HRP20190874T1 - Stereoregularni diblok polibutadieni s 1,4-cis/1,2 sindiotaktičnom strukturom dobiveni stereospecifičnom polimerizacijom - Google Patents
Stereoregularni diblok polibutadieni s 1,4-cis/1,2 sindiotaktičnom strukturom dobiveni stereospecifičnom polimerizacijom Download PDFInfo
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- HRP20190874T1 HRP20190874T1 HRP20190874TT HRP20190874T HRP20190874T1 HR P20190874 T1 HRP20190874 T1 HR P20190874T1 HR P20190874T T HRP20190874T T HR P20190874TT HR P20190874 T HRP20190874 T HR P20190874T HR P20190874 T1 HRP20190874 T1 HR P20190874T1
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- polybutadiene
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- stereoregular diblock
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- 229920002857 polybutadiene Polymers 0.000 title claims 30
- 238000012721 stereospecific polymerization Methods 0.000 title claims 3
- 239000005062 Polybutadiene Substances 0.000 claims 29
- 238000000034 method Methods 0.000 claims 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 8
- 125000003118 aryl group Chemical group 0.000 claims 7
- 239000000203 mixture Substances 0.000 claims 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 5
- -1 aliphatic phosphines Chemical class 0.000 claims 4
- 239000003446 ligand Substances 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 229910052799 carbon Inorganic materials 0.000 claims 3
- 125000005843 halogen group Chemical group 0.000 claims 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 3
- 150000003003 phosphines Chemical class 0.000 claims 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 238000004458 analytical method Methods 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 150000004700 cobalt complex Chemical class 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000002425 crystallisation Methods 0.000 claims 2
- 230000008025 crystallization Effects 0.000 claims 2
- 229910052731 fluorine Inorganic materials 0.000 claims 2
- 239000011737 fluorine Substances 0.000 claims 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 2
- 230000009477 glass transition Effects 0.000 claims 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 2
- 238000002844 melting Methods 0.000 claims 2
- 230000008018 melting Effects 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 150000002894 organic compounds Chemical class 0.000 claims 2
- 150000002902 organometallic compounds Chemical class 0.000 claims 2
- 230000000737 periodic effect Effects 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 150000001868 cobalt Chemical class 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 150000008282 halocarbons Chemical class 0.000 claims 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 150000008040 ionic compounds Chemical class 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000005673 monoalkenes Chemical class 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 150000002891 organic anions Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000000284 resting effect Effects 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229950011008 tetrachloroethylene Drugs 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 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
- C08F295/00—Macromolecular compounds obtained by polymerisation using successively different catalyst types without deactivating the intermediate polymer
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
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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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7095—Cobalt, nickel or compounds thereof
- C08F4/7096—Cobalt or compounds thereof
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- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
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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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/05—Transitioning, i.e. transition from one catalyst to another with use of a deactivating agent
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Claims (18)
1. Stereoregularni diblok polibutadien, naznačen time što se sastoji od polibutadienskog bloka koji ima 1,4-cis strukturu i polibutadienskog bloka koji ima 1,2 sindiotaktičku strukturu sljedeće formule (I):
PB1-PB2 (I)
gdje:
– PB1 odgovara polibutadienskom bloku koji ima 1,4-cis strukturu;
– PB2 odgovara polibutadienskom bloku koji ima 1,2 sindiotaktičku strukturu;
koji ima sadržaj 1,4-trans jedinica manji od 3%, molarno.
2. Stereoregularni diblok polibutadien u skladu s patentnim zahtjevom 1, naznačen time što navedeni stereoregularni diblok polibutadien ima sljedeće karakteristike:
– kod infracrvene analize (FT-IR), pojaseve tipične za nizove 1,4-cis i 1,2, centrirane na 737 cm–1 odnosno na 911 cm–1;
– kod 13C-NMR analize, signali karakteristični za prijelaze između polibutadienskog bloka koji ima 1,4- cis strukturu i polibutadienskog bloka koji ima 1,2 strukturu na 30,7 ppm, na 25,5 ppm i na 41,6 ppm.
3. Stereoregularni diblok polibutadien u skladu s patentnim zahtjevom 1 ili 2, naznačen time što, u navedenom stereoregularnom diblok polibutadienu:
– blok koji ima 1,4-cis strukturu ima temperaturu stakljenja (Tg) ispod ili jednaku –100 °C, talište (Tm) ispod ili jednako –2 °C i temperaturu kristalizacije (Tc) ispod ili jednaku –25 °C;
– blok koji ima 1,2 sindiotaktičku strukturu ima temperaturu stakljenja (Tg) ispod ili jednaku –10 °C, talište (Tm) iznad ili jednako 70 °C i temperaturu kristalizacije (Tc) iznad ili jednaku 55 °C.
4. Stereoregularni diblok polibutadien u skladu s bilo kojim od prethodnih patentnih zahtjeva, naznačen time što navedeni stereoregularni diblok polibutadien ima indeks polidisperzije (PDI) koji odgovara omjeru Mw/Mn (Mw = težinski uprosječena molekulska težina; Mn = brojevno uprosječena molekulska težina) u rasponu od 1,9 do 2,2.
5. Stereoregularni diblok polibutadien u skladu s bilo kojim od prethodnih patentnih zahtjeva, naznačen time što je u navedenom stereoregularnom diblok polibutadienu polibutadienski blok koji ima 1,4-cis strukturu amorfan, na sobnoj temperaturi u uvjetima mirovanja bez izlaganja stresu, te ima 1,4-cis sadržaj iznad ili jednako 96%, molarno, u odnosu na ukupnu molarnu količinu butadienskih jedinica prisutnih u navedenom polibutadienskom bloku koji ima 1,4-cis strukturu.
6. Stereoregularni diblok polibutadien u skladu s bilo kojim od prethodnih patentnih zahtjeva, naznačen time što u navedenom stereoregularnom diblok polibutadienu polibutadienski blok koji ima 1,2 sindiotaktičku strukturu ima sadržaj sindiotaktičkih trijada [(rr) %] iznad ili jednako 15%.
7. Stereoregularni diblok polibutadien u skladu s bilo kojim od prethodnih patentnih zahtjeva, naznačen time što se u navedenom stereoregularnom diblok polibutadienu molarni omjer 1,4-cis/1,2 kreće od 15:85 do 80:20.
8. Stereoregularni diblok polibutadien u skladu s bilo kojim od prethodnih patentnih zahtjeva, naznačen time što navedeni stereoregularni diblok polibutadien ima težinski uprosječenu molekulsku težinu (Mw) u rasponu od 100.000 g/mol do 800.000 g/mol.
9. Postupak priprave stereoregularnog diblok polibutadiena u skladu s bilo kojim od prethodnih patentnih zahtjeva, naznačen time što se sastoji u:
– podvrgavanju 1,3-butadiena potpunoj ili djelomičnoj stereospecifičnoj polimerizaciji u prisutnosti katalitičkog sustava koji sadrži najmanje jedan fosfinski ligand, kojeg se bira između ometanih alifatskih fosfina ili bidentatnih fosfina, kako bi se dobilo polibutadien s 1,4-cis živom strukturom;
– dodavanju najmanje jednog monodentatnog aromatskog fosfina i izborno 1,3-butadiena, uz nastavak navedene stereospecifične polimerizacije kako bi se dobilo navedeni stereoregularni diblok polibutadien, koji se sastoji od polibutadienskog bloka, koji ima 1,4-cis strukturu, i polibutadienskog bloka, koji ima 1,2 sindiotaktičku strukturu.
10. Postupak u skladu s patentnim zahtjevom 9, naznačen time što se navedeni kompleks kobalta s najmanje jednim fosfinskim ligandom, kojeg se bira između ometanih alifatskih fosfina ili bidentatnih fosfina, bira između kompleksa kobalta općih formula (I) ili (II):
,
gdje:
– R1 i R2, iste ili različite, se bira između nerazgranatih ili razgranatih C1-C20 alkilnih skupina, C3-C30 cikloalkilnih skupina;
– R3 se bira između nerazgranatih ili razgranatih C1-C20 alkilnih skupina, C3-C30 cikloalkilnih skupina;
– R4 i R5, iste ili različite, se bira između nerazgranatih ili razgranatih C1-C20 alkilnih skupina, C3-C30 cikloalkilnih skupina, C6-C30 arilnih skupina, a poželjnije ih se bira između metila, etila, n-propila, iso-propila, tert-butila, ciklopentila, cikloheksila, fenila;
– Y predstavlja dvovalentnu skupinu -(CH2)n-, gdje je n cijeli broj u rasponu od 1 do 5; ili dvovalentnu skupinu -NR6-, gdje R6 predstavlja atom vodika, ili nerazgranatu ili razgranatu C1-C20 alkilnu skupinu, poželjnije atom vodika; ili dvovalentnu skupinu -(CH2)m-R’-(CH2)m-, gdje R’ predstavlja izborno supstituiranu arilnu skupinu;
– X1 i X2, isti ili različiti, predstavljaju atom halogena; ili ih se bira između nerazgranatih ili razgranatih C1-C20 alkilnih skupina, skupina -OCOR7 ili skupina -OR7, gdje se R7 bira između nerazgranatih ili razgranatih C1-C20 alkilnih skupina.
11. Postupak u skladu s patentnim zahtjevom 9 ili 10, naznačen time što navedeni katalitički sustav sadrži najmanje jedan sukatalizator, kojeg se bira između organskih spojeva elementa M’ koji nije ugljik, gdje se navedeni element M’ bira između elemenata koji pripadaju skupinama 2, 12, 13 ili 14 u Periodnoj tablici elemenata.
12. Postupak u skladu s patentnim zahtjevom 11, naznačen time što se navedeni sukatalizator bira između alkilaluminijevih spojeva opće formule (III):
Al(X’)n(R8)3-n (III)
gdje X’ predstavlja atom halogena, poput klora, broma, joda, fluora; R8 se bira između nerazgranatih ili razgranatih C1-C20 alkilnih skupina, cikloalkilnih skupina, arilnih skupina, gdje su navedene skupine izborno supstituirane s jednim ili više atoma silicija ili germanija; i n je cijeli broj u rasponu od 0 do 2.
13. Postupak u skladu s patentnim zahtjevom 11, naznačen time što se navedeni sukatalizator bira između organo-oksigeniranih spojeva elementa M’ koji nije ugljik koji pripada skupinama 13 ili 14 u Periodnoj tablici elemenata, poput aluminoksana opće formule (IV):
(R9)2-Al-O-[-Al(R10)-O-]p-Al-(R11)2 (IV)
gdje R9, R10 i R11, isti ili različiti, predstavljaju atom vodika, atom halogena, poput klora, broma, joda, fluora; ili ih se bira između nerazgranatih ili razgranatih C1-C20 alkilnih skupina, cikloalkilnih skupina, arilnih skupina, gdje su navedene skupine izborno supstituirane s jednim ili više atoma silicija ili germanija; i p je cijeli broj u rasponu od 0 do 1000.
14. Postupak u skladu s patentnim zahtjevom 11, naznačen time što se navedeni sukatalizator bira između organometalnih spojeva ili smjesa organometalnih spojeva elementa M’ koji nije ugljik, koji može reagirati s kompleks kobalta s najmanje jednim fosfinskim ligandom, kojeg se bira između ometanih alifatskih fosfina ili bidentatnih fosfina, u skladu s patentnim zahtjevom 10, iz kojih se izvadi jedno- ili viševalentni anion, kako bi se dobilo, u jednu ruku, najmanje jedan neutralni spoj, a u drugu, ionski spoj, koji se sastoji od kationa koji sadrži metal (Co), koordiniran s ligandom, i nekoordinirajućeg organskog aniona, koji sadrži metal M’, gdje je negativni naboj delokaliziran na višecentričnoj strukturi, poput organskih spojeva aluminija i osobito bora, poput onih koje predstavljaju sljedeće opće formule (V), (VI) ili (VII):
[(RC)WH4-W]•[B(RD)4]–; B(RD)3; Al(RD)3; B(RD)3P; [Ph3C]+•[B(RD)4]– (V)
[(RC)3PH]+•[B(RD)4]– (VI)
[Li]+•[B(RD)4]–; [Li]+•[Al(RD)4]– (VII)
gdje je w cijeli broj u rasponu od 0 do 3, svaka skupina RC neovisno predstavlja alkilnu skupinu ili arilnu skupinu s od 1 do 10 atoma ugljika, gdje svaka skupina RD neovisno predstavlja djelomično ili posve, po mogućnosti posve, fluoriranu arilnu skupinu s od 6 do 20 atoma ugljika, P predstavlja izborno supstituirani pirolski radikal.
15. Postupak u skladu s bilo kojim od patentnih zahtjeva od 9 do 14, naznačen time što se navedeni monodentatni aromatski fosfin bira između aromatskih fosfina opće formule (VIII):
P(R)m(Ph)n (VIII)
gdje:
– R se bira između nerazgranatih ili razgranatih C1-C16 alkilnih skupina, izborno supstituiranih C3-C16 cikloalkilnih skupina, alilnih skupina, izborno supstituiranog fenila;
– Ph je izborno supstituirani fenil;
– m i n, međusobno različiti, su 1 ili 2, gdje m+n = 3.
16. Postupak u skladu s bilo kojim od patentnih zahtjeva od 9 do 15, naznačen time što se navedeni postupak provodi u prisutnosti inertnog organskog otapala, kojeg se bira između:
zasićenih alifatskih ugljikovodika, poput butana, pentana, heksana, heptana, ili njihovih smjesa;
zasićenih cikloalifatskih ugljikovodika, poput ciklopentana, cikloheksana, ili njihovih smjesa;
monoolefina, poput 1-butena, 2-butena, ili njihovih smjesa;
aromatskih ugljikovodika, poput benzena, toluena, ksilena, ili njihovih smjesa;
halogeniranih ugljikovodika, poput metilen-klorida, kloroforma, ugljičnog tetraklorida, trikloretilena, perkloretilena, 1,2-dikloretana, klorbenzena, brombenzena, klortoluena, ili njihovih smjesa.
17. Postupak u skladu s patentnim zahtjevom 16, naznačen time što se koncentracija 1,3-butadiena kojeg treba polimerizirati u navedenom inertnom organskom otapalu kreće od 5%, težinski, do 50% u odnosu na ukupnu težinu smjese 1,3-butadiena i inertnog organskog otapala.
18. Postupak u skladu s bilo kojim od patentnih zahtjeva od 9 do 17, naznačen time što se navedeni postupak provodi na temperaturi u rasponu od –70 °C do +120 °C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT001828A ITMI20131828A1 (it) | 2013-11-05 | 2013-11-05 | Polibutadieni di-blocco stereoregolari a struttura 1,4-cis/1,2 sindiotattica da polimerizzazione stereospecifica |
| EP14812612.1A EP3066139B1 (en) | 2013-11-05 | 2014-11-03 | Stereoregular diblock polybutadienes having a 1,4-cis/syndiotactic 1,2 structure from stereospecific polymerization |
| PCT/IB2014/065764 WO2015068094A1 (en) | 2013-11-05 | 2014-11-03 | Stereoregular diblock polybutadienes having a 1,4-cis/syndiotactic 1,2 structure from stereospecific polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HRP20190874T1 true HRP20190874T1 (hr) | 2019-07-12 |
Family
ID=49683904
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HRP20190874TT HRP20190874T1 (hr) | 2013-11-05 | 2019-05-13 | Stereoregularni diblok polibutadieni s 1,4-cis/1,2 sindiotaktičnom strukturom dobiveni stereospecifičnom polimerizacijom |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US10093763B2 (hr) |
| EP (1) | EP3066139B1 (hr) |
| JP (1) | JP6574190B2 (hr) |
| KR (1) | KR102223300B1 (hr) |
| CN (1) | CN105683230B (hr) |
| BR (1) | BR112016009097B1 (hr) |
| CA (1) | CA2925263C (hr) |
| EA (1) | EA031540B1 (hr) |
| ES (1) | ES2726852T3 (hr) |
| HK (1) | HK1223386A1 (hr) |
| HR (1) | HRP20190874T1 (hr) |
| HU (1) | HUE043431T2 (hr) |
| IT (1) | ITMI20131828A1 (hr) |
| MX (1) | MX2016005664A (hr) |
| MY (1) | MY172664A (hr) |
| PL (1) | PL3066139T3 (hr) |
| PT (1) | PT3066139T (hr) |
| RS (1) | RS58772B1 (hr) |
| SG (1) | SG11201603260WA (hr) |
| TR (1) | TR201907212T4 (hr) |
| TW (1) | TWI678379B (hr) |
| WO (1) | WO2015068094A1 (hr) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20131830A1 (it) * | 2013-11-05 | 2015-05-06 | Versalis Spa | Polibutadieni di-blocco stereoregolari a struttura 1,4-cis/1,2 sindiotattica da polimerizzazione stereospecifica |
| IT201700059763A1 (it) | 2017-05-31 | 2018-12-01 | Versalis Spa | Copolimeri butadiene-isoprene di-blocco e procedimento per la loro preparazione |
| IT202000028823A1 (it) | 2020-11-27 | 2022-05-27 | Consiglio Nazionale Ricerche | Copolimeri dienici a stereoblocchi e relativo processo di preparazione. |
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| US3498963A (en) | 1966-09-26 | 1970-03-03 | Japan Synthetic Rubber Co Ltd | Process for the catalytic preparation of 1,2-polybutadiene having a high percentage of vinyl configuration |
| US3522332A (en) | 1967-06-02 | 1970-07-28 | Japan Synthetic Rubber Co Ltd | Process for the preparation of 1,2-polybutadiene |
| JPS4917666B1 (hr) * | 1970-12-25 | 1974-05-02 | ||
| JPS4917667B1 (hr) | 1970-12-25 | 1974-05-02 | ||
| US3817968A (en) | 1972-11-28 | 1974-06-18 | Bridgestone Tire Co Ltd | Method of producing equibinary (cis 1.4-1.2) polybutadiene |
| DE2447203C3 (de) | 1974-10-03 | 1982-03-18 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur Herstellung von Polybutadien |
| JPS53143685A (en) | 1977-05-23 | 1978-12-14 | Japan Synthetic Rubber Co Ltd | Preparation of 1,2-polybutadiene |
| US4255296A (en) | 1977-12-02 | 1981-03-10 | Bridgestone Tire Company Limited | Polybutadiene rubber composition |
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| JPS56109204A (en) * | 1980-01-31 | 1981-08-29 | Japan Synthetic Rubber Co Ltd | Preparation of polybutadiene |
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| IT1231774B (it) | 1989-08-03 | 1991-12-21 | Enichem Anic Spa | Catalizzatore e procedimento per la polimerizzazione e per la copolimerizzazione di alfa olefine. |
| US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
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| US5189192A (en) | 1991-01-16 | 1993-02-23 | The Dow Chemical Company | Process for preparing addition polymerization catalysts via metal center oxidation |
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| US5721185A (en) | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
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Also Published As
| Publication number | Publication date |
|---|---|
| TR201907212T4 (tr) | 2019-06-21 |
| TWI678379B (zh) | 2019-12-01 |
| PT3066139T (pt) | 2019-05-31 |
| BR112016009097A2 (hr) | 2017-08-01 |
| JP6574190B2 (ja) | 2019-09-11 |
| CN105683230A (zh) | 2016-06-15 |
| MX2016005664A (es) | 2016-12-07 |
| CA2925263C (en) | 2021-11-30 |
| BR112016009097B1 (pt) | 2021-09-14 |
| ITMI20131828A1 (it) | 2015-05-06 |
| JP2016536447A (ja) | 2016-11-24 |
| HK1223386A1 (zh) | 2017-07-28 |
| CA2925263A1 (en) | 2015-05-14 |
| WO2015068094A1 (en) | 2015-05-14 |
| US20160264707A1 (en) | 2016-09-15 |
| KR102223300B1 (ko) | 2021-03-05 |
| KR20160084854A (ko) | 2016-07-14 |
| CN105683230B (zh) | 2018-07-13 |
| EA201690625A1 (ru) | 2016-12-30 |
| TW201522393A (zh) | 2015-06-16 |
| PL3066139T3 (pl) | 2019-08-30 |
| US10093763B2 (en) | 2018-10-09 |
| HUE043431T2 (hu) | 2019-08-28 |
| MY172664A (en) | 2019-12-09 |
| SG11201603260WA (en) | 2016-05-30 |
| ES2726852T3 (es) | 2019-10-09 |
| EA031540B1 (ru) | 2019-01-31 |
| EP3066139B1 (en) | 2019-02-20 |
| EP3066139A1 (en) | 2016-09-14 |
| RS58772B1 (sr) | 2019-06-28 |
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