MXPA96006540A - PROCESS FOR THE PREPARATION OF POLYMEROSVINILAROMATICOS CRISTALINOS WITH A STRUCTURAPREDOMINANTmente SINDIOTACT - Google Patents
PROCESS FOR THE PREPARATION OF POLYMEROSVINILAROMATICOS CRISTALINOS WITH A STRUCTURAPREDOMINANTmente SINDIOTACTInfo
- Publication number
- MXPA96006540A MXPA96006540A MXPA/A/1996/006540A MX9606540A MXPA96006540A MX PA96006540 A MXPA96006540 A MX PA96006540A MX 9606540 A MX9606540 A MX 9606540A MX PA96006540 A MXPA96006540 A MX PA96006540A
- Authority
- MX
- Mexico
- Prior art keywords
- represent
- different
- alkyl
- iso
- groups
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- -1 chlorine Chemical class 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 230000027455 binding Effects 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000379 polymerizing Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 3
- 230000003197 catalytic Effects 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 74
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 73
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 68
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 11
- 229920002223 polystyrene Polymers 0.000 description 11
- 241001058354 Inti Species 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 7
- JNRCLZJPHBGOOI-UHFFFAOYSA-N C1(=CC=CC=C1)C.C1(=CC=CC=C1)[Sn](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C.C1(=CC=CC=C1)[Sn](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 JNRCLZJPHBGOOI-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N Titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- AENCLWKVWIIOQH-UHFFFAOYSA-K cyclopentane;trichlorotitanium Chemical compound Cl[Ti](Cl)Cl.[CH]1C=CC=C1 AENCLWKVWIIOQH-UHFFFAOYSA-K 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- UJTMLNARSPORHR-UHFFFAOYSA-N OC2H5 Chemical compound C=C=[O+] UJTMLNARSPORHR-UHFFFAOYSA-N 0.000 description 2
- IIMIOEBMYPRQGU-UHFFFAOYSA-L Picoplatin Chemical compound N.[Cl-].[Cl-].[Pt+2].CC1=CC=CC=N1 IIMIOEBMYPRQGU-UHFFFAOYSA-L 0.000 description 2
- CLIZITAPNWYUNM-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].C1=CC=C2C([Ti+3])C=CC2=C1 Chemical compound [Cl-].[Cl-].[Cl-].C1=CC=C2C([Ti+3])C=CC2=C1 CLIZITAPNWYUNM-UHFFFAOYSA-K 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- QNPFGNWOSOIUGB-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C1C=CC=[C-]1 QNPFGNWOSOIUGB-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920001576 syndiotactic polymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- FSRLCYXRDZIJJT-UHFFFAOYSA-N 1-ethenyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(C=C)CCCC2=C1 FSRLCYXRDZIJJT-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- ZBPFHTNNYAOCTL-UHFFFAOYSA-N 6-ethenyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(C=C)=CC=C21 ZBPFHTNNYAOCTL-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- OEOUWMSQXZQDIP-UHFFFAOYSA-N CC[Al](CC)CC.CC1=CC=CC=C1 Chemical compound CC[Al](CC)CC.CC1=CC=CC=C1 OEOUWMSQXZQDIP-UHFFFAOYSA-N 0.000 description 1
- FWMGWNBHJYBRTH-UHFFFAOYSA-N CC[Ti](CC)(CC)CC Chemical compound CC[Ti](CC)(CC)CC FWMGWNBHJYBRTH-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N Cinnamic acid Chemical class OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Phenylacetylene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- 229960005235 Piperonyl Butoxide Drugs 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001721 Polyimide Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N Tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N Triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N Triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N Trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-VOTSOKGWSA-N [(E)-2-chloroethenyl]benzene Chemical compound Cl\C=C\C1=CC=CC=C1 SBYMUDUGTIKLCR-VOTSOKGWSA-N 0.000 description 1
- YMOONIIMQBGTDU-SREVYHEPSA-N [(Z)-2-bromoethenyl]benzene Chemical compound Br\C=C/C1=CC=CC=C1 YMOONIIMQBGTDU-SREVYHEPSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- WJSDHUCWMSHDCR-UHFFFAOYSA-N cinnamyl acetate Chemical compound CC(=O)OCC=CC1=CC=CC=C1 WJSDHUCWMSHDCR-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 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
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000607 poisoning Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- NQSJDHNNJIQPNW-UHFFFAOYSA-K trisodium;trichloride Chemical compound [Na+].[Na+].[Na+].[Cl-].[Cl-].[Cl-] NQSJDHNNJIQPNW-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure, which is characterized in that it comprises polymerizing vinylaromatic monomers, alone or mixed with at least one other copolymerizable, ethylenically unsaturated monomer, in the presence of a catalyst system which consists essentially of: a) a titanium or zirconium complex selected from those having the general formula: MR1R2R3R4, A1MR1R2R3, A1A2MR1R2 (I) in which the groups R1, R2, R3 and R4, equal or different, represent (iso ) C1-C10 alkyl, (iso) alkoxy, alkylamide radical, a C6-C10 aryl radical or a halogen such as chlorine, while the same or different groups A1 and A2, represent a cyclopentadienyl ligand, optionally substituted with radicals C1-C10 alkyl, or an indenyl ligand, M represents a titanium or zirconium atom, b) a cocatalyst selected from an alkyl ilaluminoxane and a boron compound having the formula (II): BX1X2X3 (II) or one of its salts, in which X1, X2 and X3, are the same or different, represent a fluorinated hydrocarbon radical of C1-C20; and c) a tin derivative having the general formula: SnR5R6R7R8 (III) in which the groups R5, R6, R7 and R8, equal or different, represent an (iso) alkyl or aryl radical of C1-C
Description
PROCESS FOR THE PREPARATION OF VINI AROMATIC CRYSTAL POLYMERS WITH A PREDOMINANTLY STRUCTURE
SINDIOTACTICA
DESCRIPTION OF THE INVENTION
The present invention relates to a process for the preparation of vinylaromatic crystalline polymers with a predominantly syndiotactic structure. More specifically, the present invention relates to a process for the preparation of crystalline polystyrene, in which the polymer chains have an essentially syndiotactic configuration and the catalyst suitable for this purpose. Polystyrene is a thermoplastic polymer obtained by polymerization of styrene radicals and is used in the production of molded articles, films, electrical materials, packaging materials, etc. It is an amorphous, atactic polymer that has excellent insulation properties and reasonable thermal resistance. For many applications, however, it is preferable to use crystalline materials with high thermal resistance and solvent resistance, characteristics which atactic polystyrene does not have.
European Patent 210,615 describes a polystyrene having a structure characterized by an extremely high degree of stereoregularity, in which phenyl substituents are arranged to provide a syndiotactic polymer. This material does not have the above disadvantages of atactic polystyrene since it is crystalline and therefore, once transformed, it can be subjected to orientation processes, it is almost completely insoluble in organic solvents and has a melting point within the range of 260- 280 ° C and therefore have high thermal resistance, comparable to or greater than that of thermoplastic condensation polymers (polyesters, polyamides, polyimides, etc.). The syndiotactic polystyrene can be prepared as described in the literature, for example in accordance with what was described in European Patent EP 272,584 or US Patent 4,978,730, by polymerization catalyzed by the compounds of Ti, Zr in presence of a cocatalyst represented by methylaluminoxane (a mixture of cyclic and linear oligomers containing the periodic units -AlCH-jO-) or, as described in European Patent Application, published 421,629, of boron-containing fluorinated group derivatives . Examples of catalysts for the synthesis of syndiotactic polystyrene mentioned in the literature are titanium halides (chloride, bromide, etc.), titanium alcoholates (methoxide, ethoxide, propoxide, isopropoxide, butoxide, etc.), titanium carboxylates, metallocenes (cyclopentadienyltitanium trichloride, dichloride, cyclopentadienyltitanium trichloride pentametilciclopenta-dieniltitanio alkoxides cyclopentadienyltitanium cyclopentadienyltitanium alkyls, alkyls pentametilciclopenta-dieniltitanio dichloride diciclopentadieniltitanio alkoxides diciclopentadieniltitanio, etc.), titanium alkyls (tetrabenzyl, tetrametiltitanio, tetraethyl -titanium, etc.) and the corresponding zirconium compounds. It has now been found that it is possible to synthesize crystalline vinylaromatic polymers and in particular crystalline polystyrene, which has a predominantly syndiotactic configuration using a novel catalyst system, which has never been described in the literature. The present invention, therefore, relates to a process for the preparation of crystalline vinylaromatic polymers having a predominantly syndiotactic structure, which comprises polymerizing vinylaromatic monomers, alone or mixed with at least one other copolymerizable, ethylenically unsaturated monomer, in the presence of a catalyst system consisting essentially of: a) a titanium or zirconium complex selected from those having the general formula:
MR1R2R3R4, A1MR1R2R3, A1A2MR1R2 (I)
wherein the groups R1 (R2, R3 and R4, equal or different, represent (iso) alkyl of C - ^ - C- ^ Q, (iso) alkoxy, alkylamide radical, an aryl radical of g-C10 or a halogen such as chlorine, while the groups A- ^ and A2, the same or different, represent a cyclopentadienyl ligand, optionally substituted with alkyl radicals of C- ^ - C- ^ Q, OR an indenyl ligand; M represents a titanium or zirconium atom; b) a cocatalyst selected from an alkylaluminoxane and a boron compound having the formula (II):
or one of its salts, in which X1 # X2 and X3, are the same or different, represent a fluorinated hydrocarbon radical of c? ~ c2o; and c) a tin derivative having the general formula:
SnR5R6R7R8 (III) in which the groups R5, Rg, R7 and Rg / same or different, represent an (iso) alkyl or aryl of C1-C1Q radical. With respect to traditional catalyst systems, the compounds based essentially on (a) and (b), the catalyst system of the present invention causes increases in one or more of the following parameters: activity of the catalyst system; molecular weight of the syndiotactic polystyrene obtained; degree of stereoregularity of the polymer. The compounds having the general formula (I) are products known in the literature and are described in European Patent 210,615 or in United States Patent 4,978,730. Typical examples of the titanium or zirconium complexes having the formula (I), particularly suitable for the present invention are Ti (CH2CgH5) 4; Ti (OCH3) 4;
Ti (OC2H5) 4; Ti (OC3H7) 4; Ti (Oi-C3H7) 4; Ti (OC4H9) 4; Ti [N < CH3) 2] V Ti [N (C2H5) 2] 4; Ti [N (C3H7) 2JV Ti [N (i-C3H7) 2] 4; Ti [N (C4H9) 2] 4; CpTiCl3; CpTi (OCH3) 3; CpTi (OC2H5) 3; CpTÍ (OCjH7) 3; CpTÍ (OÍ-C3H7) 3? CpTiÍOC ^ H,) ^ CpTi [N (CH3) 2] 3; CpTi [N (C2H5) 2] 3; CpTi [N (C3H7.}. 2] 3; CpTi [N (i-C3H7) 2] 3 cpti [N (c4H9) 2] 3 # - cptici3; cp * ti (0CH3) 3; cp * ti (oc2H5) 3; Cp'Ti (OC3H7) 3; Cp * Ti (Oi-C3H7) 3 Cp * Ti (OC4H9) 3; Cp * TÍ [N (CH3) 2] 3; Cp * TÍ [N (C2H5) 2] 3; Cp * TÍ [N (C3H7) 2] 3; Cp * Ti [N (i-c3H7) 2] 3; Cp * Ti [N (C4H9) 233; InTiCl3; lnTi (OCH3) 3; InTi (0C2H5) 3; inTi (OC3H7) 3; InTi (Oi-C3H7) 3; InTi (0C4H9) 3 InTi [N (CH3) 2] 3; InTi [N (C2H5) 2] 3; InTi [N (C3H7) 233;
InTi [N (i-C3H7) 2] 3; InTi [N (C4H9) 2] 3; etc., and the corresponding derivatives of Zirconium. (Cp = cyclopentadienyl; In = indenyl; Cp * = pentamethyl-cyclopentadienyl). The titanium or zirconium compounds having the general formula (I) are added to the polymerization mixture in such an amount that the molar ratio of vinylaromatic monomer / M (M = titanium or zirconium) is between 1,000 and 200,000, preferably between 10,000 and 150,000. The alkylaluminoxane cocatalyst consists essentially of mixtures of products having a linear or cyclic or box structure. In the first case The structure is represented by the general formula (IV):
while in the second case by the general formula (V)
wherein m represents an integer between 1 and 40 and R 'an alkyl radical of C - ^ - C ^, preferably of C-j-Cg, - an aryl radical of Cg-C20, preferably of Cg-C12; a C7-C20 aralkyl or alkylaryl radical, preferably C7-C12; or a C3-C2Q cycloalkyl radical, preferably C? -Cg; or an O-R 'radical, in which R' represents an alkyl radical of preferably C? -C4 * an aryl radical of
Cg-C20, preferably Cg-C12; or a halogen atom, such as chlorine, fluorine or bromine, with the proviso that not all radicals R ^ are contemporaneously O-R 'or halogens. The box structure was described in Molecular Symposium, Vol. 97, 1995. The above cocatalysts, having the general formula (IV) and (V) are known in the literature and were described, for example, in Patent Applications.
European, published 272,584 and 421,659 or in U.S. Patent 4,978,730. Cocatalysts having the general formula (II), or its salt, are known in the literature and described in European Patent Applications, published 421,659 and 482,934. Preferred cocatalysts between those having the general formulas (II), (IV) or (V) is methylaluminoxane (MAO), a mixture of linear oligomers with an average m of between 10 and 20 and cyclic oligomers with average m of between 10 and 20. and 20. The cocatalyst is generally used in amounts such that the molar ratio of aluminum / M is between 50 and 2,000 or such that the boron / M ratio is between 0.5 and 10. The preferred tin derivatives of the present invention are Sn (CH 3) 4; Sn (C2H5) 4; Sn (C3H7) 4; Sn (i-C3H7) 4; Sn (C4Hg) 4; Sn (CgH5) 4; Sn (CH2CgH5) 4; etc. These compounds are added to the polymerization mixture in such an amount that the molar ratio of Sn / M is between 0.01 and 100, preferably between 0.1 and 50. According to the process of the present invention, the catalyst system described in above may also optionally consist of an alkylaluo in which the alkyl group contains from 1 to 6 carbon atoms, for example trimethylaluminum, triethylaluminum, triisobutylaluminum, etc., in amounts such that the molar ratio of alkylaluminum / M is between 0 and 800. The term "vinylaromatic polymers" as used in the present description and in the claims, refers essentially to styrene polymers and styrene derivatives and relative copolymers containing up to 20 mole% of another monomer copolymerizable selected from those having the general formula (V):
CH2 = CH - R "(V)
wherein R "represents a hydrogen atom or an alkyl radical of C ^ -Cg or a C4-C12 cycloalkyl radical.The styrene derivatives comprise alkylstyrenes, in which the alkyl group contains from 1 to 4 carbon atoms, show halogenated, C-, C4-alkoxystyrenes, carboxystyrenes, vinylnaphthalenes, such as alpha- or beta-vinylnaphthalene, vinyltetrahydronaphthalene such as 1, 2, 3, 4-tetrahydro-6-vinylnaphthalene, etc. Typical examples of substituted styrenes are p-methylstyrene, m-methylstyrene, alone or mixed together, ethylstyrene, butylstyrene, p-tert-butylstyrene, dimethylstyrene, chlorostyrene, bromostyrene, fluorostyrene, chloromethyl-styrene, methoxystyrene, acetoxymethylstyrene, etc. The polymerization reaction can be carried out mass or solvent In the second case, the solvent may consist of aliphatic or aromatic hydrocarbons or their mixtures and is used in quantities such that the volume ratio of solvent / monomer The numbers are between 0 and 10. The preferred solvent is toluene. More specifically, according to the general procedure adopted for this type of reaction, vinylaromatic monomers are subjected to treatment, before polymerization, to eliminate catalytic poisonings, such as phenol, water, phenylacetylene stabilizers and consisting of distillation, steps on columns containing activated molecular sieves or activated alumina, etc. The monomers and optionally, the solvent are charged to the reaction equipment together with the possible aluminum alkyl and cocatalyst. After a time ranging from 5 seconds to 30 minutes, the catalyst system comprising the titanium complex having the general formula (I) and the tin derivative having the general formula (III) is added, preferably in the form of a solution. The reaction proceeds for times ranging from 15 minutes to 10 hours at temperatures between 20 and 100 ° C. In the end, the obtained polymer is recovered using traditional methods. Some illustrative but non-limiting examples are provided for a better understanding of the present invention and its modality. Analysis procedures:
The percentage of the syndiotactic polymer is determined by extracting the polymer with acetone or methyl ethyl ketone (MEK) at the boiling point for 10-20 hours. The degree of stereoregularity is determined by L3 carbon nuclear magnetic resonance spectroscopy as described in U.S. Patent 4,680,353. The molecular weights of the polymers obtained were determined by Gel Percent Chromatography in trichlorobenzene at 135 ° C. The percentages indicated in the examples are relative percentages.
COMPARATIVE EXAMPLE 1
16 ml of styrene (0.140 moles) purified by the passage in a column of basic alumina, 2 ml of a solution
0. 01 M in tetramethyltin toluene (2 x 10"5 moles) and then 0.5 ml of a 0.01 M solution in toluene of (pentamethylcyclopentadienyl) titanium trichloride (5 x 10 ~ 6 moles), are introduced into a subsequent test tube in an inert atmosphere The reaction is carried out for 2 hours at 60 ° C
At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl. No solid product is obtained.
COMPARATIVE EXAMPLE 2
16 ml of styrene (0.140 moles) purified by the passage in a basic alumina column, 0.75 ml of a 2 M solution in triethylaluminum toluene (1.5 x 10 ~ 3 moles), 2 ml of a 0.01 M solution in tetramethyltin toluene (2 x 10"^ moles) and then 0.5 ml of a 0.01 M solution in toluene of (pentamethylcyclopentadienyl) titanium trichloride (5 x 10" 6 moles), are introduced into a subsequent test tube in an inert atmosphere. The reaction is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 126 mg (0.9% yield) of atactic polystyrene are obtained.
COMPARATIVE EXAMPLE 3
16 ml of styrene (0.140 moles) purified by the passage in a basic alumina column and 0.96 ml of a 1.57 M solution in toluene of methylaluminoxane (1.5 x 10 ~ 3 moles) are introduced into a subsequent test tube in an inert atmosphere . After 5 minutes, 0.5 ml of a 0.01 M solution in toluene of tetra ethyl ethyl (5 x 10 ~ 6 moles) is added. The reaction is carried out for 5 hours at 60 ° C.
At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 711 mg (4.9% yield) of atactic polystyrene are obtained. Average molecular weight weight (Mw): 78,000; Average number of molecular weight (Mn): 14,000.
COMPARATIVE EXAMPLE 4
ml of styrene (0.175 moles) purified by the passage in a basic alumina column and 1.2 ml of a 1.57 M solution in toluene of methylaluminoxane (1.88 x 10 ~ 3 moles) are introduced into a subsequent test tube in an inert atmosphere . After 5 minutes, 0.5 ml of a 0.0125 M solution in toluene of (pentamethylcyclopentadienyl) titanium trichloride (6.25 x 10 ~ 6 moles) is added. The reaction is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 1.13 g (6.2% yield) of the polymer are obtained. The fraction insoluble in methyl ethyl ketone (MEK): 77%. 13-C NMR analysis showed that the insoluble fraction had a percentage of syndiotactic dyads of 99.99%. Average molecular weight weight (Mw): 300,000; Average number of molecular weight (Mn): 167,000.
COMPARATIVE EXAMPLE 5
ml of styrene (0.175 moles) purified by the passage in a basic alumina column and 1.2 ml of a 1.57 M solution in toluene of methylaluminoxane (1.88 x 10"3 moles) are introduced into a subsequent test tube in an inert atmosphere After 5 minutes, 0.5 ml of a 0.0125 M solution in toluene of titanium tetraethoxide (6.25 x 10 ~ 6 moles) is added in. The reaction is carried out for 5 hours at 60 ° C.
At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 1.38 g (7.6% yield) of the polymer are obtained.
The fraction insoluble in methyl ethyl ketone (MEK): 86%. The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads of 99.5%. Average molecular weight weight (Mw): 368,000; Average number of molecular weight (Mn): 164,000.
COMPARATIVE EXAMPLE 6
ml of styrene (0.175 moles) purified by the passage in a basic alumina column and 1.2 ml of a 1.57 M solution in toluene of ethylaluminoxane (1.88 x 10"3 moles) are introduced into a subsequent test tube in an inert atmosphere After 5 minutes, 2.2 ml of a 0.0285 M solution in toluene of (indenyl) titanium trichloride (6.25 x 10 ~ 6 moles) are added in. The reaction is carried out for 2 hours at 60 ° C. The mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered, the solid is again suspended in methanol, filtered and dried under vacuum to obtain 2.11 g (11.6% yield) of the polymer. Insoluble fraction in methyl ethyl ketone (MEK): 86% The analysis by NMR-C showed that the insoluble fraction had a percentage of syndiotactic dyads of 99.5% Average weight of molecular weight (Mw): 250,000 Average number of molecular weight ( Mn): 127,000.
COMPARATIVE EXAMPLE 7
ml of styrene (0.175 moles) purified by the passage in a column of basic alumina and 1.2 ml of a 1.57 M solution in toluene of methylaluminoxane (1.88 x
"3 moles) are introduced into a subsequent test tube in an inert atmosphere.After 5 minutes, 0.5 rnl of a 0.0125 M solution in toluene of sodium trichloride is added.
(cyclopentadienyl) titanium (6.25 x 10"6 moles) The reaction is carried out for 2 hours at 60 ° C.
At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 4.18 g (31.6% yield) of the polymer are obtained. The fraction insoluble in methyl ethyl ketone (MEK): 89.3%. The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads of 97.8%. Average molecular weight weight (Mw): 93,000;
Average number of molecular weight (Mn): 50,000.
COMPARATIVE EXAMPLE 8
22. 9 ml of styrene (0.2 moles) purified by the passage in a basic alumina column and 0.4 ml of a 1.57 M solution in toluene of methylaluminoxane (6 x 10 ~ 4 moles) are introduced into a subsequent test tube in an inert atmosphere . After S minutes, 0.2 ml of a 0.01 M solution in toluene of (cyclopentadienyl) titanium trichloride (2 x 10"6 moles) is added.The reaction is carried out for 2 hours at 60 ° C. The mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered, the solid is again suspended in methanol, filtered and dried under vacuum to obtain 4.55 g (21.9% yield) of the polymer. insoluble in methyl ethyl ketone (MEK): 85% The analysis by 13 C-NMR showed that the insoluble fraction had a percentage of syndiotactic dyads of 98.5% Average molecular weight (Mw): 132,000 Average number of molecular weight (Mn) ): 47,000.
EXAMPLE 1 16 mi of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.51 x 10 ~ 3 moles I, 0.5 ml of a 0.01 M solution in toluene of tetra ethyltin (5 x 10-moles) and then 0.5 ml of a 0.01 M solution in toluene of (pentamethylcyclopentadienyl) titanium trichloride (5 x 10 ~ 6 moles), are introduced into a subsequent test tube in an inert atmosphere. The reaction is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered, the solid is again suspended in methanol, filtered and dried under vacuum, 1.84 g (yield of 12.7%) of the polymer are obtained, the fraction insoluble in methyl ethyl ketone (MEK):
65% The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads greater than 99.99%. Average molecular weight weight (Mw): 505,000; Average number of molecular weight (Mn): 221,000.
EXAMPLE 2
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.5 x 10"3 moles), 2 ml of a 0.01 M solution in tetramethyltin toluene (2 x 10 ~ 5 moles) and then 0.5 ml of a 0.01 M solution in toluene of (pentamethylcyclopentadienyl) titanium trichloride (5 x 10 ~ 6 moles), are introduced into a subsequent test tube in an inert atmosphere. It is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered.The solid is suspended again in methanol, filtered and dried under vacuum 2.5 g (yield of 17.7%) of the polymer are obtained The fraction insoluble in methyl ethyl ketone (MEK): 76% The analysis by 13 C-NMR showed that the insoluble fraction had a percentage of syndiotactic dyads greater than 99.99%. average molecular weight (Mw): 1,350,000; Average number of molecular weight (M) n): 300,000.
EXAMPLE 3
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.5 x 10"3 moles), 2 ml of a 0.01 M solution in tetraphenyl tin toluene (2 x 10"5 moles) and then 0.5 ml of a 0.01 M solution in toluene of (pentamethylcyclopentadienyl) titanium trichloride (5 x 10 ~ 6 moles), are introduced into a subsequent test tube in an inert atmosphere. The reaction is carried out for 2 hours at 60 ° C.
At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 2.13 g (14.6% yield) of the polymer are obtained. The fraction insoluble in methyl ethyl ketone (MEK): 79%. The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads greater than 99.99%. Average molecular weight weight (Mw): 590,000; Average number of molecular weight (Mn): 257,000.
EXAMPLE 4
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.48 ml of a 1.57 M solution in MAO toluene (7.5 x 10 ~ 4 moles), 2 ml of a 0.01 M solution in tetraphenyl tin toluene (2 x 10 ~ 5 moles) and then 0.5 ml of a 0.01 M solution in toluene of (pentamethylcyclopentadienyl) titanium trichloride (5 x 10"^ moles), are introduced into a subsequent test tube in an inert atmosphere. It is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered.The solid is suspended again in methanol, filtered and dried under vacuum 1.39 g (9.6% yield) of the polymer are obtained, the fraction insoluble in methyl ethyl ketone (MEK): 84%, The analysis by 13 C-NMR showed that the insoluble fraction had a percentage of syndiotactic dyads greater than 99.99%. average molecular weight (Mw): 624,000; Average number of molecular weight (Mn) : 300,000.
EXAMPLE 5
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.5 x 10"3 moles), 0.5 ml of a 0.01 M solution in tetramethyltin toluene (5 x 10"6 moles) and then 0.5 ml of a 0.01 M solution in toluene of titanium tetraethoxide (5 x 10" 6 moles) are introduced into a subsequent test tube in an inert atmosphere.
The reaction is carried out for 5 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 3.13 g (21.5% yield) of the polymer are obtained. The fraction insoluble in methyl ethyl ketone (MEK): 79%. The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads of 99.4%. Average molecular weight weight (Mw): 352,000; Average number of molecular weight (Mn): 166,000.
EXAMPLE 6
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.5 x 10 ~ 3 moles), 2 ml of a 0.01 M solution in tetramethyltin toluene (2 x 10"5 moles) and then 0.5 ml of a 0.01 M solution in toluene of titanium tetraethoxide (5 x 10" 6 moles) are introduced into a subsequent test tube in an inert atmosphere. The reaction is carried out for 5 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 2.04 g (14% yield) of the polymer are obtained. The insoluble fraction in methyl ethyl ketone (MEK): 84%. The 13-C NMR analysis showed that the insoluble fraction had a percentage of syndiotactic dyads of 99.6%. Average molecular weight weight (Mw): 390,000; Average number of molecular weight (Mn): 190,000.
EXAMPLE 7
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.5 x 10"3 moles), 2 ml of a 0.01 M solution in tetraphenyl tin toluene (2 x 10"5 moles) and then 0.5 ml of a 0.01 M solution in toluene of titanium tetraethoxide (5 x 10" ^ moles), are introduced into a subsequent test tube in an inert atmosphere. Hold for 5 hours at 60 ° C.
At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 1.8 g (12.4% yield) of the polymer are obtained.
The insoluble fraction in methyl ethyl ketone (MEK): 53%. The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads of 99.5%. Average molecular weight weight (Mw): 364,000; Average number of molecular weight (Mn): 186,000.
EXAMPLE 8
ml of styrene (0.175 moles) purified by the passage in a basic alumina column, 1.2 ml of a 1.57 M solution in MAO toluene (1.88 x 10 ~ 3 moles), 2.35 ml of a 0.0013 M solution in tetramethyltin toluene (3.12 x 10 ~ 6 moles) and a 0.0027 M solution of (indenyl) titanium trichloride (6.25 x 10 ~ 6 moles) are introduced into a subsequent test tube in an inert atmosphere. The reaction is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 3.65 g (20% yield) of the polymer are obtained. The fraction insoluble in methyl ethyl ketone (MEK):
94% The 13-C NMR analysis showed that the insoluble fraction had a percentage of syndiotactic dyads of 99.6%. Average molecular weight weight (Mw): 233,000; Average number of molecular weight (Mn): 99,000.
EXAMPLE 9
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.5 x 10 ~ 3 moles), 2 ml of a 0.01 M solution in tetraphenyl tin toluene (2 x 10"5 moles) and then 0.5 ml of a 0.01 M solution in toluene of (cyclopentadienyl) titanium trichloride (5 x 10-6 moles), are introduced into a subsequent test tube in an inert atmosphere. It is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered.The solid is suspended again in methanol, filtered and dried under vacuum Obtained 6.13 g (42.1% yield) of the polymer The fraction insoluble in methyl ethyl ketone (MEK): 84% The 1 C-NMR analysis showed that the insoluble fraction had a percentage of syndiotactic dyads of 98.1%.
Average molecular weight weight (Mw): 140,000; Average number of molecular weight (Mn): 52,000.
EXAMPLE 10
16 ml of styrene (0.14 moles) purified by the passage in a basic alumina column, 0.96 ml of a 1.57 M solution in MAO toluene (1.5 x 10 ~ 3 moles), 0.5 ml of a 0.01 M solution in tetramethyltin toluene (5 x 10 ~ 6 moles) and then 0.5 ml of a 0.01 M solution in toluene of (cyclopentadienyl) titanium trichloride (5 x 10 ~ 6 moles), are introduced into a subsequent test tube in an inert atmosphere. The reaction is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 3.16 g (21.7% yield) of the polymer are obtained. The fraction insoluble in methyl ethyl ketone (MEK):
75% The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads of 98.2%. Average molecular weight weight (Mw): 124,000; Average number of molecular weight (Mn): 63,000.
EXAMPLE 11
22. 9 ml of styrene (0.2 moles) purified by the passage in a basic alumina column, 0.2 ml of a 1.57 M solution in MAO toluene (3 x 10 ~ 4 moles), 2 ml of a 0.01 M solution in tetraphenyl tin toluene (5 x 10"5 moles), they are introduced into a subsequent test tube in an inert atmosphere.After 5 minutes, 0.2 ml of a 0.01 M solution in toluene of (cyclopentadienyl) titanium trichloride (2 x 10") is added. 6 moles). The reaction is carried out for 2 hours at 60 ° C. At the end, the mixture is suspended in 200 ml of methanol containing 2 ml of concentrated HCl and filtered. The solid is again suspended in methanol, filtered and dried under vacuum. 4.33 g (20.8% yield) of the polymer are obtained. The fraction insoluble in methyl ethyl ketone (MEK): 90%. The analysis by 13-C NMR showed that the insoluble fraction had a percentage of syndiotactic dyads of 98.3%. Average molecular weight weight (Mw): 146,000; Average number of molecular weight (Mn): 86,000.
Claims (11)
1. A process for the preparation of crystalline vinyl aromatic polymers with a predominantly syndiotactic structure, which is characterized in that it comprises polymerizing vinylaromatic monomers, alone or mixed with at least one other copolymerizable ethylenically unsaturated monomer, in the presence of a catalyst system consisting essentially of: a) a titanium or zirconium complex selected from those having the general formula: MR1R2R3R, A1MR1R2R3, A1A2MR1R2 (I) wherein the groups R- ^, R2"R3 and R4, equal or different, represent (iso) alkyl of C 1 -cyo (iso) alkoxy, alkylamide radical, an aryl radical of Cg-C- ^ Q or a halogen such as chlorine, while the groups A- ^ and A2, the same or different, represent a cyclopentadienyl ligand, optionally substituted with alkyl radicals of C-^ - C- ^ Q, OR an indenyl ligand; M represents a titanium or zirconium atom; b) a cocatalyst selected from an alkylaluminoxane and a boron compound having the formula (II): BX-j ^^ (II) Or one of its salts, in which X- ^, X2 and X3, are the same or different, represent a fluorinated hydrocarbon radical of C1-C20; and c) a tin derivative having the general formula: SnR5R6R7R8 (III) wherein the groups R5, Rg, R7 and Rg, equal or different, represent an (iso) alkyl or aryl radical of C ^ -C-jo.
2. The process according to claim 1, characterized in that the molar ratio of the vinylaromatic monomer / M is between 1,000 and 200,000.
3. The process in accordance with the claim 1 or 2, characterized in that the cocatalyst is used in amounts such that the molar ratio of aluminum / M is between 50 and 2,000 or the boron / M ratio is between 0.5 and 10.
4. The process according to any of the previous claims, characterized in that the tin derivative is added to the polymerization mixture in such an amount that the molar ratio of Sn / M is between 0.01 and 100.
5. The process according to any of the preceding claims, characterized in that the above catalyst system comprises an alkyl aluminum wherein the alkyl group contains from 1 to 6 carbon atoms.
6. The process according to claim 5, characterized in that the molar ratio of alkylaluminium / M is between 0 and 800.
7. The process according to any of the previous claims, characterized in that the polymerization reaction is carried out in bulk or in a solvent.
8. The process according to claim 7, characterized in that the solvent is used in amounts such that the volume ratio of solvent / monomers is between 0 and 10.
9. The process according to any of the previous claims, characterized in that the polymerization is carried out at temperatures between 20 and 100 ° C.
10. A catalytic composition characterized in that it comprises: a) a titanium complex selected from those having the general formula: MR-LR2R3R4, A1MR1R2R3, A1A2MR1R2 (I) wherein the groups R- ^ R2, R3 and R4, equal or different, represent (iso) alkyl of c? "ci0 '(iso) alkoxy, alkylamido radical, an aryl radical of g-C1Q or a halogen such as chloro , while the groups A- ^ and A, the same or different, represent a cyclopentadienyl ligand, optionally substituted with alkyl radicals of C-, - C- ^ Q, OR an indenyl ligand, M represents a titanium or zirconium atom; ) a cocatalyst selected from an alkylaluminoxane and a boron compound having the formula (II): -D? -i? «^? (II) or one of its salts, in which X- ^, X2 and X3, are the same or different, represent a fluorinated hydrocarbon radical of c? _ c2o; c) a tin derivative having the general formula: SnR5R6R7R8 (III) in which the same or different groups R5, Rg, R7 and RQ I represent an (iso) alkyl or aryl radical of C- ^ - C- ^ Q.
11. The use of a catalytic composition comprises: a) a titanium or zirconium complex selected from those having the general formula: MR1R2R3R4, A1MR1R2R3, A1A2MR1R2 (I) wherein the groups R- ^ R2, R3 and R4, the same or different, represent (iso) alkyl of c? ci0 '(iso) alkoxy, alkylamide radical, an aryl radical of gC- ^ Q or a halogen such as chlorine, while the same or different groups A- ^ and A2 represent-a cyclopentadienyl ligand, optionally substituted with alkyl radicals of C-, -C-, Q, O an indenyl ligand; M represents a titanium or zirconium atom; b) a cocatalyst selected from an alkylaluminoxane and a boron compound having the formula (II): BX ^ X ^ (II) or one of its salts, in which X- ^, X2 and X3, are the same or different, represent a fluorinated hydrocarbon radical of? _ c2o; and c) a tin derivative having the general formula: SnR5R6R7R8 (III) wherein the groups R5, Rg, R7 and Rg, equal or different, represent an (iso) alkyl or aryl radical in the preparation of crystalline vinylaromatic polymers having a predominantly syndiotactic structure.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MIMI95A002701 | 1995-12-21 | ||
IT95MI002701A IT1277677B1 (en) | 1995-12-21 | 1995-12-21 | PROCEDURE FOR THE PREPARATION OF CRYSTALLINE VINYLAROMATIC POLYMERS WITH PREDOMINANTLY SYNDIOTACTIC STRUCTURE |
Publications (2)
Publication Number | Publication Date |
---|---|
MXPA96006540A true MXPA96006540A (en) | 1997-06-01 |
MX9606540A MX9606540A (en) | 1997-06-28 |
Family
ID=11372771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
MX9606540A MX9606540A (en) | 1995-12-21 | 1996-12-17 | Process for the preparation of crystalline vinylaromatic polymers having an essentially syndiotactic structure. |
Country Status (11)
Country | Link |
---|---|
US (1) | US5728784A (en) |
EP (1) | EP0780405B1 (en) |
JP (1) | JPH09183811A (en) |
AT (1) | ATE176248T1 (en) |
CA (1) | CA2191361A1 (en) |
DE (1) | DE69601457T2 (en) |
DK (1) | DK0780405T3 (en) |
ES (1) | ES2128815T3 (en) |
GR (1) | GR3029595T3 (en) |
IT (1) | IT1277677B1 (en) |
MX (1) | MX9606540A (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6274752B1 (en) | 1996-02-20 | 2001-08-14 | Northwestern University | Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations |
US5856256A (en) * | 1996-02-20 | 1999-01-05 | Northwestern University | Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations |
US6291695B1 (en) | 1996-02-20 | 2001-09-18 | Northwestern University | Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon |
IT1286031B1 (en) * | 1996-10-24 | 1998-07-07 | Enichem Spa | PROCESS FOR THE PRODUCTION OF VINYLAROMATIC POLYMERS WITH A HIGH DEGREE OF SYNDIOTAXY |
EP0954540B1 (en) | 1997-01-14 | 2004-07-28 | SABIC Polypropylenes B.V. | A process for polymerizing olefins |
NL1004992C2 (en) * | 1997-01-14 | 1998-07-15 | Dsm Nv | Use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins. |
ITMI980934A1 (en) * | 1998-04-30 | 1999-10-30 | Enichem Spa | PROCEDURE FOR THE PREPARATION OF PRODUCTS BASED ON VINYLAROMATIC POLYMERS WITH A PREDOMINALLY SYNDIOTACTIC STRUCTURE |
CN1117106C (en) * | 1999-06-24 | 2003-08-06 | 中国石油化工集团公司 | Syndiotactic poly styrene polymer |
US6982306B2 (en) | 2003-11-26 | 2006-01-03 | Chevron Phillips Chemical Company, L.P. | Stannoxy-substituted metallocene catalysts for olefin and acetylene polymerization |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1276748C (en) | 1985-07-29 | 1990-11-20 | Michitake Uoi | Styrene polymers |
IL84798A (en) | 1986-12-15 | 1991-09-16 | Montedison Spa | Production of crystalline vinyl aromatic polymers having mainly a syndiotactic structure |
US4978730A (en) | 1987-12-24 | 1990-12-18 | Idemitsu Kosan Company Limited | Process for producing styrene-based polymers and catalyst for use therein |
IT1231774B (en) * | 1989-08-03 | 1991-12-21 | Enichem Anic Spa | CATALYST AND PROCEDURE FOR THE POLYMERIZATION AND COPOLYMERIZATION OF ALFA OLEFINE. |
US5326837A (en) * | 1992-11-20 | 1994-07-05 | Mobil Oil Corporation | Catalyst systems for syndiospecific polymerization of styrenes |
EP0675139B1 (en) * | 1994-03-31 | 1998-10-14 | Idemitsu Kosan Co., Ltd. | Process for producing styrenic polymer |
IT1276801B1 (en) * | 1995-06-30 | 1997-11-03 | Enichem Spa | PROCEDURE FOR THE PREPARATION OF CRYSTALLINE VINYLAROMATIC POLYMERS WITH PREDOMINANTLY SYNDIOTACTIC STRUCTURE |
US5644009A (en) * | 1995-11-27 | 1997-07-01 | Industrial Technology Research Institute | Catalyst composition for preparing high syndiotacticity polystyrene from styrene of other arylethylene monomers and processes using the same |
-
1995
- 1995-12-21 IT IT95MI002701A patent/IT1277677B1/en active IP Right Grant
-
1996
- 1996-11-12 DK DK96118100T patent/DK0780405T3/en active
- 1996-11-12 EP EP96118100A patent/EP0780405B1/en not_active Expired - Lifetime
- 1996-11-12 DE DE69601457T patent/DE69601457T2/en not_active Expired - Fee Related
- 1996-11-12 ES ES96118100T patent/ES2128815T3/en not_active Expired - Lifetime
- 1996-11-12 AT AT96118100T patent/ATE176248T1/en not_active IP Right Cessation
- 1996-11-26 CA CA002191361A patent/CA2191361A1/en not_active Abandoned
- 1996-11-27 US US08/757,251 patent/US5728784A/en not_active Expired - Fee Related
- 1996-12-17 MX MX9606540A patent/MX9606540A/en not_active Application Discontinuation
- 1996-12-24 JP JP8343764A patent/JPH09183811A/en active Pending
-
1999
- 1999-03-05 GR GR990400682T patent/GR3029595T3/en unknown
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1311580C (en) | Process for producing crystalline vinyl aromatic polymers having mainly a syndiotactic structure | |
EP0224097A1 (en) | Process for production of styrene polymers | |
US4990580A (en) | Process for production of styrene polymers | |
JPH04296306A (en) | Production of styrenic production and catalyst therefor | |
US5023304A (en) | Process for producing styrene-based polymer | |
MXPA96006540A (en) | PROCESS FOR THE PREPARATION OF POLYMEROSVINILAROMATICOS CRISTALINOS WITH A STRUCTURAPREDOMINANTmente SINDIOTACT | |
US5728784A (en) | Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure | |
US5830959A (en) | Process for the production of vinylaromatic polymers with a high degree of syndiotacticity | |
EP0751154B1 (en) | Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure | |
EP0796875B1 (en) | Process for the preparation of crystalline vinylaromatic polymers with a predominant syndiotactic structure | |
EP0770630B1 (en) | Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure | |
JPH01294705A (en) | Preparation of styrene polymer and catalyst therefor | |
US5780567A (en) | Syndiotactic terpolymers of styrene | |
MXPA96002523A (en) | PROCESS FOR THE PREPARATION OF POLYMEROSVINILAROMATICOS CRISTALINOS WITH A STRUCTURAPREDOMINANTmente SINDIOTACT | |
EP0994126B1 (en) | Process for the preparation of vinylaromatic polymers with a high degree of syndiotacticity | |
JP2931642B2 (en) | Method for producing styrenic polymer and its catalyst | |
KR100503359B1 (en) | Metallocene catalyst for styrene polymerization and polymerization process using the same | |
JPS63172705A (en) | Manufacture of crystalline vinyl aromatic polymer having mainly syndiotactic structure | |
KR100570420B1 (en) | Method for Preparing Syndiotactic Polystyrenes and Syndiotactic Polystyrenes Produced Thereby | |
JPH0813853B2 (en) | Method for producing styrene polymer and its catalyst |