过使用作为内供体的含有邻苯二甲酸酯的催化剂和作为外供体的(环戊基)2Si(OCH3)2,或作为内部供体的所述1,3-二醚来制备。
所述丙烯-乙烯-己烯-1聚合物是利用EP申请1012195中所示的聚合方法产生的。
详细地说,所述方法包含在催化剂存在的反应条件下将单体馈送到所述聚合区,并从所述聚合区收集聚合物产物。在所述方法中,生长的聚合物颗粒在快速流化条件下向上流动通过所述聚合区(上升管)之一(第一),离开所述上升管并进入另一个(第二)聚合区(下降管),在重力的作用下通过这里以致密形式向下流动,离开所述下降管并被重新引入到所述上升管中,从而建立上升管和下降管之间的聚合物的循环。
在下降管中,固体的密度值高,接近聚合物的容积密度。因此,压力正增益可以沿流动方向获得,使其可以在没有特殊机械装置帮助的情况下将聚合物重新引入到上升管中。以这种方式设置了“环路”循环,其由两个聚合区之间的压力的平衡并通过引入系统中的水头损失来定义。
通常,上升管中的快速流化条件是通过将包含有关单体的气体混合物馈送给所述上升管建立的。优选的是,气体混合物的馈送在适当情况下通过使用气体分布器装置,将聚合物再引入到所述上升管中的点以下实现的。气体输送到上升管中的速度高于操作条件下的输送速度,优选为2到15m/s。
通常,离开上升管的聚合物和气体混合物被输送到固/气分离区。固/气分离可以通过使用常规的分离装置来实现。聚合物从分离区进入下降管。离开分离区的气体混合物被压缩、冷却并转移到上升管,如果合适的话,加入补充的单体和/或分子量调节剂。转移可通过气体混合物的再循环管线来实现。
对聚合物在两个聚合区之间的循环的控制可以通过使用适用于控制固体,诸如,机械阀的流量的装置计量离开下降管的聚合物的量来实现。
操作参数,诸如,温度,是烯烃聚合方法中通常使用的那些操作参数,例如,50到120℃。
此第一阶段方法可以在0.5到10MPa,优选为1.5到6MPa之间的操作压力下进行。
有利地是,一种或多种惰性气体被保持在聚合区中,数量是,惰性气体的分压的总和优选为气体总压力的5到80%。所述惰性气体可以是,举例而言,氮气或丙烷。
各种催化剂在所述上升管的任一点被输送到上升管。然而,它们也可以在下降管的任一点被馈送。所述催化剂可以处于任何物理状态,因此,可以使用固状或液态的催化剂。
给出下面的例子是为了说明本发明而不是限制的目的。
实施例
表征方法
-熔融温度和结晶温度:通过差示扫描量热法(DSC)确定。称量6±1mg,加热到220±1℃,速率为20℃/min并在220±1℃下在氮气流中保持2分钟,并且此后以20℃/min的速率冷却到40±2℃,由此在此温度下保持2分钟来使样品结晶。然后,在温度上升速率为20℃/min,到达220±1℃的情况下,样品再次熔化。记录熔化扫描,获得温谱图,并由此读取熔融温度和结晶温度。
-熔体流动速率:根据方法ISO1133(230℃,5Kg)确定。
-二甲苯可溶性:如下确定。
将2.5g聚合物和250ml的二甲苯放入装有冷凝器和磁力搅拌器的玻璃烧瓶中。在30分钟内,温度升至溶剂的沸点。然后在回流下保持如此得到的清液并再搅拌30分钟。然后封闭的烧瓶在冰水浴中保持30分钟,并在25℃恒温水浴中保持30分钟。在快速滤纸上过滤如此形成的固体。将100ml滤液倒入预先称重的铝容器中,其在氮气流下在加热盘上加热,通过蒸发除去溶剂。然后将容器在真空下保持在80℃烘箱中,直到得到恒重为止。然后计算室温下可溶于二甲苯的聚合物的重量百分比。
-1-己烯和乙烯的含量:由三元共聚物的13C-NMR光谱确定。
NMR分析。当AV-600光谱仪在150.91MHz、120℃下、以傅立叶变换模式工作时,获得13C NMR光谱。丙烯CH的峰值用作内标准(internal reference),在28.83。使用下列参数得到13C NMR光谱:
使用以下关系式由二价元素(diad)来计算1-己烯和乙烯的总量作为摩尔百分数:
[P]=PP+0.5PH+0.5PE
[H]=HH+0.5PH
[E]=EE+0.5PE
根据下表来已经算出丙烯/1-己烯/乙烯共聚物的13C NMR光谱的分配:
区域 | 化学位移 | 分配 | 序列 |
1 | 46.93-46.00 | Sαα | PP |
2 | 44.50-43.82 | Sαα | PH |
3 | 41.34-4.23 | Sαα | HH |
4 | 38.00-37.40 | Sαγ+Sαδ | PE |
5 | 35.70-35.0 | 4B4 | H |
6 | 35.00-34.53 | Sαγ+Sαδ | HE |
7 | 33.7533.20 | CH | H |
8 | 33.24 | Tδδ | EPE |
9 | 30.92 | Tβδ | PPE |
10 | 30.76 | Sγγ | XEEX |
11 | 30.35 | Sγδ | XEEE |
12 | 29.95 | Sδδ | EEE |
13 | 29.35 | 3B4 | H |
14 | 28.94-28.38 | CH | P |
15 | 27.43-27.27 | Sβδ | XEE |
16 | 24.67-24.53 | Sββ | XEX |
17 | 23.44-23.35 | 2B4 | H |
18 | 21.80-19.90 | CH3 | P |
19 | 14.22 | CH3 | H |
屈服伸长:根据ISO527测量。
断裂伸长:根据ISO527测量
断裂应力:根据ISO527测量。
冲击试验:ISO9854
抗水压性:根据ISO方法1167-1测量
用于机械分析的样品
根据ISO294-2已经得到的样品
弯曲模量
根据ISO178确定。
拉伸模量
根据ISO527确定
实施例1和比较实施例2
根据EP1012195中所述,在包含聚合设备的厂房中在催化剂存在的情况下通过使丙烯、乙烯和1-己烯在连续条件下聚合来制备共聚物。
将催化剂传送到聚合设备,该设备包含两个相互连接的圆柱形反应器,即上升管和下降管。通过从气体/固体分离器回收气体在上升管中建立快速流化条件。在实施例1-5中没有使用阻碍投料(barrier feed)。
所用催化剂包含通过类推EP-A-728769中的实施例5制备的催化剂组分,但是使用微球状的MgCl2·1.7C2H5OH来代替MgCl2·2.1C2H5OH。这样的催化剂组分与作为外部供体的二环戊基二甲氧基硅烷(DCPMS)以及三乙基铝(TEA)一起使用。
排出反应器的聚合物颗粒经过蒸汽处理以除去反应性单体和挥发性物质,然后干燥。表1示出了主要操作条件和所产生的聚合物的特性。
表1
实施例 | 1 | COMP2 | |
TEA/固体催化剂组分,g/g | 4 | 5 | |
TEA/DCPMS,g/g | 4 | 5 | |
C6/(C3q+C6),mol/mol | 上升管 | 0.03 | 0.03 |
C6/(C3+C6),mol/mol | 下降管 | 0.038 | 0.038 |
C2/(C3+C2),mol/mol | 上升管 | 0.023 | 0.022 |
C2/(C3+C2),mol/mol | 下降管 | 0.0035 | 0.004 |
C2乙烯;C3丙烯;;C61-己烯
表2记录了所得材料的性质:
表2
Ex1 | Comp ex2 |
MFR5Kg/230℃ | g/10min | 1,03 | 1 |
C6-NMR | % | 2,6 | 2.8 |
C2-NMR | % | 1,7 | 1.3 |
X.S. | % | 6.6 | 6.5 |
ISO表征 | |||
弯曲模量24h | MPa | 830 | 910 |
拉伸模量24h | MPa | 750 | 930 |
IZOD0℃24h | kJ/m2 | 8 | 5.2 |
屈服应力 | % | 26 | 27.1 |
断裂伸长 | kJ/m2 | 360 | 390 |
Tm | ℃ | 136 | 135 |
Tc | ℃ | 93 | 95 |
已经产生外径为22mm且壁厚为2.8mm的挤出管并经过冲击试验和抗内压性试验。表3记录了结果
表3
通过使用本发明的材料opf得到的管材的冲击试验表示相对于比较实施例,结果得到了改善。
Claims (6)
1.一种含有丙烯、乙烯和1-己烯的三元共聚物,其中:
(i)1-己烯衍生单元的含量范围为1wt%到3.2%;
(ii)乙烯衍生单元的含量高于1.4t%,并满足下列关系式(1):
C2<C6-0.2 (1)
其中,C2是乙烯衍生单元的含量wt%,且C6为1-己烯衍生单元的含量wt%;
(iii)熔体流动速率(MFR)(ISO1133230℃,5kg)范围为0.1到3.9g/10min;
(iv)熔融温度范围为130℃到138℃;优选为132℃到136℃。
2.根据权利要求1所述的三元共聚物,其中1-己烯衍生单元的含量范围为1.5wt%到3.0,且乙烯衍生单元的含量高于1.5wt%。
3.根据权利要求1-2中任一项所述的三元共聚物,其中关系式(1)为C2<C6-0.3。
4.根据权利要求1-3中任一项所述的三元共聚物,其中熔体流动速率(MFR)(ISO1133230℃,2.16kg)范围为0.5到1.9g/10min;
5.一种管材系统和片材,其包含根据权利要求1到4所述的聚烯烃组合物。
6.一种单或多层管材和片材,其中至少一层包含根据权利要求1所述的聚烯烃组合物。
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EP11191865.2A EP2602102A1 (en) | 2011-12-05 | 2011-12-05 | Propylene-based terpolymers for pipes |
EP11191865.2 | 2011-12-05 | ||
PCT/EP2012/074390 WO2013083575A1 (en) | 2011-12-05 | 2012-12-05 | Propylene-based terpolymers for pipes |
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CN112469746A (zh) * | 2018-07-27 | 2021-03-09 | Sabic环球技术有限责任公司 | 用于管道的基于丙烯的三元共聚物组合物 |
CN112469747A (zh) * | 2018-07-27 | 2021-03-09 | Sabic环球技术有限责任公司 | 制备基于丙烯的三元共聚物的方法 |
CN114761222A (zh) * | 2020-01-27 | 2022-07-15 | Sabic环球技术有限责任公司 | 用于管的基于丙烯的三元共聚物组合物 |
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CN107001507B (zh) * | 2014-12-03 | 2018-07-24 | 巴塞尔聚烯烃意大利有限公司 | 用于容器的基于丙烯的三元共聚物 |
US11407867B2 (en) | 2017-11-09 | 2022-08-09 | Basell Poliolefine Italia S.R.L. | Heat-shrinkable label |
EP3830189B1 (en) | 2018-07-27 | 2024-02-21 | SABIC Global Technologies B.V. | Propylene-based terpolymer composition for pipes |
WO2024013126A1 (en) | 2022-07-11 | 2024-01-18 | Borealis Ag | A process for preparing propylene-ethylene random copolymers for pipe applications |
WO2024013128A1 (en) | 2022-07-11 | 2024-01-18 | Borealis Ag | A propylene-ethylene random copolymer for pipe applications |
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RU2599251C2 (ru) | 2016-10-10 |
BR112014012516B1 (pt) | 2020-10-13 |
EP2788181B1 (en) | 2018-07-04 |
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IN2014CN04060A (zh) | 2015-09-04 |
CN104271342B (zh) | 2018-04-10 |
US20140332109A1 (en) | 2014-11-13 |
BR112014012516A2 (pt) | 2017-06-06 |
WO2013083575A1 (en) | 2013-06-13 |
RU2014125552A (ru) | 2016-01-27 |
EP2602102A1 (en) | 2013-06-12 |
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