TW201522401A - 用於改質乙烯系聚合物及共聚物的方法 - Google Patents
用於改質乙烯系聚合物及共聚物的方法 Download PDFInfo
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- TW201522401A TW201522401A TW103138589A TW103138589A TW201522401A TW 201522401 A TW201522401 A TW 201522401A TW 103138589 A TW103138589 A TW 103138589A TW 103138589 A TW103138589 A TW 103138589A TW 201522401 A TW201522401 A TW 201522401A
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- polymer
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920001577 copolymer Polymers 0.000 title claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229920000642 polymer Polymers 0.000 title claims description 21
- 239000005977 Ethylene Substances 0.000 title abstract description 11
- 150000001540 azides Chemical class 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 150000002978 peroxides Chemical class 0.000 claims description 35
- 229920006163 vinyl copolymer Polymers 0.000 claims description 31
- 229920001684 low density polyethylene Polymers 0.000 claims description 14
- 239000004702 low-density polyethylene Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- -1 t-butylperoxy Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 150000001451 organic peroxides Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- HQNSWBRZIOYGAW-UHFFFAOYSA-N 2-chloro-n,n-dimethylpyridin-4-amine Chemical compound CN(C)C1=CC=NC(Cl)=C1 HQNSWBRZIOYGAW-UHFFFAOYSA-N 0.000 claims description 2
- DALNRYLBTOJSOH-UHFFFAOYSA-N 3,3,5,7,7-pentamethyl-1,2,4-trioxepane Chemical compound CC1CC(C)(C)OOC(C)(C)O1 DALNRYLBTOJSOH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- XMRSVLCCIJUKDQ-UHFFFAOYSA-N n-diazobenzenesulfonamide Chemical compound [N-]=[N+]=NS(=O)(=O)C1=CC=CC=C1 XMRSVLCCIJUKDQ-UHFFFAOYSA-N 0.000 claims description 2
- QQIVNUPLBOUZMR-UHFFFAOYSA-N trioxepane Chemical compound C1CCOOOC1 QQIVNUPLBOUZMR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 108091005960 Citrine Proteins 0.000 description 2
- 240000005572 Syzygium cordatum Species 0.000 description 2
- 235000006650 Syzygium cordatum Nutrition 0.000 description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011035 citrine Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- MGVWYCXYUZTAFA-UHFFFAOYSA-N C(CC(O)(C(=O)N=[N+]=[N-])CC(=O)N=[N+]=[N-])(=O)N=[N+]=[N-] Chemical compound C(CC(O)(C(=O)N=[N+]=[N-])CC(=O)N=[N+]=[N-])(=O)N=[N+]=[N-] MGVWYCXYUZTAFA-UHFFFAOYSA-N 0.000 description 1
- TXZAKDUEWQCQKM-UHFFFAOYSA-N C=CCC.CC1(CC(=CC=C1)C1=CC=CC=C1)C Chemical compound C=CCC.CC1(CC(=CC=C1)C1=CC=CC=C1)C TXZAKDUEWQCQKM-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004082 amperometric method Methods 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- HSVFKFNNMLUVEY-UHFFFAOYSA-N sulfuryl diazide Chemical compound [N-]=[N+]=NS(=O)(=O)N=[N+]=[N-] HSVFKFNNMLUVEY-UHFFFAOYSA-N 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/27—Compounds containing a nitrogen atom bound to two other nitrogen atoms, e.g. diazoamino-compounds
- C08K5/28—Azides
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/14—Peroxides
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- 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
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- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- 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
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/36—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with nitrogen-containing compounds, e.g. by nitration
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
- Organic Insulating Materials (AREA)
Abstract
本發明揭示用於官能化乙烯系(共)聚合物之方法，其包括以下步驟：使乙烯系(共)聚合物在範圍100至250℃之溫度下與式(I)之疊氮化物接觸：
□其中Y為：
□m為0或1，n為0或1，n+m=1或2，及X為具有1至12個碳原子之直鏈或分支鏈脂族或芳香族烴基，其視情況地包含雜原子。
Description
本發明係關於用於官能化及改質乙烯系(共)聚合物之方法、可藉由該等方法得到之經官能化及經改質之乙烯系(共)聚合物、及其於電纜生產之用途。
一般之電纜及電纜芯線之應用包括至少一個由一或多個聚合物材料層包圍的導體。
在一些電纜(包括中壓(MV)、高壓(HV)及特高壓(EHV)電纜)中，導體由若干層(包括內部半導體層、絕緣層及外部半導體層)包圍。電纜之外部半導體層可為不可剝離的(即結合的及不可剝落的)或可剝離的(即非結合的及可剝落的)。導體可由內部半導體層包圍，該內部半導體層一般包括由導電性碳黑填充之交聯乙烯系共聚物。絕緣層一般由低密度聚乙烯(LDPE)(其經交聯賦予其所需之長期性質)製造。外部半導體層仍然係交聯半導體乙烯系共聚物層，且其通常藉由金屬配線強化或藉由薄片(金屬遮罩材料)覆蓋。
電纜通常藉由在導體上擠壓層而產生。該等聚乙烯或乙烯系共聚物層中之一者或多者隨後經交聯以改良其在高溫下之抗變形性，機械強度及/或耐化學性。自由基引發劑(諸如過氧化物)通常在擠壓該(等)層之前或過程中併入層材料中。在擠壓及形成電纜後，使電纜經歷由自由基引發劑引發之交聯步驟。
在自由基乙烯系(共)聚合物交聯之習知方法中，源自過氧化物分解產物之殘留揮發物諸如甲烷，呈空隙的形式殘留在電纜中，或呈高度可燃氣體物質的形式釋放。本發明之另一目的為提供用於使聚乙烯交聯之方法，其允許使用較低量過氧化物，從而得到較低量揮發物及仍然具有良好的交聯性能。
現已發現，若乙烯系(共)聚合物首先用檸康醯亞胺型疊氮化物官能化，則自由基交聯更快及更有效地發生，此意味著需要較低量之過氧化物。
此外，已發現用檸康醯亞胺型疊氮化物之該官能化作用可影響(共)聚合物之極性，從而導致例如與塗料層之更佳相容性。
此外，該官能化作用可用於增加長鏈分支之數量，藉以改變(共)聚合物之流變性，從而得到增強之熔融強度。
本發明因此係關於用於製備經官能化之乙烯系(共)聚合物之方法，其包括以下步驟：使乙烯系(共)聚合物在範圍100至250℃之溫度下與式(I)之疊氮化物接觸：
其中Y為：
m為0或1，n為0或1，n+m=1或2，及X為具有1至12個碳原子之直鏈或分支鏈脂族或芳香族烴基，其視情況地包含雜原子。
本發明亦關於一種用於改質乙烯系(共)聚合物之方法，其包括以下步驟：
根據上述方法製備經官能化之乙烯系(共)聚合物，使該經官能化之乙烯系(共)聚合物與有機過氧化物接觸以形成聚合物/過氧化物混合物，及在範圍140至300℃之溫度下加熱該聚合物/過氧化物混合物。
該方法導致(共)聚合物之流變性改質。取決於精確之條件，結果為交聯(共)聚合物或具有增強之熔融強度之(共)聚合物。可藉由高過氧化物水平達成交聯，且可在低過氧化物水平下達成增強之熔融強度。精確之水平取決於(共)聚合物之類型、過氧化物之類型及(共)聚合物之官能化水平。
術語乙烯系(共)聚合物包括乙烯均聚合物及基於乙烯及一或多種其他單體之共聚物。
乙烯系共聚物之實例為基於乙烯-丙烯之共聚物(EPM)、乙烯-丙烯-二烯三元共聚物(EPDM)、乙烯乙酸乙烯酯(EVA)、乙烯丙烯酸丁酯(EBA)、乙烯丙烯酸乙酯(EEA)及聚烯烴彈性體(POE)；後者為乙烯與辛烯或丁烯之共聚物。
乙烯均聚物(即聚乙烯)一般係根據其密度來分類。高密度聚乙烯(HDPE)定義為密度大於或等於0.941g/cm3；中等密度聚乙烯(MDPE)定義為0.926至0.940g/cm3之密度範圍；低線性密度聚乙烯(LLDPE)定義為0.915至0.925g/cm3之密度範圍；低密度聚乙烯(LDPE)定義為0.910至0.940g/cm3之密度範圍；極低密度聚乙烯(VLDPE)定義為0.880至0.915g/cm3之密度範圍。
所有該等乙烯均聚物均可用於本發明之方法中。然而，LDPE為最佳之使用類型。LDPE為較佳的乙烯系(共)聚合物，因為其具有可撓性及良好的機械強度。
用於本發明之方法中的疊氮化物具有式：
其中Y為：
m為0或1，n為0或1，n+m=1或2，較佳為1，及X為具有1至12個碳原子之直鏈或分支鏈脂族或芳香族烴基，其視情況地包含雜原子。
式(I)之檸康疊氮化物可以純正形式使用，但亦可呈與對應之衣康疊氮化物(itaconazide)混合之形式。
當X包含雜原子時，其較佳地具有以下結構之一者：
其中Z、Q及P為自1至6之整數，及R係選自由H、烷基、芳基、苯基及經取代之苯基組成之群。
然而，更佳地，X為具有1至12個(更佳1至6個，最佳2至4個)碳原子之脂族烷二基。
用於本發明之方法中的最佳疊氮化物為：
或
即各自為4-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯基疊氮(亦稱為檸康醯亞胺苯磺醯基疊氮)及2-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)乙基羰醯疊氮(亦稱為檸康醯亞胺-C2-疊氮甲酸酯)。
有若干種使疊氮化物與聚合物反應之機制，其取決於疊氮化物之類型及聚合物之類型。疊氮化物一般熱分解為兩種類型之氮烯：單重態(主要)及三重態(次要)。單重態之氮烯與完全飽和之聚合物鏈之反應導致疊氮化物插入聚合物鏈中。單重態及三重態氮烯與不飽和物之反應導致在碳碳雙鍵上之加成反應，其亦導致接枝。聚乙烯為具有僅僅少量不飽和鍵之飽和聚合物，該等不飽和鍵源自在聚合過程中之不完全性。在EPDM中，不飽和鍵部分特意藉由使用第三單體植入聚合物主鏈中。
與不飽和聚合物之反應亦可藉由在「點擊」反應中在相當低溫下之接枝，隨後進行加熱步驟(在此步驟中除去氮氣)而完成。
乙烯系(共)聚合物與疊氮化物係在範圍自100至250℃，較佳140至230℃，最佳150至220℃之溫度下接觸。可用不同方式實施接觸，包括熔融摻合、在雙輥軸研磨機中混合、擠壓、從常見之溶劑中混合等。亦可將疊氮化物混合至經混合之乙烯系(共)聚合物(即已經油、填
料及其他可選添加劑諸如抗降解劑、著色劑等混合之乙烯系(共)聚合物)中。
將疊氮化物以0.1至5phr(重量份/一百重量份(共)聚合物)之較佳量，更佳0.2至4phr，最佳0.3至3phr與乙烯系(共)聚合物混合。
在使乙烯系(共)聚合物交聯之過程中，經官能化之乙烯系(共)聚合物與有機過氧化物之最初接觸係在低於過氧化物之安全處理溫度下實施。過氧化物之安全處理溫度係當焦化時間(ts2)長於20分鐘之溫度。焦化時間使用動模在流變儀中根據ISO 6502：1991測量。
用此方法測得之安全處理溫度亦可在AkzoNobel手冊「Crosslinking elastomers and thermoplastics(2011)」中找到。
合適之有機過氧化物包括二烷基過氧化物及三氧雜環庚烷。明確言之，較佳的過氧化物為3,3,5,7,7-五甲基-1,2,4三氧雜環庚烷(安全處理溫度：180℃)、2,5-二甲基-2,5-二(第三丁基過氧基)己炔-3(安全處理溫度：145℃)、2,5-二甲基-2,5-二(第三丁基過氧基)己烷(安全處理溫度：135℃)、二(第三丁基過氧異丙基)苯(安全處理溫度：135℃)、過氧化二異丙苯(安全處理溫度：170℃)、及過氧化第三丁基異丙苯(安全處理溫度：135℃)。
過.氧化物可以液體或熔融形式添加至經官能化之乙烯系(共)聚合物之珠粒或顆粒中，並允許分散至該等珠粒或顆粒中。此較佳在低於80℃，更佳低於60℃，及最佳20至40℃之範圍內之溫度下完成。
或者，將過氧化物及經官能化之乙烯系(共)聚合物在低於該過氧化物之安全處理溫度下擠壓或熔融混合。另一種方法涉及在雙輥軸研磨機上將過氧化物與經接枝之乙烯系(共)聚合物混合。
有機過氧化物係以0.1至5重量%之較佳量，更佳0.2至4重量%，及最佳0.3至3重量%用於本發明之方法中，該用量係基於含過氧化物之混合物(包括過氧化物、經官能化之乙烯系(共)聚合物、填料及添加
劑)之總重量計。
可在此階段添加另外之組分，諸如抗氧化劑、阻燃劑、焦化阻滯劑、助劑、抗靜電劑、顏料、著色劑、水樹阻滯劑、潤滑劑及/或助滑劑。在聚乙烯之情況中，所有該等添加劑一般係以相對較小之量(通常低於總混合物之3重量%)使用。
水樹阻滯劑之實例為聚乙二醇(PEG)，例如PEG-2000；分子重量2000Da之聚乙二醇。
焦化阻滯劑之實例為第三丁基氫醌及α-甲基苯乙烯二聚物(4,4-二甲基-2,4-聯苯-1-丁烯)。
助劑之實例為：TMAIC(異氰尿酸三甲基烯丙酯)、TAIC(異氰尿酸三烯丙酯)、TAC(三烯丙基氰尿酸酯)、TRIM(三羥甲基丙烷三甲基丙烯酸酯)、二乙烯苯、HVA-2(N,N'-伸苯基雙馬來醯亞胺)及Perkalink 900(1,3-雙(檸康醯亞胺基甲基)苯)。
其他可以更高量使用之添加劑為強化型填料例如碳黑及矽石(尤其對於乙烯系共聚物)或非強化型礦物填料。後者可以至多60重量%之量添加。電子可傳導碳黑可以至多8重量%之量添加。
在將過氧化物與經官能化之乙烯系(共)聚合物接觸之後並在任一另外之熱處理之前，過氧化物/(共)聚合物混合物可以所需形式成形。為成形，需要加熱以熔融或軟化乙烯系(共)聚合物。該成形可在模具(壓縮、注射或轉移模塑)、擠壓機(其中成形模具可安裝在擠壓頭)、或壓光機(為將聚合物熔體處理成薄片或薄膜)中實施，或藉由薄膜發泡或熱成型。
可用任何方法加熱混合物至所需溫度。實例為：在模具(壓縮、注射或轉移模塑)中加熱；在(飽和蒸汽或氮氣填充之)管式烘箱中加熱；在鹽浴中加熱；及在熱空氣中使用烘箱或紅外照射加熱。
溫度較佳在140至300℃，較佳在150至250℃，及最佳在160至
230℃。
在一較佳實施例中，本發明之方法應用於生產包括由一或多個層包圍之電性導體(即一或多者線)之電纜，其中至少一層包括交聯乙烯系(共)聚合物。較佳地，該交聯乙烯系(共)聚合物為絕緣層之一部分，及/或該電纜之外衣層。
該電纜生產包括較佳藉由(共)擠壓在導體上施加一或多個包括聚合物組合物之層之步驟，其中至少一層包括交聯乙烯系(共)聚合物。若電纜必須包含兩個或更多個層，則各層可以個別步驟擠壓，或該等層之兩者或多者可以相同擠壓步驟共擠壓。
根據本實施例，該經官能化之乙烯系(共)聚合物、該有機過氧化物及任何其他可選組分可在引入至擠壓機之前在混合機中混合。或者，其可個別地添加至擠壓機中並在其中混合。在擠壓機中，使混合物經歷高溫(一般高於聚合物之熔點)，並在導體上經(共)擠壓以形成電纜層。
在形成該(等)電纜層之後，使聚合物在範圍140至300℃，較佳150至250℃，最佳160至230℃之溫度下交聯。在交聯步驟過程中之壓力較佳地最高為20bar，更佳最高13bar，最佳10至15bar。氛圍較佳為惰性，例如氮氣或飽和蒸汽。隨後使交聯電纜較佳在加壓條件下在冷卻媒劑諸如氮氣、油或水中冷卻。
實例
實例1：LDPE之改質
將LDPE(BPD2000 Ineos出品)與0、1或2phr檸康苯磺醯基疊氮在Thermo Scientific Haake PTW16,40L/D實驗室擠壓機上一起擠壓。擠壓機混合區域中之溫度落於180至230℃，螺桿速度為150rpm，產量為1kg/hr，在擠壓機中之停留時間約為90秒。該等設置足夠完全降解疊氮化物，如FT-IR光譜測定法證實。
擠壓後，截斷經接枝之LDPE壓出物並在60℃下以不同劑量水平將液體過氧化第三丁基異丙基(Trigonox® T，AkzoNobel出品)加入至截斷的聚合物珠粒中，以允許該過氧化物快速且均勻地併入聚合物顆粒中。在LDPE上吸收過氧化物之後，在180℃下使用流變儀(阿爾法科技(Alfa technologies)流變儀MDR 2000)評估固化速度及交聯密度。
在另一實驗中，藉由將特定量之交聯LDPE沉浸於回流二甲苯(約為140℃)中以測定不溶物(凝膠)之含量來測量交聯LDPE之凝膠百分數。其為測定最終固化狀態之工業方法。
結果指示於下表中。記錄的為固化速度之指示：t5、t50及t90，其為達到最終之最大交聯密度之5、50及90%之所需時間。在流變儀中測得之△扭矩(△S)係用作交聯LDPE之交聯密度之指示。
可從實驗中觀察，該疊氮化物之接枝具有兩個優勢：固化速度之增強(t90之縮短)及固化水平之增強(△S及凝膠%之增加)。檸康疊氮化物含量之效果取決於過氧化物劑量之水平。在低過氧化物劑量水平下，檸康疊氮化物水平從1增加至2phr並不導致性質之進一步增強。
當提高過氧化物水平時，檸康疊氮化物之增加對交聯密度之效果變得更明顯。此展示了檸康疊氮化物之量及過氧化物之量可經精細調整以允許控制固化速度及交聯密度。
實例2：EPM之改質
用實例1中使用之檸康疊氮化物改質無不飽和鍵之乙烯-丙烯共聚物(EPM)。為達成此目的，將含有碳黑填料及油(見表2之組合物)之基於EPM之化合物與2份/100份橡膠(phr)之檸康苯磺醯基疊氮混合，並在150至180℃下，於班伯里型密閉式混合機中熱處理，以允許疊該氮化物接枝於EPM上。
在用疊該氮化物改質EPM化合物之後，使用雙輥軸研磨機，將3phr之Perkadox® 14-40B-pd(AkzoNobel出品)(=佔碳酸鈣之40重量%雙(第三丁基過氧化異丙基)苯)，相當於0.4重量%之純過氧化物，與EPM混合。
藉由在170℃加熱，使EPM固化。
使用電流測定法(阿爾法科技流變儀MDR 2000)評估固化速度及交聯密度。結果指示於表2中。
作為比較實驗，將未改質之EPM與過氧化物混合，並以相同之方式交聯。
在流變儀中測得之△扭矩(△S)係交聯EPM之交聯密度之指示。可觀察出該疊氮化物之接枝具有兩個優勢：增強固化速度(較短的t90)及增強固化水平(△S之增加)。
Claims (15)
- 一種用於官能化乙烯系(共)聚合物之方法，其包括以下步驟：使乙烯系(共)聚合物在範圍100至250℃之溫度下與式(I)之疊氮化物接觸：
- 如請求項1或2之方法，其中該乙烯系(共)聚合物為LDPE。
- 如請求項1或2之方法，其中該乙烯系(共)聚合物為EPM。
- 如前述請求項中任一項之方法，其中該疊氮化物係選自4-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯基疊氮(亦稱為檸康醯亞胺苯磺醯基疊氮)及2-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)乙基羰醯疊氮(亦稱為檸康醯亞胺-C2-疊氮甲酸酯)。
- 如前述請求項中任一項之方法，其中該乙烯系(共)聚合物與該疊氮化物係在範圍140至230℃之溫度下接觸。
- 如前述請求項中任一項之方法，其中該疊氮化物係以0.1至5phr之量與該乙烯系(共)聚合物混合。
- 一種用於改質乙烯系(共)聚合物之方法，其包括以下步驟：根據請求項1至6中任一項之方法，製備經官能化之乙烯系(共) 聚合物，使該經官能化之乙烯系(共)聚合物與有機過氧化物接觸以形成聚合物/過氧化物混合物，及在範圍140至300℃之溫度下加熱該聚合物/過氧化物混合物。
- 如請求項7之方法，其中該聚合物/過氧化物混合物係在加熱之前經成形。
- 如請求項8之方法，其中該聚合物/過氧化物混合物係藉由擠壓成形。
- 如請求項7至8中任一項之方法，其中該有機過氧化物為二烷基過氧化物或三氧雜環庚烷。
- 如請求項10之方法，其中該過氧化物係選自由3,3,5,7,7-五甲基-1,2,4三氧雜環庚烷、2,5-二甲基-2,5-二(第三丁基過氧基)己炔-3、2,5-二甲基-2,5-二(第三丁基過氧)己烷、二(第三丁基過氧異丙基)苯、過氧化二異丙苯及過氧化第三丁基異丙苯所組成之群。
- 一種經官能化之乙烯系(共)聚合物，其可藉由請求項1至6中任一項之方法得到。
- 一種經改質之乙烯系(共)聚合物，其可藉由請求項7至11中任一項之方法得到。
- 一種如請求項12之經官能化之乙烯系(共)聚合物於製造電纜之用途。
- 一種電纜，其包括一或多個如請求項13之經改質之乙烯系(共)聚合物之層。
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| ??13191976.3 | 2013-11-07 | ||
| EP13191976 | 2013-11-07 |
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| TWI627197B TWI627197B (zh) | 2018-06-21 |
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| US (1) | US9688783B2 (zh) |
| EP (1) | EP3066151A1 (zh) |
| JP (1) | JP6306176B2 (zh) |
| KR (1) | KR20160084842A (zh) |
| CN (1) | CN105705563B (zh) |
| CA (1) | CA2928332A1 (zh) |
| MX (1) | MX2016005599A (zh) |
| RU (1) | RU2671352C2 (zh) |
| SA (1) | SA516371025B1 (zh) |
| TW (1) | TWI627197B (zh) |
| WO (1) | WO2015067533A1 (zh) |
| ZA (1) | ZA201602832B (zh) |
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| RU2662006C2 (ru) * | 2013-11-07 | 2018-07-23 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Способ модификации полимеров |
| EP3240681B1 (en) * | 2014-12-30 | 2018-11-14 | Dow Global Technologies LLC | Sulfonylazide derivative for tie layer |
| MX2017013392A (es) * | 2015-04-24 | 2018-01-30 | Akzo Nobel Chemicals Int Bv | Proceso para modificar polimeros. |
| JP2018513257A (ja) | 2015-04-24 | 2018-05-24 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． | ポリマーを官能化する方法 |
| US11708432B2 (en) * | 2017-12-18 | 2023-07-25 | Borealis Ag | Crosslinkable composition without antioxidant and beneficial methane formation with reduced crosslinking |
| EP3729472B1 (en) | 2017-12-18 | 2024-02-14 | Borealis AG | Cable made from crosslinkable composition without antioxidant and with beneficial methane formation |
| US11708431B2 (en) | 2017-12-18 | 2023-07-25 | Borealis Ag | Polymer composition comprising a polyethylene |
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| US3205206A (en) | 1962-10-15 | 1965-09-07 | Hercules Powder Co Ltd | Modifying polymers |
| US4352938A (en) | 1969-07-18 | 1982-10-05 | Hercules Incorporated | Epoxy-azidoformate compounds |
| US3631182A (en) * | 1970-05-21 | 1971-12-28 | Hercules Inc | Aliphatic bis(azidoformate)s |
| US4031068A (en) * | 1976-07-26 | 1977-06-21 | Uniroyal Inc. | Non-migratory sulfonyl azide antioxidants |
| DE2919841A1 (de) | 1979-05-16 | 1980-11-20 | Siemens Ag | Verfahren zur phototechnischen herstellung von reliefstrukturen |
| DE2919823A1 (de) * | 1979-05-16 | 1980-11-20 | Siemens Ag | N-azidosulfonylaryl-maleinimide sowie deren verwendung |
| DE3342851A1 (de) | 1983-11-26 | 1985-06-05 | Merck Patent Gmbh, 6100 Darmstadt | Fotolacke |
| DE69528941T2 (de) | 1994-09-19 | 2003-09-18 | Sentinel Products Corp., Hyannis | Vernetzte Schaumstrukturen von hauptsächlich linearen Polyolefinen und Verfahren zur Herstellung |
| TWI287536B (en) * | 2000-04-18 | 2007-10-01 | Ind Tech Res Inst | Method for preparing azide photo-initiators |
| ATE285438T1 (de) * | 2001-08-31 | 2005-01-15 | Borealis Tech Oy | Verfahren zur herstellung von vernetzten polyolefinen |
| US20060246283A1 (en) * | 2003-08-18 | 2006-11-02 | Brown Geoffrey D | Cable insulation compositions with enhanced rheology and processability |
| JP4372662B2 (ja) | 2004-10-26 | 2009-11-25 | 株式会社神戸製鋼所 | 形状検出装置及び形状検出プログラム |
| JP2011523968A (ja) * | 2008-06-06 | 2011-08-25 | ダウ グローバル テクノロジーズ エルエルシー | ポリプロピレンおよびオレフィンインターポリマーの反応処理された高耐熱性組成物 |
| RU2394854C1 (ru) * | 2008-10-23 | 2010-07-20 | Общество С Ограниченной Ответственностью "Группа Полипластик" | Способ получения композиции для перекисносшитого полиэтилена |
| BRPI0923985B1 (pt) * | 2009-03-31 | 2019-10-08 | Dow Global Technologies Llc | Película multicamada e artigo fabricado |
| US8883870B2 (en) * | 2010-09-15 | 2014-11-11 | Dow Global Technologies Llc | Propylene-alpha-olefin copolymer compositions with improved foaming window |
| US9388276B2 (en) | 2011-02-25 | 2016-07-12 | University Of Massachusetts | Monomers and polymers for functional polycarbonates and poly(ester-carbonates) and PEG-co-polycarbonate hydrogels |
| RU2662006C2 (ru) | 2013-11-07 | 2018-07-23 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Способ модификации полимеров |
| CA2928000A1 (en) | 2013-11-07 | 2015-05-14 | Akzo Nobel Chemicals International B.V. | Cyclic carbonate azide |
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- 2014-10-31 CA CA2928332A patent/CA2928332A1/en not_active Abandoned
- 2014-10-31 WO PCT/EP2014/073418 patent/WO2015067533A1/en active Application Filing
- 2014-10-31 KR KR1020167014339A patent/KR20160084842A/ko not_active Application Discontinuation
- 2014-10-31 MX MX2016005599A patent/MX2016005599A/es unknown
- 2014-10-31 CN CN201480058504.7A patent/CN105705563B/zh not_active Expired - Fee Related
- 2014-10-31 US US15/034,720 patent/US9688783B2/en not_active Expired - Fee Related
- 2014-10-31 EP EP14792803.0A patent/EP3066151A1/en not_active Withdrawn
- 2014-10-31 JP JP2016527298A patent/JP6306176B2/ja not_active Expired - Fee Related
- 2014-11-06 TW TW103138589A patent/TWI627197B/zh not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI627197B (zh) | 2018-06-21 |
| MX2016005599A (es) | 2016-07-21 |
| JP2017500379A (ja) | 2017-01-05 |
| JP6306176B2 (ja) | 2018-04-04 |
| CA2928332A1 (en) | 2015-05-14 |
| RU2016121181A (ru) | 2017-12-08 |
| SA516371025B1 (ar) | 2017-10-24 |
| ZA201602832B (en) | 2017-04-26 |
| RU2016121181A3 (zh) | 2018-06-06 |
| CN105705563B (zh) | 2018-03-23 |
| CN105705563A (zh) | 2016-06-22 |
| KR20160084842A (ko) | 2016-07-14 |
| US9688783B2 (en) | 2017-06-27 |
| EP3066151A1 (en) | 2016-09-14 |
| WO2015067533A1 (en) | 2015-05-14 |
| RU2671352C2 (ru) | 2018-10-30 |
| US20160347876A1 (en) | 2016-12-01 |
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