ITSA20090013A1 - CIS-MIXED COMPOUNDS OF 1.4-POLIBUTADIENE REINFORCED WITH MICRO AND NANOPARTICLES OF POLYSTYRENE SINDIOTATTICO CRYSTALLINE PRODUCED BY A SINGLE STAGE CATALYTIC PROCESS - Google Patents
CIS-MIXED COMPOUNDS OF 1.4-POLIBUTADIENE REINFORCED WITH MICRO AND NANOPARTICLES OF POLYSTYRENE SINDIOTATTICO CRYSTALLINE PRODUCED BY A SINGLE STAGE CATALYTIC PROCESS Download PDFInfo
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- ITSA20090013A1 ITSA20090013A1 IT000013A ITSA20090013A ITSA20090013A1 IT SA20090013 A1 ITSA20090013 A1 IT SA20090013A1 IT 000013 A IT000013 A IT 000013A IT SA20090013 A ITSA20090013 A IT SA20090013A IT SA20090013 A1 ITSA20090013 A1 IT SA20090013A1
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- Prior art keywords
- styrene
- spsa
- sps
- segments
- copolymer
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 25
- 230000008569 process Effects 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 title claims description 20
- 230000003197 catalytic effect Effects 0.000 title claims description 8
- 239000004793 Polystyrene Substances 0.000 title claims description 6
- 229920002223 polystyrene Polymers 0.000 title claims description 6
- 239000002105 nanoparticle Substances 0.000 title claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 39
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 22
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920006030 multiblock copolymer Polymers 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007848 Bronsted acid Substances 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 238000010382 chemical cross-linking Methods 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Chemical group 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 230000000704 physical effect Effects 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000005062 Polybutadiene Substances 0.000 description 16
- 229920002857 polybutadiene Polymers 0.000 description 16
- -1 alumina Chemical class 0.000 description 13
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 125000005353 silylalkyl group Chemical group 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-O phenylazanium Chemical compound [NH3+]C1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-O 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000006492 halo alkyl aryl group Chemical group 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000003106 haloaryl group Chemical group 0.000 description 2
- 125000002034 haloarylalkyl group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ITYXDCHVYRDZDC-UHFFFAOYSA-N 1,1,1,2-tetrachlorooctane Chemical compound CCCCCCC(Cl)C(Cl)(Cl)Cl ITYXDCHVYRDZDC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001432959 Chernes Species 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920006978 SSBR Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 235000017957 Xanthosoma sagittifolium Nutrition 0.000 description 1
- 240000001781 Xanthosoma sagittifolium Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940095643 calcium hydroxide Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YJVQNSXZGFXJKY-UHFFFAOYSA-N n-methyl-n-(1-phenylethyl)prop-2-yn-1-amine Chemical compound C#CCN(C)C(C)C1=CC=CC=C1 YJVQNSXZGFXJKY-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229920006135 semi-crystalline thermoplastic polymer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012721 stereospecific polymerization Methods 0.000 description 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Description
DESCRIZIONE DESCRIPTION
a corredo di una domanda di brevetto per invenzione industriale dal titolo: accompanying a patent application for industrial invention entitled:
MESCOLE DI C/A-l,4-POLIBUTADIENE RINFORZATE CON MICRO E NANOPARTICELLE DI POLISTIRENE SINDIOTATTICO CRISTALLINO PRODOTTE MEDIANTE UN SINGOLO PROCESSO CATALITICO A STADI. COMPOUNDS OF C / A-1, 4-POLYBUTADIENE REINFORCED WITH MICRO AND NANOPARTICLES OF CRYSTALLINE SYNDIOTACTIC POLYSTYRENE PRODUCED BY MEANS OF A SINGLE STAGE CATALYTIC PROCESS.
INTRODUZIONE ALL’INVENZIONE INTRODUCTION TO THE INVENTION
Mescole polimeriche a base di m-l,4-polibutadienc, rinforzate con composti inorganici (ossidi metallici quali allumina, ossidi di ferro e magnesio; ossidi metallici idrati come idrossido di alluminio, di magnesio e calcio; silicati e silice; nerofumo; fibre di carbonio e di vetro) o polimeri termoplastici (poliuretano, polietilene, polistirene atattico e copolimeri stirene-acrilonitrile (SAN)), sono generalmente utilizzate dall’industria della gomma per specifiche applicazioni sia statiche che dinamiche. Polymeric compounds based on m-1, 4-polybutadien, reinforced with inorganic compounds (metal oxides such as alumina, iron and magnesium oxides; hydrated metal oxides such as aluminum, magnesium and calcium hydroxide; silicates and silica; carbon black; carbon fibers and glass) or thermoplastic polymers (polyurethane, polyethylene, atactic polystyrene and styrene-acrylonitrile (SAN) copolymers), are generally used by the rubber industry for specific static and dynamic applications.
Mescole di cA-l,4-polibutadiene con polimeri termoplastici come polietilene [T. Muraki; M, Tajima, improvements in rubber for medicai or pharmaceutìcai artides. Eur. Pat. Àppi. (1989) EP 324554 Al 19890719] o poliolefine stcreoregolari, come polipropilene isotattico e sindiotattico, sono state utilizzate per la produzione di termoplastici vulcanizzabili [W. Wcng; S. Jacob; P. Jiang; A,H. Dekmezian; A. K. Mchta; J. R. Ayers; D. J. Lohse; P. W. Manders; P. Arjunan, Processes far preparing thermoplastic vulcanizates and articles. PCT Int. Appi. (2007) WO 2007142742 Al], Per questi materiali sono state proposte applicazioni di uso statico per la produzione di tappi o contenitori caratterizzati da buone proprietà meccaniche e scarsa permeabilità a solventi organici. Mixtures of cA-1,4-polybutadiene with thermoplastic polymers such as polyethylene [T. Muraki; M, Tajima, improvements in rubber for medicai or pharmaceutìcai artides. Eur. Pat. Àppi. (1989) EP 324554 Al 19890719] or stregular polyolefins, such as isotactic and syndiotactic polypropylene, have been used for the production of vulcanizable thermoplastics [W. Wcng; S. Jacob; P. Jiang; A, H. Dekmezian; A. K. Mchta; J. R. Ayers; D. J. Lohse; P. W. Manders; P. Arjunan, Processes far preparing thermoplastic vulcanizates and articles. PCT Int. Appi. (2007) WO 2007142742 A1]. For these materials, applications of static use have been proposed for the production of caps or containers characterized by good mechanical properties and poor permeability to organic solvents.
Tali mescole polimeriche sono tipicamente preparate mediante: i) miscelazione meccanica dei due polimeri in opportuni miscelatori (Banbury mixer); il) precipitazione da soluzione dei due polimeri; Hi) polimerizzazione in si/it del polimero termoplastico in presenza di soluzioni diluite di cri- 1,4-polibutadiene. Such polymeric blends are typically prepared by: i) mechanical mixing of the two polymers in suitable mixers (Banbury mixer); ii) solution precipitation of the two polymers; Hi) polymerization in si / it of the thermoplastic polymer in the presence of dilute solutions of crystalline 1,4-polybutadiene.
Oggetto della presente invenzione è un nuovo metodo di sintesi di mescole costituite da una matrice di cri- 1,4-polibutadiene rinforzata con mieto e nano particelle di polistirene sindiotattico semicristallino, ottenute in un processo multistadio condotto in un singolo reattore in presenza di un catalizzatore organometallico di un metallo di transizione o un lantanoide. The object of the present invention is a new method of synthesis of mixtures consisting of a matrix of crystalline-1,4-polybutadiene reinforced with meto and nano particles of syndiotactic semi-crystalline polystyrene, obtained in a multistage process carried out in a single reactor in the presence of a catalyst organometallic of a transition metal or a lanthanide.
Oggetto della presente invenzione è il ruolo del polistirene sindiotattico scmicristallino quale agente rinforzante di elastomeri polidienici prodotti secondo la procedura sopra descritta. The object of the present invention is the role of syndiotactic scmicrystalline polystyrene as a reinforcing agent of polydidene elastomers produced according to the procedure described above.
Costituisce inoltre parte integrante della presente invenzione l’uso di un copolimero multiblocco, costituito da segmenti di polistirene sindiotattico separati da un’unità o da segmenti polimerici di un monomero A, avente la funzione di compatibilizzare mescole di cri- 1,4-polibutadiene e polistirene sindiotattico. Questo terzo componente della mescola è prodotto nello stesso reattore in un processo multistadio sequenziale o aggiunto successivamente alle mescole di di m-l,4-polibutadiene e polistirene sindiotattico. The use of a multiblock copolymer, consisting of syndiotactic polystyrene segments separated by a unit or polymeric segments of a monomer A, having the function of compatibilizing mixtures of crystalline 1,4-polybutadiene and syndiotactic polystyrene. This third component of the blend is produced in the same reactor in a sequential multistage process or added subsequently to the mixtures of di m-1, 4-polybutadiene and syndiotactic polystyrene.
La scoperta della polimerizzazione stereospecifica di 1,3-butadiene catalizzata da composti di metalli di transizione, attivati con composti alchilici di Alluminio, risale agli albori della catalisi Ziegier-Natta. Tctraalogcnuri di Titanio T1X4(X = CI, Br, I) attivati con composti trialchilici di alluminio A1R3(R = Me, Et, i-Bu) catalizzano, in solventi idrocarburici aromatici, la formazione di cA-l,4-po]tbutadiene con alto grado di selettività [G. Natta, L. Porri, Elastomcrs by coordinatcd anionic mechanism, A. Diene elastomers. In Polymer Chemistiy of Synthetic Elastomers, Kennedy, J. P., Tornqvist, E,, Eds.; Wiley-Intcrscience: New York, 1969; Vol.2, pp.597-678], La frazione molare di unità c/s- 1,4-, XCÌS-M, in catena polimerica è compresa tra 0.65 (X = Cl) e 0.95 (X = I), mentre la distribuzione delle masse molecolari è ampia, in accordo con la natura eterogenea e multisito dei catalizzatori, come osservato per le poliolefme risultanti dagli stessi sistemi catalitici. The discovery of the stereospecific polymerization of 1,3-butadiene catalyzed by transition metal compounds, activated with aluminum alkyl compounds, dates back to the dawn of Ziegier-Natta catalysis. T1X4 titanium chloride halides (X = CI, Br, I) activated with aluminum trialkyl compounds A1R3 (R = Me, Et, i-Bu) catalyze, in aromatic hydrocarbon solvents, the formation of cA-1,4-po] tbutadiene with a high degree of selectivity [G. Natta, L. Porri, Elastomcrs by coordinatcd anionic mechanism, A. Diene elastomers. In Polymer Chemistiy of Synthetic Elastomers, Kennedy, J. P., Tornqvist, E ,, Eds .; Wiley-Intcrscience: New York, 1969; Vol. 2, pp.597-678], The mole fraction of units c / s- 1,4-, XCI-M, in the polymer chain is between 0.65 (X = Cl) and 0.95 (X = I), while the distribution of the molecular masses is wide, in accordance with the heterogeneous and multisite nature of the catalysts, as observed for the polyolefms resulting from the same catalytic systems.
cA-l,4-Polibutadiene con più elevato grado di stereoregolarità (.rcl5-i,4> 0.95) è stato successivamente ottenuto con catalizzatori omogenei costituiti da sali organici di Cobalto, come ad es. Co(ottanoato)2, attivati con melila] lumossano (MAO) [P. Racanelli, L. Porri, Eur. Polym. J. 1970, 6, 751], cA-1,4-Polybutadiene with a higher degree of stereoregularity (.rcl5-i, 4> 0.95) was subsequently obtained with homogeneous catalysts consisting of organic cobalt salts, such as e.g. Co (octanoate) 2, activated with melila] lumoxane (MAO) [P. Racanelli, L. Porri, Eur. Polym. J. 1970, 6, 751],
1! MAO c un composto a bassa massa molecolare, solubile in toluene, risultante dalla lenta reazione di idrolisi a temperatura ambiente deiralluminio trimctile (AlMej). Allumossanì derivati dall’ alluminiotriisobutile, denominati TIBAO, sono più solubili del MAO in toluene c risultano anche solubili in solventi idrocarburici alifatici. 1! MAO is a low molecular mass compound, soluble in toluene, resulting from the slow hydrolysis reaction of trimctyl aluminum (AlMej) at room temperature. Alumoxane derived from aluminum triisobutyl, called TIBAO, are more soluble than MAO in toluene and are also soluble in aliphatic hydrocarbon solvents.
Allumossani modificati (MMAO), solubili in solventi idrocarburici alifatici, possono essere inoltre ottenuti per trattamento di MAO con Al-iBu3. Modified alumoxanes (MMAO), soluble in aliphatic hydrocarbon solvents, can also be obtained by treating MAO with Al-iBu3.
La polimerizzazione altamente c;.y-l,4 specifica di l ,3-butadiene è stata inoltre ottenuta con tricarbossilati di Neodimio [S, Zhiquan, O. Jun, W. Fusong, H. B. Zhenya, J Poìym Sci A, 1980, 18, 3345; G. Ricci, S. Italia, F, Cabassi, L. Porri Poiym Commuti 1987, 25, 223] o addotti NdCl3(L) (dove L = piridina, tetraidrofurano, dimctilsolfossido) [J.H. Yang, M, Tsutsui, Z. Chen, D. Bergbreiter Macromolecules 1982, 15, 230] attivati con miscele di composti trialchilici e dialchilmonoalogenuri di Alluminio. In questo caso > 0.99 e la distribuzione delle masse molecolari è di circa 2. The highly specific polymerization of 1,3-butadiene was also achieved with Neodymium tricarboxylates [S, Zhiquan, O. Jun, W. Fusong, H. B. Zhenya, J Poìym Sci A, 1980, 18, 3345 ; G. Ricci, S. Italia, F, Cabassi, L. Porri Poiym Commuti 1987, 25, 223] or adducts NdCl3 (L) (where L = pyridine, tetrahydrofuran, dimethyl sulfoxide) [J.H. Yang, M, Tsutsui, Z. Chen, D. Bergbreiter Macromolecules 1982, 15, 230] activated with mixtures of trialkyl compounds and aluminum dialkyl monohalides. In this case> 0.99 and the distribution of the molecular masses is about 2.
Taube e collaboratori hanno evidenziato che composti triallilici di Neodimio, Nd{C3H5)3, producono c/s-I,4-polibutadiene con elevata selettività e strette distribuzioni delle masse molecolari a temperature di polimerizzazione relativamente elevate, come 50°C [S. Maiwald, C. Sommer, G. Mìillcr, R. Taube Macromol. Chem. Phys. 2001, 202, 1446]. Taube and collaborators showed that neodymium triallyl compounds, Nd {C3H5) 3, produce c / s-I, 4-polybutadiene with high selectivity and narrow molecular mass distributions at relatively high polymerization temperatures, such as 50 ° C [S. Maiwald, C. Sommer, G. Mìillcr, R. Taube Macromol. Chem. Phys. 2001, 202, 1446].
Hou e collaboratori hanno riportato la polimerizzazione vivente ed altamente c/s- 1,4 specifica di butadiene e isoprene catalizzata da complessi alchilcationici delle tene rare con leganti bisfosfinofcnilammidici [L. Zhang, T. Suzuki, Y. Luo, M. Nishiura, Z. Hou Angew. Chem. hit. Ed. 2007, 46, 1909-1913]. Hou and collaborators reported the living and highly c / s-1,4 specific polymerization of butadiene and isoprene catalyzed by alkylcationic complexes of rare tenes with bisphosphine polyamide ligands [L. Zhang, T. Suzuki, Y. Luo, M. Nishiura, Z. Hou Angew. Chem. hit. Ed. 2007, 46, 1909-1913].
E’ stato inoltre riportato che composti ciclopentadienilici di Titanio, di formula CpTiCl3(Cp = η<5>- C5H5), attivati con MAO, producono cìs- 1,4-polibutadiene, con .TCÌS-I 4= 0.80, unità 1 ,2-viniliche isolate in catena polimerica con composizione xviniie.\y compresa tra 0.12 e 0.20 e tracce (< 0.01) di unità isolate di trans- 1,4 [L. Oliva, P. Longo, A. Grassi, P. Ammendola, C. Pcllecchia Makromol, Chem. Rapid Commuti. 1990, II, 519-524], La temperatura di transizione vetrosa del m-l,4-polibutadiene prodotto con catalizzatori ciclopentadienilici di Titanio è di -97°C e la distribuzione delle masse molecolari di circa 2. 11 derivato trialchilico CpTiMe3 attivato con forti acidi di Lewis, come BiCsFs^, catalizza a temperature inferiori a -20°C la polimerizzazione vivente di 1 ,3-butadiene: sono stati ottenuti campioni di c/s-l,4-polibutadiene con massa molecolare media numerale di 200KDa [A. Miyazavva, T, Kase, K. Soga Macromoìecules 2000, 33 , 2796], La polimerizzazione dello stirene catalizzata da composti ciclopentadienilici di Titanio, di formula Cp'TiCfi {Cp' = η<5>- C5Hs, η<5>- C5Me5, Indenile; X = F, CI, Br, F) attivati con MAO, e composti alchilici Cp'TiR3(Cp - η<5>- CsMes, R = CH3, CELPh) attivati da forti addi di Lewis, quali B(C6F5)_3 e [CPh3][B{C6F5)4], o da acidi di Bronsted, quali perfluoroarilborati di anilinio [PhNHjJfBfQFj^], produce polistirene sindiotattico con elevata attività ed elevata stereo c regio specificità [N. Ishihara, M. Kuramoto, M.Uot, Macromoìecules 1988, 27, 3356; R. E. Campbell, Eur. Pat. Appi. 421659, 1991; C. Pellecchia, P. Longo, A. Proto, A. Zambelli, Makromol. Chem., Rapid Commurt. 1992,73, 265]. Il polistirene sindiotattico è un polimero termoplastico semicristallino caratterizzato da una temperatura di transizione vetrosa (Tg) di circa 105°C e una temperatura di fusione (7m) di 273°C. II polistirene sindiotattico presenta alta resistenza termica, elevata velocità di cristallizzazione, buone proprietà isolanti, eccellenti caratteristiche di processabilità, stabilità dimensionale e bassa capacità di assorbimento di umidità [M. Malanga, Adv. Mater. 2000, 72, 1869]. It has also been reported that cyclopentadienyl compounds of Titanium, of the formula CpTiCl3 (Cp = η <5> - C5H5), activated with MAO, produce cis-1,4-polybutadiene, with TCIS-I 4 = 0.80, unit 1, 2-vinyls isolated in polymer chain with composition xviniie. Y comprised between 0.12 and 0.20 and traces (<0.01) of isolated units of trans-1,4 [L. Oliva, P. Longo, A. Grassi, P. Ammendola, C. Pcllecchia Makromol, Chem. Rapid Switch. 1990, II, 519-524], The glass transition temperature of m-1,4-polybutadiene produced with titanium cyclopentadienyl catalysts is -97 ° C and the molecular mass distribution of about 2. 11 trialkyl derivative CpTiMe3 activated with strong acids Lewis's, as BiCsFs ^, catalyzes the living polymerization of 1,3-butadiene at temperatures below -20 ° C: samples of c / s-1,4-polybutadiene with numeral average molecular mass of 200KDa were obtained [A. Miyazavva, T, Kase, K. Soga Macromoìecules 2000, 33, 2796], The polymerization of styrene catalyzed by cyclopentadienyl compounds of Titanium, of the formula Cp'TiCfi {Cp '= η <5> - C5Hs, η <5> - C5Me5 , Indenile; X = F, CI, Br, F) activated with MAO, and alkyl compounds Cp'TiR3 (Cp - η <5> - CsMes, R = CH3, CELPh) activated by strong Lewis addi, such as B (C6F5) _3 and [CPh3] [B {C6F5) 4], or from Bronsted acids, such as anilinium perfluoroarylborates [PhNHjJfBfQFj ^], produces syndiotactic polystyrene with high activity and high stereo c regio specificity [N. Ishihara, M. Kuramoto, M.Uot, Macromoìecules 1988, 27, 3356; R. E. Campbell, Eur. Pat. Appi. 421659, 1991; C. Pellecchia, P. Longo, A. Proto, A. Zambelli, Makromol. Chem., Rapid Commurt. 1992,73, 265]. Syndiotactic polystyrene is a semicrystalline thermoplastic polymer characterized by a glass transition temperature (Tg) of about 105 ° C and a melting temperature (7m) of 273 ° C. Syndiotactic polystyrene exhibits high thermal resistance, high crystallization rate, good insulating properties, excellent processability characteristics, dimensional stability and low moisture absorption capacity [M. Malanga, Adv. Mater. 2000, 72, 1869].
Hou ha riportato che composti monociclopentadienilici di Scandio di fonnula (C5Me4SiMe3)Sc(CH2SiMe3)2(THF) attivati con [Ph3C][B(C6Fi)4] possono essere utilizzati per la polimerizzazione vivente c sindiotatticospecifìca delio stirene [Y. Luo, J. Baldamus, Z. f lou ./. Am. Chem, Soc. 2004, 126, 13910]. Hou reported that monocyclopentadienyl compounds of Scandium di fonnula (C5Me4SiMe3) Sc (CH2SiMe3) 2 (THF) activated with [Ph3C] [B (C6Fi) 4] can be used for living c syndiotactic specific polymerization of styrene [Y. Luo, J. Baldamus, Z. f lou ./. Am. Chem, Soc. 2004, 126, 13910].
Composti ciclopentadienilici di Titanio di fonnula Cp'TiCl3(Cp’= η<5>- C5H5, η<5>-05Με5, Ind; X = F, Cl, Br, F) attivati con MAO, e quelli di fonnula generale Cp'TiRj(Cp — η<5>- CyMej, R = CHj, CH2Ph), attivati da foni acidi di Lewis, quali B(C6FJ)3e [CPh3][B(C F ) ], o da acidi di Bronsted, quali perfluoroarilborati di anilinio [PhNH3][B(C(,F ) ], copolimerizzano 1,3-butadienc e stirene produccndo, in opportune condizioni sperimentali, copolimeri a blocchi costituiti da segmenti di polistircne sindiotattico e segmenti di cw-l,4-polibutadiene, [A, Zambclli, A. Grassi, M. Caprio, D.E. Bowen Slyrene-butadiene block copolymer Eur. Pat. Appi. (2004) EP 1 0t3 683 Bl], La microstruttura di detti copolimeri può essere di seguito così schematizzata: Cp'TiCl3 titanium cyclopentadienyl compounds (Cp '= η <5> - C5H5, η <5> -05Με5, Ind; X = F, Cl, Br, F) activated with MAO, and those of general form Cp' TiRj (Cp - η <5> - CyMej, R = CHj, CH2Ph), activated by Lewis acid phones, such as B (C6FJ) 3e [CPh3] [B (C F)], or by Bronsted acids, such as perfluoroarylborates of anilinium [PhNH3] [B (C (, F)], copolymerize 1,3-butadiene and styrene producing, under suitable experimental conditions, block copolymers consisting of syndiotactic polystyrcne segments and cw-1,4-polybutadiene segments, [ A, Zambclli, A. Grassi, M. Caprio, D.E. Bowen Slyrene-butadiene block copolymer Eur. Pat. Appi. (2004) EP 1 0t3 683 Bl], The microstructure of said copolymers can be schematized below:
I rapporti di reattività rt= ABB^BS Cr2= Assise (A'// è la costante cinetica relativa all’addizione di un’unità monomerica M/air estremità della catena polimerica crescente dopo un’unità monomerica My), detenninati dalla composizione del copolimero definita a livello di diadi [A. Zambellì, M. Caprio, A. Grassi, D, E. Bowen Macromol. Chern. Phys. 2000, 201. 393] hanno rispettivamente valori compresi nell’ intervallo 3-÷8<χ>IO<2>e 4÷6<X>10<"!>. II loro prodotto κρ2è compreso nell’intervallo 93÷380 in accordo con la struttura bloccosa determinata sperimentalmente mediante analisi<13>C NMR. Copolimeri con frazione molare di stirene xs compresa neH’intervallo di composizione 0,29-0,81 sono stati ottenuti variando la composizione di alimentazione nell’intervallo di rapporti molari S/B compreso tra 5-14, Copolimeri caratterizzati da un lunghezza media di blocco di unità stireniche ns uguali o superiori a 8 e sindiotatticità delle omoscqucnze stireniche nrr > 98% risultano cristallini per la presenza di fasi cristalline polistireniche sindiotattichc nella forma cristallina δ attribuita mediante diffrazione a raggi X delle polveri e spettroscopia<!3>CP MAS in stato solido [M. Caprio, M.C. Serra, D. E. Bowen, A. Grassi Macromolecules 2002, i5, 9315; C, Cuomo, M.C. Serra, M. Gonzalcz Maupoey, A. Grassi Macromolecules 2007, 40, 7089], Copolimeri con composizione percentuale in moli di stirene comprese tra 42.6-81.0 mostrano temperature di fusione di 235-254°C. The reactivity ratios rt = ABB ^ BS Cr2 = Assise (A '// is the kinetic constant relating to the addition of a monomer unit M / air at the end of the polymer chain increasing after a monomer unit My), determined by the composition of the copolymer defined at the level of dyads [A. Zambellì, M. Caprio, A. Grassi, D, E. Bowen Macromol. Chern. Phys. 2000, 201. 393] have values respectively included in the interval 3- ÷ 8 <χ> IO <2> and 4 ÷ 6 <X> 10 <"!>. Their product κρ2 is included in the interval 93 ÷ 380 according to with the block structure determined experimentally by <13> C NMR analysis. Copolymers with mole fraction of styrene xs within the composition range 0.29-0.81 were obtained by varying the feed composition in the range of molar ratios S / B between 5-14, Copolymers characterized by an average block length of styrenic units ns equal to or greater than 8 and syndiotacticity of styrenic homoscquessions nrr> 98% are crystalline due to the presence of syndiotactic polystyrene crystalline phases in the crystalline form δ attributed by diffraction X-ray of powders and spectroscopy <! 3> CP MAS in solid state [M. Caprio, M.C. Serra, D. E. Bowen, A. Grassi Macromolecules 2002, i5, 9315; C, Cuomo, M.C. Serra, M. Gonzalcz Maupoey, A . Grassi Macromolecules 2007, 40, 7089], Cop olymers with a percentage composition of styrene in moles ranging from 42.6-81.0 show melting temperatures of 235-254 ° C.
I copolimeri stirene-butadiene ottenuti mediante polimerizzazione radicalica in emulsione (ESBR) presentano unità butadieniche concatenate prevalentemente trans- 1,4 (>65%), sequenze stireniche stereo irregolari e la distribuzione dei due monomcri in catena polimerica è statistica come si evince dai rapporti di reattività r\= 1.38 e r; = 0.82 [Kirk-Othmer. Encyclopeclia of Chemical Technology·, 4th Ed, Wiley. Voi. 7. pag.178]. Il risultante rinforzo fisico operato dalle sequenze stireniche in queste gomme è modesto e le gomme SBR presentano scarse proprietà meccaniche. The styrene-butadiene copolymers obtained by radical emulsion polymerization (ESBR) have predominantly trans-1,4 (> 65%) concatenated butadiene units, irregular stereo styrene sequences and the distribution of the two monomers in the polymer chain is statistical as can be seen from the ratios reactivity r \ = 1.38 and r; = 0.82 [Kirk-Othmer. Encyclopeclia of Chemical Technology ·, 4th Ed, Wiley. Vol. 7. page 178]. The resulting physical reinforcement by the styrene sequences in these rubbers is modest and the SBR rubbers exhibit poor mechanical properties.
Copolimeri stirene-butadiene ottenuti mediante polimerizzazione anionica in soluzione con iniziatori Litio-alchilici in solventi idrocarburici (SSBR), presentano proprietà migliori rispetto alle ESBR in virtù del maggior contenuto in m-l,4-polibutadiene (30÷50%) e di una distribuzione più bloccosa del polibutadiene, come si evince dai rapporti di reattività r\= 12.5 e r>= 0.1. Styrene-butadiene copolymers obtained by anionic polymerization in solution with lithium-alkyl initiators in hydrocarbon solvents (SSBR), have better properties than ESBRs by virtue of the higher content in m-1, 4-polybutadiene (30 ÷ 50%) and of a more block of polybutadiene, as can be seen from the reactivity ratios r \ = 12.5 and r> = 0.1.
Un più limitato numero di esempi riguarda la polimerizzazione dell’isoprene catalizzata da metalli di transizione c la sua copolimerizzazione con lo stirene. Polimeri stereoregolari delFisoprene sono stati ottenuti con catalizzatori Ziegler Natta eterogenei o supportati, tram- 1,4-Poli isoprene (> 85% in moli) è stato ottenuto con catalizzatori al Titanio o miscele di alogenuri di Vanadio con composti trialchilici di Alluminio [G. Natta, L. Porri, L. Fiore Gazz. Chim. Ital. 1959, 89 , 761; G. Natta, L. Porri, P. Corradini, D. Morero Chini, lnd. 1958, 40, 362]. Catalizzatori a base di complessi del Ferro producono 3,4-poliisoprenc (fino al 99% in moli) con elevata efficienza [Y. Nakayama, Y. Baba, H. Yasuda, K. Kawakita, N. Ueyama Macromolecules 2003, 36, 7953], 3,4-Poliisoprene isotattico è stato ottenuto con regio- e stcrcoselettività estremamente elevate {mmmm > 99%) usando eatalizzatori a base di lantanidi [L. Zhang, Y. Luo, Z. Hou J. Am. Chem. Soc. 2005, 127 , 14562]. Copolimeri dello stirene con isoprene in un ampio intervallo di composizione sono stati ottenuti utilizzando un catalizzatore ciclopentadicnilico di titanio, Ti(p<5>-CsH5)(p<2>-MBMP)Cl (MBMP = 2,2'-metilenebis(6-/(?rz-butil-4-mctilfenosso) I rapporti di reattività rs= k\\tk\s e ri = Assisi calcolati dalla concentrazione in diadi [C. Cuomo, M.C. Serra, M. Gonzalez Maupoey, A, Grassi Macromolecules 2007, 40, 7089] sono rispettivamente 18 e 0.3, con un prodotto dei rapporti di reattività rtr; = 5.4 corrispondente ad una natura bloccosa dei copolimeri. A more limited number of examples concerns the polymerization of isoprene catalyzed by transition metals and its copolymerization with styrene. Stereoregular polymers of isoprene were obtained with heterogeneous or supported Ziegler Natta catalysts, with 1,4-Polyisoprene (> 85% in moles) was obtained with titanium catalysts or mixtures of vanadium halides with aluminum trialkyl compounds [G. Natta, L. Porri, L. Fiore Gazz. Chim. Ital. 1959, 89, 761; G. Natta, L. Porri, P. Corradini, D. Morero Chini, lnd. 1958, 40, 362]. Iron complex-based catalysts produce 3,4-polyisoprene (up to 99% by moles) with high efficiency [Y. Nakayama, Y. Baba, H. Yasuda, K. Kawakita, N. Ueyama Macromolecules 2003, 36, 7953], 3,4-Isotactic polyisoprene was obtained with extremely high regio- and stcrcoselectivities (mmmm> 99%) using analyzers at base of lanthanides [L. Zhang, Y. Luo, Z. Hou J. Am. Chem. Soc. 2005, 127, 14562]. Copolymers of styrene with isoprene in a wide composition range were obtained using a titanium cyclopentadicylic catalyst, Ti (p <5> -CsH5) (p <2> -MBMP) Cl (MBMP = 2,2'-methylenebis (6 - / (? rz-butyl-4-methylphenox) The reactivity ratios rs = k \\ tk \ s and ri = Assisi calculated from the concentration in dyads [C. Cuomo, M.C. Serra, M. Gonzalez Maupoey, A, Grassi Macromolecules 2007 , 40, 7089] are respectively 18 and 0.3, with a product of the reactivity ratios rtr; = 5.4 corresponding to a blocky nature of the copolymers.
DESCRIZIONE SINTETICA DELL’INVENZIONE BRIEF DESCRIPTION OF THE INVENTION
La presente invenzione riguarda un processo catalitico che consente di ottenere mescole di cA-l,4-polibutadiene e polistirene sindiotattico, indicati da questo punto in poi rispettivamente come PB e sPS, mediante una polimerizzazione sequenziale a stadi realizzata in un singolo reattore. Durante tale processo può essere anche prodotto un copolimero multiblocco, denominato come sPSA, costituito da segmenti di polistirene sindiotattico cristallino covalentemente legati a unità monomeriche o segmenti polimerici di un secondo monomero A. Il monoraero A , generalmente un diene coniugato come 1,3-butadiene e isoprene, può essere anche diviniibenzene, monomeri stirenici di fonnula generale CH:=CH-(C6H4)XR' (dove X= (CH;)ncon n = 0, 1, 2 R' = -CH=CH2). Il monomero A c in grado di copolimerizzare con lo stirene, modulando la cristallinità dei segmenti polistircnici sindiotattici e determinare una loro temperatura di fusione compresa nell’intervallo di temperature 130-270°C, prevalentemente nell’ intervallo 190-260°C, La presenza del monomero A nella catena copolimerica rende inoltre possibile l’ancoraggio del copolimero alla matrice di PB mediante un processo di reticolazione chimica o fìsica. The present invention relates to a catalytic process which allows to obtain mixtures of cA-1, 4-polybutadiene and syndiotactic polystyrene, indicated from this point onwards respectively as PB and sPS, by means of a sequential polymerization in stages carried out in a single reactor. During this process, a multiblock copolymer can also be produced, referred to as sPSA, consisting of segments of crystalline syndiotactic polystyrene covalently bonded to monomer units or polymeric segments of a second monomer A. Monoromer A, generally a conjugated diene such as 1,3-butadiene and isoprene, it can also be diviniibenzene, styrene monomers of general form CH: = CH- (C6H4) XR '(where X = (CH;) n with n = 0, 1, 2 R' = -CH = CH2). The monomer A c able to copolymerize with styrene, modulating the crystallinity of the syndiotactic polystyrene segments and determining their melting temperature in the 130-270 ° C temperature range, mainly in the 190-260 ° C range, of monomer A in the copolymer chain also makes it possible to anchor the copolymer to the PB matrix by means of a chemical or physical crosslinking process.
Il processo catalitico, oggetto della presente invenzione, consta di due o tre stadi a seconda del numero di componenti della mescola da sintetiz.zare. Permette quindi di produrre: i) mescole binarie di polistirene sindiotattico con cA-l,4-polìbutadienc (sPS-PB); U) mescole binarie del cis-1,4-polibutadiene con un copolimero multiblocco stirene-comonomero A (sPSA-PB); Hi) mescole ternarie del tipo sPS-sPSA-PB. The catalytic process, object of the present invention, consists of two or three stages depending on the number of components of the mixture to be synthesized. It therefore allows to produce: i) binary compounds of syndiotactic polystyrene with cA-1,4-polybutadienc (sPS-PB); U) binary blends of cis-1,4-polybutadiene with a styrene-comonomer A multiblock copolymer (sPSA-PB); Hi) ternary compounds of the sPS-sPSA-PB type.
Nel primo stadio di detto processo viene condotta la polimerizzazione dello stirene per produrre sPS con massa molecolare media numerale di 30-50KDa, stereoregolarità di tipo sindiotattico (>95%) c cristallinità di circa il 55%. Nell’ultimo stadio viene condotta la polimerizzazione di 1,3 butadiene con formazione di PB con massa molecolare media numerale M„ compresa tra 20KDa e 2MDa. In the first stage of said process the polymerization of the styrene is carried out to produce sPS with an average molecular mass of 30-50KDa, stereoregularity of the syndiotactic type (> 95%) and crystallinity of about 55%. In the last stage, the polymerization of 1.3 butadiene is carried out with the formation of PB with an average molecular mass M "between 20KDa and 2MDa.
Tra i due stadi di polimerizzazione può essere inserito un ulteriore processo catalitico, in cui il reattore viene alimentato con idonee concentrazioni di un monomero A in grado di copolimerizzare con lo stirene non reagito e formare copolimeri a blocchi dello stirene c del monomcro A. 11 copolimero multiblocco ha peso molecolare medio ponderale compreso tra 20KDa e 60KDa, è costituito da almeno due segmenti polimerici, di cui uno di polistirene sindiotattico, comprende almeno 10 unità di stirene concatenate in modo stercoregolarc di tipo sindiotattico separate da unità di A. A further catalytic process can be inserted between the two polymerization stages, in which the reactor is fed with suitable concentrations of a monomer A capable of copolymerizing with the unreacted styrene and forming block copolymers of styrene c of monomer A. 11 copolymer multiblock has a weight average molecular weight between 20KDa and 60KDa, is made up of at least two polymeric segments, one of which is syndiotactic polystyrene, includes at least 10 stercoregularly linked syndiotactic styrene units separated by A.
1! processo oggetto della presente invenzione consente un facile controllo della composizione della mescola nei suoi diversi componenti mediante il controllo dell’alimentazione del reattore. In particolare: i) il tempo di polimerizzazione del primo stadio definisce la composizione finale di sPS nella mescola; iìj l’introduzione di idonee concentrazioni de! monomero A allo stato gassoso, liquido o soluzioni determina la composizione, la lunghezza media dei blocchi copolimerici e la concentrazione del copolimero sPSA; iti) l’ultimo stadio definisce la composizione di PB della mescola. 1! process object of the present invention allows easy control of the composition of the mixture in its various components by controlling the feed of the reactor. In particular: i) the polymerization time of the first stage defines the final composition of sPS in the blend; iìj the introduction of suitable concentrations of monomer A in the gaseous, liquid or solutions state determines the composition, the average length of the copolymer blocks and the concentration of the sPSA copolymer; iti) the last stage defines the PB composition of the compound.
Viene inoltre descritta, e costituisce parte integrante della presente invenzione, l’importante azione di rinforzante di sPS e l’azione compatibilizzantc svolta dal copolimero multiblocco sPSA prodotto in sito con le mescole di PB e sPS o aggiunto al termine del processo di polimerizzazione. Nel caso in cui A è 1,3-butadiene, il copolimero sPSB, con composizione pari almeno al 40% in moli di stirene e in concentrazione compresa neirintervailo 0.1-20% in peso dcil’intera mescola, preferibilmente intorno a 2%, favorisce la dispersione di micro- e nanoparticellc di polistirene sindiotattìco nella mescola e promuove l’inclusione di frazioni consistenti della gomma all’ interno delle particelle di sPS. It is also described, and constitutes an integral part of the present invention, the important reinforcing action of sPS and the compatibilizing action carried out by the sPSA multiblock copolymer produced on site with the PB and sPS compounds or added at the end of the polymerization process. In the case where A is 1,3-butadiene, the sPSB copolymer, with a composition equal to at least 40% by moles of styrene and in a concentration comprised within 0.1-20% by weight of the entire mixture, preferably around 2%, favors the dispersion of syndiotactic polystyrene micro- and nanoparticles in the compound and promotes the inclusion of consistent rubber fractions within the sPS particles.
Caratteristica dei campioni cosi ottenuti è una temperatura fusione osservato neirintervailo di temperatura compreso tra 130-260°C, aggiuntiva rispetto alla fusione della forma cristallina δ di sPS tipicamente osservata a circa 270°C. Characteristic of the samples thus obtained is a melting temperature observed in the temperature range between 130-260 ° C, additional to the melting of the crystalline form δ of sPS typically observed at about 270 ° C.
Le proprietà delle mescole ottenute con il processo oggetto della presente invenzione risultano completamente differenti da quelle ottenute per miscelazione meccanica di PB e sPS o realizzate mediante precipitazione da soluzione dei due polimeri disciolti o sospesi in solventi. Nella miscelazione meccanica a caldo dei due polimeri l’elevata temperatura di fusione di sPS e la sua durezza impediscono infatti un’efficiente miscelazione lasciando le dimensioni delle particelle dì sPS utilizzate come rinforzante nell’ordine delle decine di micrometri. The properties of the blends obtained with the process object of the present invention are completely different from those obtained by mechanical mixing of PB and sPS or made by precipitation from a solution of the two polymers dissolved or suspended in solvents. In the hot mechanical mixing of the two polymers, the high melting temperature of sPS and its hardness in fact prevent efficient mixing, leaving the size of the sPS particles used as a reinforcer in the order of tens of micrometers.
Con il processo oggetto della presente invenzione è possibile sintetizzare mescole di PB e sPS in cui le dimensioni delle particelle di termoplastico rinforzante possono variare da! micron fino a decine di nanometri. Tali mescole, dopo vulcanizzazione e/o reticolazione, sono caratterizzate da buone proprietà meccaniche, quali elevato modulo di Young, tenacità, sforzo a rottura ed elongazione a proprietà possono essere facilmente modulate al variare della composizione della mescola, tempi di reticolazione o vulcanizzazione, peso molecolare medio dei componenti e Γ indice di polidispersità dei prodotti polimerici. With the process object of the present invention it is possible to synthesize mixtures of PB and sPS in which the dimensions of the reinforcing thermoplastic particles can vary from! microns down to tens of nanometers. These compounds, after vulcanization and / or crosslinking, are characterized by good mechanical properties, such as high Young's modulus, toughness, stress at break and elongation and properties can be easily modulated as the composition of the compound varies, crosslinking or vulcanization times, weight molecular average of the components and Γ polydispersity index of the polymeric products.
DETTAGLIATA DESCRIZIONE DELL’INVENZIONE DETAILED DESCRIPTION OF THE INVENTION
COMPOSIZIONE DELLE MESCOLE COMPOSITION OF THE COMPOUNDS
Le mescole oggetto della presente invenzione contengono: i) PB in composizione percentuale in peso compresa tra 0.1 e 99.9%; ii) sPS in composizione percentuale in peso compresa 0.1 e 99.9%; tii) un copolimero multiblocco di polistirene sindiotattico con un comonomero A (sPSA) in quantità compresa tra 0.1-20% in peso dell’intera mescola; iv) agenti reticolanti e/o vulcanizzanti; v) additivi in quantità variabile. The compounds object of the present invention contain: i) PB in a percentage composition by weight comprised between 0.1 and 99.9%; ii) sPS in percentage composition by weight between 0.1 and 99.9%; tii) a syndiotactic polystyrene multiblock copolymer with a comonomer A (sPSA) in an amount ranging from 0.1-20% by weight of the entire compound; iv) crosslinking and / or vulcanizing agents; v) additives in variable quantities.
Il PB prodotto nel processo oggetto della presente invenzione ha un contenuto in unità C/A- 1 ,4 di circa 70-90%, preferibilmente 80%, e inoltre comprende unità 1,2-viniliche isolate in catena polimerica in concentrazione variabile tra 10% e 20% e unità trans- 1 ,4 isolate (< 1%) fino a un massimo di 9%, Ha una massa molecolare media numerale M„ compresa tra 20KDa e 2MDa, un indice di polidispersità MJMa(dove Mwè la massa molecolare media ponderale) compreso tra 1.8 e 3.4, preferibilmente 2,0, e una temperatura di transizione vetrosa intorno a -95°C. The PB produced in the process object of the present invention has a content in C / A-1, 4 units of about 70-90%, preferably 80%, and also comprises 1,2-vinyl units isolated in the polymeric chain in a concentration ranging from 10 % and 20% and isolated trans-1, 4 units (<1%) up to a maximum of 9%, It has a numeral average molecular mass M "between 20KDa and 2MDa, a polydispersity index MJMa (where Mw is the molecular mass weight average) between 1.8 and 3.4, preferably 2.0, and a glass transition temperature around -95 ° C.
sPS ha una massa molecolare media numerale Mncompresa tra 30KDa e 50KDa con grado di sindiotatticità di almeno 90%, preferibilmente > 95%, meglio se > 98%, espresso come frazione molare delle pentadi rrrr (successione di cinque unità monomeriche con configurazione alternata), determinata mediante analisi<13>C NMR in soluzione di tetracloroctano~c/2(40mg/mi) a 100°C [N, Ishihara, T. Seimiya, M. Kuramoto, M. Uoi Macromolecitles, 1986, 19, 2464]. sPS has a numeral average molecular mass Mn comprised between 30KDa and 50KDa with a degree of syndiotacticity of at least 90%, preferably> 95%, preferably> 98%, expressed as a mole fraction of the pentads rrrr (succession of five monomer units with alternating configuration), determined by analysis <13> C NMR in solution of tetrachloroctan ~ c / 2 (40mg / ml) at 100 ° C [N, Ishihara, T. Seimiya, M. Kuramoto, M. Uoi Macromolecitles, 1986, 19, 2464].
Il copolimero multiblocco sPSA ha una massa molecolare media ponderale Mwcompresa tra 20KDa e 60KDa, indice di poiidispersità MjMncompreso tra 1.9 e 2.4, composizione elevata in stirene in catena polimerica, pari almeno al 40% in moli, ed è costituito da almeno un segmento cristallino o cristallizzabile di polistirene sindiotattico costituito da almeno 10 unità stireniche, aventi stereoregolarità sindiotattica esprimibile come frazione molare di pentadi rrrr di almeno 90%. Nel copolimero multiblocco è inoltre presente almeno un’unità di un monomero A, generalmente un diene coniugato come 1,3-butadicne e isoprene, che può anche essere divinilbenzene, monomeri stirenici di fonnula generale CHi^CH-tCéHjJXR' (dove X= (CH2)n con n = 0, 1, 2 R' = -CH=CH2). Nel caso specifico in cui il comonomcro A è 1,3-butadiene, il copolimero multiblocco avrà una composizione percentuale in moli tra 40-60% in stirene, una temperatura di fusione dei segmenti polistirenici in catena di circa 190-260°C e una temperatura di transizione vetrosa dei segmenti polibutadienici di circa -97°C. The sPSA multiblock copolymer has a weight average molecular mass Mw between 20KDa and 60KDa, polydispersity index MjMn between 1.9 and 2.4, high styrene composition in the polymer chain, equal to at least 40% by moles, and consists of at least one crystalline segment or crystallizable of syndiotactic polystyrene consisting of at least 10 styrene units, having syndiotactic stereoregularity expressed as a mole fraction of pentad rrrr of at least 90%. In the multiblock copolymer there is also present at least one unit of a monomer A, generally a conjugated diene such as 1,3-butadicne and isoprene, which can also be divinylbenzene, styrene monomers of general form CHi ^ CH-tCéHjJXR '(where X = ( CH2) n with n = 0, 1, 2 R '= -CH = CH2). In the specific case in which the comonomcro A is 1,3-butadiene, the multiblock copolymer will have a percentage composition in moles between 40-60% in styrene, a melting temperature of the polystyrene segments in the chain of about 190-260 ° C and a glass transition temperature of the polybutadiene segments of about -97 ° C.
PROCESSO PROCESS
Le mescole sono sintetizzate mediante un processo sequenziale a stadi, il cui numero dipende dal numero di componenti della mescola. In tutti gli stadi viene utilizzato preferenzialmente lo stesso catalizzatore, ma possono essere utilizzati anche diversi catalizzatori organometallici da introdurre nel reattore all’inizio di ciascuno stadio di polimerizzazione, II processo di polimerizzazione viene condotto in soluzione di solventi idrocarburici, alifatici o aromatici, preferibilmente esano o toluene, a temperatura compresa tra -20 e 130°C, più comunemente tra 20°C e 80°C, preferibilmente a 25°C. The blends are synthesized by a sequential step process, the number of which depends on the number of components in the blend. The same catalyst is preferably used in all stages, but different organometallic catalysts can also be used to be introduced into the reactor at the beginning of each polymerization stage.The polymerization process is carried out in a solution of hydrocarbon, aliphatic or aromatic solvents, preferably hexane or toluene, at a temperature between -20 and 130 ° C, more commonly between 20 ° C and 80 ° C, preferably at 25 ° C.
I catalizzatori utilizzabili per la realizzazione del processo oggetto della presente invenzione sono tutti i composti la cui formula può essere scelta nei gruppo costituito da CpMX3, CpMX2, MX4e MX3,dove Cp rappresenta un composto aromatico anionico di fonnula CjRnHj.,, in cui R è un gruppo alchilico, arilico, alehilarilico, arilalchilico, aloalchilico, aloarilico, aloalchilarilico, aloarilalchilico, sililalchilico, sililarilico, sililalcarilico, sililarilalchilico, alosililalchilico, alosililarilico, alosiiilatcarilico, alosiliarilalchilico, sililaloalchilico, sililaloarilico, sililaloalcarilico, sililaloarilalcbilico, alcosso, sdosso; inoltre R può anche essere NRS, PR'i, SR' e BRS. Nella fonnula CsRnHs-n, n rappresenta un intero da 0 a 5. M è un metallo dei gruppo 3 (Se, Y, La), gruppo 4 (Ti, Zr, Hf) o lantanoide della Tavola Periodica e X può essere idrogeno, alogeno, un gruppo alchilico, arilico, alehilarilico, arilalchilico, aloalchilico, aloarilico, aloalchilarilico, aloarilalchilico, sililalchilico, sililarilico, sililalcarilico, sililarilalchilico, alosililalchilico, alosililarilico, alosililalcarilico, alosiliarilalchilico, sililaloalchilico, sililaloarilico, sililaloalcarilico, sililaloarilalchilico, alcosso, sdosso, NR2, PRS, SR' e BR';. Per MX3, X può essere un acido organico contenente da 1 a 20 atomi di carbonio, come ad esempio acetilacetonato, acetato, benzoato, salicilaldeide, trifluoroacctato. The catalysts that can be used for carrying out the process object of the present invention are all the compounds whose formula can be chosen from the group consisting of CpMX3, CpMX2, MX4 and MX3, where Cp represents an anionic aromatic compound of form CjRnHj. ,, in which R is an alkyl, aryl, alehylaryl, arylalkyl, haloalkyl, haloaryl, haloalkylaryl, haloarylalkyl, silylalkyl, silylaryl, silylalkyl, silylarylalkyl, alosilylalkyl, alosilylaryl, silylatalkyl, silylarylalkyl, silylarylalkyl, silylarylalkyl, silylarylalkyl, alkylalkyl, alkylalkyl, alkylalkyl, alkylalkyl, alkylalkyl, alkylalkyl, alkyl moreover R can also be NRS, PR'i, SR 'and BRS. In the form CsRnHs-n, n represents an integer from 0 to 5. M is a metal of group 3 (Se, Y, La), group 4 (Ti, Zr, Hf) or lanthanide of the Periodic Table and X can be hydrogen, halogen, an alkyl, aryl, alehylaryl, arylalkyl, haloalkyl, haloaryl, haloalkylaryl, haloarylalkyl, silylalkyl, silylaryl, silylalkyl, silylarylalkyl, alosilylalkyl, alosilylaryl, silylalkyl, alkaloalkyl, silylalkyl, alkaloalkyl, alkoxyl, alkoxyl, alkoxyl, alkaryl PRS, SR 'and BR'; For MX3, X can be an organic acid containing from 1 to 20 carbon atoms, such as for example acetylacetonate, acetate, benzoate, salicylaldehyde, trifluoroactate.
I cocatalizzatori sono allumossani, lineari o ciclici, come il metilallumossano (MAO), il metilallumossano modificato (MMAO), o forti acidi di Lewis, quali B(C6F5)3e [CPh3][B(C6F5)4], o acidi di Bronsted, quali perfluoroarilborati di anilinio [PhNH j[B(C6Fs) ]. Il rapporto molare Al/M tra del cocatalizzatore e il metallo del catalizzatore è compreso tipicamente 10: 1-10000:1, preferibilmente 400: 1-1500: 1; il rapporto molare B/M tra il boro del cocatalizzatore e il metallo del catalizzatore è generalmente 0.7: 1-1.5: 1. The cocatalysts are alumoxanes, linear or cyclic, such as methylalumoxane (MAO), modified methylalumoxane (MMAO), or strong Lewis acids, such as B (C6F5) 3e [CPh3] [B (C6F5) 4], or Bronsted acids , such as anilinium perfluoroarylborates [PhNH j [B (C6Fs)]. The molar ratio Al / M between the cocatalyst and the metal of the catalyst is typically 10: 1-10000: 1, preferably 400: 1-1500: 1; the molar ratio B / M between the cocatalyst boron and the catalyst metal is generally 0.7: 1-1.5: 1.
La quantità di catalizzatore impiegata è tipicamente di 5<χ>10<'5>-5<χ>IO<"4>moli per l * l0<~3>-5 moli di monomero; il catalizzatore può essere introdotto nell’ambiente di reazione nel primo stadio del processo sequenziale oggetto della seguente invenzione, o alternativamente aggiunto all’inizio di ogni stadio. The amount of catalyst used is typically 5 <χ> 10 <'5> -5 <χ> 10 <"4> moles for l * 10 <~ 3> -5 moles of monomer; the catalyst can be introduced into the environment reaction in the first stage of the sequential process object of the following invention, or alternatively added at the beginning of each stage.
Il processo oggetto della presente invenzione prevede la polimerizzazione sindiotattico-specifica dello stirene per un tempo scelto opportunamente per raggiungere la desiderata conversione monomerica. La successiva alimentazione del reattore con il comonomero A produce una frazione copolimerica intimamente mescolata, eventualmente chimicamente legata alle catene di polistirenc sindiotattico. Nel caso in cui il monomero A è 1,3-butadienc, il reattore è alimentato con butadiene gassoso, liquido o in soluzione in modo da produrre una concentrazione in soluzione compresa tra 0.01M e 0.4M. Infine, raggiunta di 1,3-butadiene (concentrazione variabile tra 1M e 4M) porta alla formazione di una fase elastomerica, la cui concentrazione è controllata calibrando opportunamente il tempo di polimerizzazione. Il processo viene completato aggiungendo un antiossidante ed un agente reticolante. The process object of the present invention provides for the syndiotactic-specific polymerization of styrene for a time suitably chosen to achieve the desired monomer conversion. The subsequent feeding of the reactor with the comonomer A produces an intimately mixed copolymer fraction, possibly chemically bound to the syndiotactic polystyrene chains. If the monomer A is 1,3-butadiene, the reactor is fed with gaseous, liquid or solution butadiene to produce a solution concentration between 0.01M and 0.4M. Finally, reached 1,3-butadiene (variable concentration between 1M and 4M) leads to the formation of an elastomeric phase, whose concentration is controlled by appropriately calibrating the polymerization time. The process is completed by adding an antioxidant and a cross-linking agent.
L’agente reticolante può essere un perossido organico, zolfo e suoi composti organici, ossidi metallici. Esempi di perossidi organici sono dicumiiperossido, t-butilperbenzoato, t-butilperossi-3-esino, 1,1 -bis(t The crosslinking agent can be an organic peroxide, sulfur and its organic compounds, metal oxides. Examples of organic peroxides are dicumihyperoxide, t-butylperbenzoate, t-butylperoxy-3-hexine, 1,1 -bis (t
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013683A1 (en) * | 1998-12-21 | 2000-06-28 | The Goodyear Tire & Rubber Company | Styrene-butadiene block copolymer |
| EP1661949A1 (en) * | 2003-08-15 | 2006-05-31 | Dynasol Elastomeros, S.A. De C.V. | Polymeric composition having elastomeric properties over wide temperature ranges, and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013683A1 (en) * | 1998-12-21 | 2000-06-28 | The Goodyear Tire & Rubber Company | Styrene-butadiene block copolymer |
| EP1661949A1 (en) * | 2003-08-15 | 2006-05-31 | Dynasol Elastomeros, S.A. De C.V. | Polymeric composition having elastomeric properties over wide temperature ranges, and preparation method thereof |
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