CN1119358C - Syndiotactic polystyrene catalyst and its preparation and application - Google Patents
Syndiotactic polystyrene catalyst and its preparation and application Download PDFInfo
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- CN1119358C CN1119358C CN99125503A CN99125503A CN1119358C CN 1119358 C CN1119358 C CN 1119358C CN 99125503 A CN99125503 A CN 99125503A CN 99125503 A CN99125503 A CN 99125503A CN 1119358 C CN1119358 C CN 1119358C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 107
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 36
- 239000010936 titanium Substances 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 239000003446 ligand Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 17
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 9
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 7
- 125000006278 bromobenzyl group Chemical group 0.000 claims description 6
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 6
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 abstract description 10
- 229920002223 polystyrene Polymers 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 125000002877 alkyl aryl group Chemical group 0.000 abstract 1
- 239000003426 co-catalyst Substances 0.000 abstract 1
- 150000002605 large molecules Chemical class 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 26
- -1 6-tertiary butyl-4-methylphenoxy Chemical group 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 21
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 21
- 238000005406 washing Methods 0.000 description 17
- MGYHIKCCZXKOKG-UHFFFAOYSA-N C(C)C(=O)C(=O)CC(CC)C Chemical compound C(C)C(=O)C(=O)CC(CC)C MGYHIKCCZXKOKG-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000010189 synthetic method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- MVRMGIVMEQWKSK-UHFFFAOYSA-N 1-phenylhexane-3,4-dione Chemical compound CCC(=O)C(=O)CCC1=CC=CC=C1 MVRMGIVMEQWKSK-UHFFFAOYSA-N 0.000 description 4
- MKAUELPAFGMJIE-UHFFFAOYSA-N 3-benzyl-1,1,1-trifluoropentane-2,4-dione Chemical compound FC(C(=O)C(C(C)=O)CC1=CC=CC=C1)(F)F MKAUELPAFGMJIE-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- LVMIOLNODODDMM-UHFFFAOYSA-N 1,1,1-trifluoro-3-methylpentane-2,4-dione Chemical compound CC(=O)C(C)C(=O)C(F)(F)F LVMIOLNODODDMM-UHFFFAOYSA-N 0.000 description 2
- QHRQGSBXUVRVLO-UHFFFAOYSA-N 1,1,1-trifluoro-3-phenylpentane-2,4-dione Chemical compound FC(F)(F)C(=O)C(C(=O)C)C1=CC=CC=C1 QHRQGSBXUVRVLO-UHFFFAOYSA-N 0.000 description 2
- KLTPYBVFWXAWMB-UHFFFAOYSA-N 3-butyl-1,1,1-trifluoropentane-2,4-dione Chemical compound C(CCC)C(C(C)=O)C(C(F)(F)F)=O KLTPYBVFWXAWMB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VCKABTFLUQGPME-UHFFFAOYSA-N C(C)C(C(C)=O)C(C(F)(F)F)=O Chemical compound C(C)C(C(C)=O)C(C(F)(F)F)=O VCKABTFLUQGPME-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- AVAYHINFKCDOBV-UHFFFAOYSA-N 3-butyl-1,1,1-trifluoropentane-2,4-dione titanium Chemical compound [Ti].C(CCC)C(C(C)=O)C(C(F)(F)F)=O AVAYHINFKCDOBV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 1
- GEXSKFPJCMDVCP-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C(C)C(C(C)=O)C(C(F)(F)F)=O Chemical compound [Cl-].[Cl-].[Ti+2].C(C)C(C(C)=O)C(C(F)(F)F)=O GEXSKFPJCMDVCP-UHFFFAOYSA-L 0.000 description 1
- QJYXVEIKMAPHNJ-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C(C1=CC=CC=C1)C(C(C)=O)C(C(F)(F)F)=O Chemical compound [Cl-].[Cl-].[Ti+2].C(C1=CC=CC=C1)C(C(C)=O)C(C(F)(F)F)=O QJYXVEIKMAPHNJ-UHFFFAOYSA-L 0.000 description 1
- WRGHEBXJMAIYLO-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C(CCC)C(C(C)=O)C(C(F)(F)F)=O Chemical compound [Cl-].[Cl-].[Ti+2].C(CCC)C(C(C)=O)C(C(F)(F)F)=O WRGHEBXJMAIYLO-UHFFFAOYSA-L 0.000 description 1
- KJQGCGPDVSCYRH-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C1(=CC=CC2=CC=CC=C12)C1=CC=CC=C1CC(C(C)=O)C(C(F)(F)F)=O Chemical compound [Cl-].[Cl-].[Ti+2].C1(=CC=CC2=CC=CC=C12)C1=CC=CC=C1CC(C(C)=O)C(C(F)(F)F)=O KJQGCGPDVSCYRH-UHFFFAOYSA-L 0.000 description 1
- YNUBMIZLYRFLGW-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C1(=CC=CC=C1)C(C(C)=O)C(C(F)(F)F)=O Chemical compound [Cl-].[Cl-].[Ti+2].C1(=CC=CC=C1)C(C(C)=O)C(C(F)(F)F)=O YNUBMIZLYRFLGW-UHFFFAOYSA-L 0.000 description 1
- QWENKFSGDVNELV-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].CC(C(C)=O)C(C(F)(F)F)=O Chemical compound [Cl-].[Cl-].[Ti+2].CC(C(C)=O)C(C(F)(F)F)=O QWENKFSGDVNELV-UHFFFAOYSA-L 0.000 description 1
- TVFSCFCSLVQZCA-UHFFFAOYSA-J [Cl-].[Ti+4].C(C)C(=O)C(=O)C.[Cl-].[Cl-].[Cl-] Chemical group [Cl-].[Ti+4].C(C)C(=O)C(=O)C.[Cl-].[Cl-].[Cl-] TVFSCFCSLVQZCA-UHFFFAOYSA-J 0.000 description 1
- NDURKLKAFIELSO-UHFFFAOYSA-N [Ti].C(C)C(C(C)=O)C(C(F)(F)F)=O Chemical compound [Ti].C(C)C(C(C)=O)C(C(F)(F)F)=O NDURKLKAFIELSO-UHFFFAOYSA-N 0.000 description 1
- DMDREOQUBOGERX-UHFFFAOYSA-N [Ti].C(C1=CC=CC=C1)C(C(C)=O)C(C(F)(F)F)=O Chemical compound [Ti].C(C1=CC=CC=C1)C(C(C)=O)C(C(F)(F)F)=O DMDREOQUBOGERX-UHFFFAOYSA-N 0.000 description 1
- GUVGATDVRWNCHU-UHFFFAOYSA-N [Ti].C1(=CC=CC2=CC=CC=C12)C1=CC=CC=C1CC(C(C)=O)C(C(F)(F)F)=O Chemical compound [Ti].C1(=CC=CC2=CC=CC=C12)C1=CC=CC=C1CC(C(C)=O)C(C(F)(F)F)=O GUVGATDVRWNCHU-UHFFFAOYSA-N 0.000 description 1
- 238000003811 acetone extraction Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- FLULSIQYMOLNGT-UHFFFAOYSA-N titanium 1,1,1-trifluoro-3-methylpentane-2,4-dione Chemical compound [Ti].CC(C(C)=O)C(C(F)(F)F)=O FLULSIQYMOLNGT-UHFFFAOYSA-N 0.000 description 1
- KFLIPQMEEHFYJN-UHFFFAOYSA-N titanium 1,1,1-trifluoro-3-phenylpentane-2,4-dione Chemical compound [Ti].C1(=CC=CC=C1)C(C(C)=O)C(C(F)(F)F)=O KFLIPQMEEHFYJN-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-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
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
一种合成间规聚苯乙烯的催化剂及其制备方法与合成应用，该催化剂具有的通式表达式为：式中R′和R″相同或不相同，分别选自C1～C12的烷基、C6～C10芳基或C1～C12的全氟烷基，其中所述的芳基为苯基或烷基取代的苯基，R选自C1～C12的烷基、C6～C14烷芳基或C1～C12的全氟烷基，M选自IVB族金属元素，X为卤素，n为1～4的整数。由四氯化钛与3位带有取代基的β-二酮或其衍生物反应而生成，该催化剂具有较高的催化活性，与助催化剂铝氧烷配合使用，可制得具有较高分子量的，间规度为94～98%的聚苯乙烯。
A catalyst for synthesizing syndiotactic polystyrene and its preparation method and synthesis application. The catalyst has a general formula expression: in the formula, R' and R" are the same or different, and are respectively selected from C 1 to C 12 alkanes C 6 -C 10 aryl or C 1 -C 12 perfluoroalkyl, wherein the aryl is phenyl or phenyl substituted by alkyl, R is selected from C 1 -C 12 alkyl, C 6 ~C 14 alkaryl or C 1 ~C 12 perfluoroalkyl, M is selected from group IVB metal elements, X is halogen, n is an integer of 1 to 4. Composed of titanium tetrachloride and 3-position with It is produced by the reaction of β-diketone or its derivatives of the substituent. The catalyst has high catalytic activity. It can be used in conjunction with the co-catalyst aluminoxane to obtain a high molecular weight compound with a syndiotacticity of 94-98%. of polystyrene.
Description
The present invention relates to a kind of syndiotactic polystyrene catalyst and preparation method thereof and application, specifically, is a kind of syndiotactic polystyrene catalyst that contains beta-diketon class part and preparation method thereof and application.
To the chain backbone spatial orientation, the polystyrene molecule has random a-PS according to polystyrene molecular side chain phenyl ring, complete same i-PS, three kinds of different steric configurations of rule s-PS.Macromolecules, 19,2464 (1986) have reported a kind of high reactivity syndiotactic polystyrene catalyst CpTiCl that is proposed by N.Ishihara
3Macromol.Chem.Macromol.Symp in 1993,66,203 have reported that employing prepares normality polystyrene resin between height with two (the 6-tertiary butyl-4-methylphenoxy) titanium dichloride/MAO systems of sulphur bridge.
It is the catalyst system of the synthesis of syndiotactic polystyrene of Primary Catalysts with the beta-diketon titanium chloride that CN1158859A discloses a kind of.The preferred Primary Catalysts of this patent is methyl ethyl diketone titanium chloride and diphenylpropane-1,3-dione(DPPO) titanium chloride.Though this catalyzer can prepare normality and the higher polystyrene of heat resisting temperature between height, catalyst activity is still on the low side, and the molecular weight of polystyrene is not high.
USP4,808,680 to disclose a kind of general formula be CpZrR
3The luxuriant zirconium compounds of list, Cp in the formula is the cyclopentadienyl that cyclopentadienyl or alkyl replace, R is that halogen, alkoxyl group or expression formula are the beta-diketon ion of R '-C (O)-CH-C (O)-R ', and the R ' in the expression formula is less than 12 alkyl or aryl for carbonatoms.But this patent has only provided the example of cyclopentadiene tri-chlorination zirconium and cyclopentadiene three (phenoxy group) zirconium, and this catalyst activity is low, and normality and heat resisting temperature are all lower between the poly styrene polymer that makes.
The purpose of this invention is to provide the catalyzer of normality, high molecular weight polystyrene between a kind of synthetic height, this catalyzer has high polymerization activity.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
It is Primary Catalysts that a further object of the present invention provides with above-mentioned catalyzer, the method for synthesis of syndiotactic polystyrene.
We find, contain the polyphenylacetylene catalyst of β 3-diketonate ligand, and the substituting group on 3 carbon of beta-diketonate ligand has a significant impact catalytic activity.When the substituting group on 3 carbon is electron donating group, can increase the stability of catalyst active center, therefore can improve catalytic activity, and the substituting group of the large volume on 3 carbon there is good promoter action to the upright structure that improves polymkeric substance.The present invention utilizes this characteristic exactly, by connect different substituting groups on 3 carbon of beta-diketonate ligand catalyzer is carried out modification, to improve the reactivity worth of catalyzer.
Catalyzer provided by the invention has following general expression:
R ' and R in the formula " identical or inequality, be selected from C respectively
1～C
12Alkyl, C
6～C
10Aryl or C
1～C
12Perfluoroalkyl, wherein said aryl is the phenyl that phenyl or alkyl replace; Preferred R ' and R " are C
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or phenyl.
Described R is selected from C
1～C
12Alkyl, C
6～C
14Alkaryl or C
1～C
12Perfluoroalkyl, preferred C
1～C
6Alkyl, C
1～C
3Perfluoroalkyl, phenyl, benzyl or naphthalene benzyl.
M is selected from IVB family metallic element, as titanium, zirconium or hafnium, and preferred titanium,
X is a halogen, preferred chlorine,
N is 1～4 integer.
Catalyzer provided by the invention comparatively preferably has: (3-methyl-methyl ethyl diketone)-titanous chloride, two (3-methyl-methyl ethyl diketone)-titanium dichloride, three (3-methyl-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-methyl-methyl ethyl diketone) titanium, (3-ethyl-methyl ethyl diketone)-titanous chloride, two (3-ethyl-methyl ethyl diketone)-titanium dichloride, three (3-ethyl-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-ethyl-methyl ethyl diketone) titanium, (3-propyl group-methyl ethyl diketone)-titanous chloride, two (3-propyl group-methyl ethyl diketone)-titanium dichloride, three (3-propyl group-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-propyl group-methyl ethyl diketone) titanium, (3-sec.-propyl-methyl ethyl diketone)-titanous chloride, two (3-sec.-propyl-methyl ethyl diketone)-titanium dichloride, three (3-sec.-propyl-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-sec.-propyl-methyl ethyl diketone) titanium, (3-butyl-methyl ethyl diketone)-titanous chloride, two (3-butyl-methyl ethyl diketone)-titanium dichloride, three (3-butyl-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-butyl-methyl ethyl diketone) titanium, (3-phenyl-methyl ethyl diketone)-titanous chloride, two (3-phenyl-methyl ethyl diketone)-titanium dichloride, three (3-phenyl-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-phenyl-methyl ethyl diketone) titanium, (3-benzyl-methyl ethyl diketone)-titanous chloride, two (3-benzyl-methyl ethyl diketone)-titanium dichloride, three (3-benzyl-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-benzyl-methyl ethyl diketone) titanium, (3-naphthalene benzyl-methyl ethyl diketone)-titanous chloride, two (3-naphthalene benzyl-methyl ethyl diketone)-titanium dichloride, three (3-naphthalene benzyl-methyl ethyl diketone)-monochlor(in)ate titaniums, four (3-naphthalene benzyl-methyl ethyl diketone) titanium, (3-methyl-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-methyl-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-methyl-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-methyl-diphenylpropane-1,3-dione(DPPO)) titanium, (3-ethyl-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-ethyl-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-ethyl-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-ethyl-diphenylpropane-1,3-dione(DPPO)) titanium, (3-propyl group-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-propyl group-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-propyl group-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-propyl group-diphenylpropane-1,3-dione(DPPO)) titanium, (3-sec.-propyl-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-sec.-propyl-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-sec.-propyl-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-sec.-propyl-diphenylpropane-1,3-dione(DPPO)) titanium, (3-butyl-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-butyl-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-butyl-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-butyl-diphenylpropane-1,3-dione(DPPO)) titanium, (3-phenyl-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-phenyl-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-phenyl-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-phenyl-diphenylpropane-1,3-dione(DPPO)) titanium, (3-benzyl-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-benzyl-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-benzyl-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-benzyl-diphenylpropane-1,3-dione(DPPO)) titanium, (3-naphthalene benzyl-diphenylpropane-1,3-dione(DPPO))-titanous chloride, two (3-naphthalene benzyl-diphenylpropane-1,3-dione(DPPO))-titanium dichloride, three (3-naphthalene benzyl-diphenylpropane-1,3-dione(DPPO))-monochlor(in)ate titaniums, four (3-naphthalene benzyl-diphenylpropane-1,3-dione(DPPO)) titanium, (3-methyl-trifluoroacetylacetone)-titanous chloride, two (3-methyl-trifluoroacetylacetone)-titanium dichloride, three (3-methyl-trifluoroacetylacetone)-monochlor(in)ate titaniums, four (3-methyl-trifluoroacetylacetone) titanium, (3-ethyl-trifluoroacetylacetone)-titanous chloride, two (3-ethyl-trifluoroacetylacetone)-titanium dichloride, three (3-ethyl-trifluoroacetylacetone)-monochlor(in)ate titaniums, four (3-ethyl-trifluoroacetylacetone) titanium, (3-propyl group-trifluoroacetylacetone)-titanous chloride, two (3-propyl group-trifluoroacetylacetone)-titanium dichloride, three (3-propyl group-trifluoroacetylacetone)--titanium chlorides, four (3-propyl group-trifluoroacetylacetone) titanium, (3-sec.-propyl-trifluoroacetylacetone)-titanous chloride, two (3-sec.-propyl-trifluoroacetylacetone)-titanium dichloride, three (3-sec.-propyl-trifluoroacetylacetone)-monochlor(in)ate titaniums, four (3-sec.-propyl-trifluoroacetylacetone) titanium, (3-butyl-trifluoroacetylacetone)-titanous chloride, two (3-butyl-trifluoroacetylacetone)-titanium dichloride, three (3-butyl-trifluoroacetylacetone)-monochlor(in)ate titaniums, four (3-butyl-trifluoroacetylacetone) titanium, (3-phenyl-trifluoroacetylacetone)-titanous chloride, two (3-phenyl-trifluoroacetylacetone)-titanium dichloride, three (3-phenyl-trifluoroacetylacetone)-monochlor(in)ate titaniums, four (3-phenyl-trifluoroacetylacetone) titanium, (3-benzyl-trifluoroacetylacetone)-titanous chloride, two (3-benzyl-trifluoroacetylacetone)-titanium dichloride, three (3-benzyl-trifluoroacetylacetone)-monochlor(in)ate titaniums, four (3-benzyl-trifluoroacetylacetone) titanium, (3-naphthalene benzyl-trifluoroacetylacetone)-titanous chloride, two (3-naphthalene benzyl-trifluoroacetylacetone)-titanium dichloride, three (3-naphthalene benzyl-trifluoroacetylacetone)-monochlor(in)ate titaniums, four (3-naphthalene benzyl-trifluoroacetylacetone) titanium.
Catalyzer provided by the invention can be by two kinds of method preparations.First method may further comprise the steps:
(1) beta-diketone compound is dissolved in ether solvent, press 1: 1 mixed of solute mol ratio, stirring with the aqueous solution of tetraethyl-fluoride amine then, remove and anhydrate and ether solvent, the gained solid is dissolved with chloroform or methylene dichloride, by adding expression formula with 1: 1 mol ratio of beta-diketone compound is the halohydrocarbon of RA, stirring reaction under the reflux temperature, preferably reacted 1～2 hour, remove and desolvate, residue promptly obtains the 3-R-beta-diketonate ligand through underpressure distillation or recrystallization, and wherein the general expression that has of beta-diketone compound is R '-C (O)-CH
2-C (O)-R ", " implication is identical with substituting group in the catalyzer, and A is a halogen for described R, R ' and R.
(2) in the presence of organic solvent, make MX
4Under reflux temperature, react according to 1: 1～4 mol ratio with the 3-R-beta-diketonate ligand, filter or remove and desolvate.MX
4M is selected from IVB family metallic element in the formula, and X is a halogen.
Ether solvent in the above-mentioned preparation process is tetrahydrofuran (THF) or ether, and organic solvent is ether or methylene dichloride.
In the above-mentioned preparation step poly-(1), when if the beta-diketone compound selected for use is methyl ethyl diketone, with the halohydrocarbon back flow reaction after, the most handy ether washing reaction thing after-filtration, the filtrate distillation is removed again and desolvate, residue adopts distillation under vacuum to obtain the 3-R-beta-diketonate ligand.
In the above-mentioned preparation step poly-(1), when if the beta-diketone compound of selecting for use is diphenylpropane-1,3-dione(DPPO) or trifluoroacetylacetone, with the halohydrocarbon back flow reaction after, the most handy ether washing reaction thing after-filtration, the filtrate distillation is removed again and desolvate, residue adopts dehydrated alcohol to carry out obtaining the 3-R-beta-diketonate ligand behind the recrystallization.
Second kind of preparation method of catalyzer of the present invention may further comprise the steps:
(1) beta-diketone compound is dissolved in chloroform, by adding sodium hydride with 1: 1 mol ratio of beta-diketone compound, stirred at least 20 minutes, be chilled to room temperature after being heated to the reflux temperature reaction, be the halohydrocarbon of RA by adding expression formula again with 1: 1 mol ratio of beta-diketone compound, stirring reaction under the reflux temperature adds [Cu (NH then in reaction solution
3)
6] SO
4The aqueous solution, remove by filter insolubles, filtrate is used extracted with diethyl ether, and organic phase distillation is desolvated to remove, residue under reduced pressure distills or recrystallization promptly obtains the 3-R-beta-diketonate ligand, wherein the general expression that has of beta-diketone compound is R '-C (O)-CH
2-C (O)-R ", " implication is identical with substituting group in the catalyzer, and A is a halogen for described R, R ' and R.
(2) in the presence of organic solvent, make MX
4Under reflux temperature, react according to 1: 1～4 mol ratio with the 3-R-beta-diketonate ligand, filter or remove and desolvate MX
4M is selected from IVB family metallic element in the formula, and X is a halogen.
The organic solvent of above-mentioned second method (2) in the step is ether or methylene dichloride.
When second method (1) step, described beta-diketone compound was selected from methyl ethyl diketone, the residue that reacts last gained under reduced pressure distilled and can obtain the 3-R-acetyl acetone ligands.
When second method (1) step, described beta-diketone compound was selected from diphenylpropane-1,3-dione(DPPO) or trifluoroacetylacetone, the residue that reacts last gained needed with the dehydrated alcohol recrystallization to obtain the 3-R-beta-diketonate ligand.
Among described two kinds of preparation methods, R ' and R " are C in the used beta-diketone compound preferred formula expression formula of (1) step
1～C
3Alkyl, C
6～C
10Aryl or C
1～C
3The material of perfluoroalkyl; Comparatively preferably R ' and R " are the beta-diketone compound of methyl, ethyl, propyl group, sec.-propyl, phenyl or tolyl; More preferred beta-diketone compound is methyl ethyl diketone, diphenylpropane-1,3-dione(DPPO) or trifluoroacetylacetone.
Two kinds of methods (1) go on foot among the used halohydrocarbon RA, and R is selected from C
1～C
12Alkyl, C
6～C
14Alkaryl or C
1～C
12Perfluoroalkyl, preferred C
1～C
6Alkyl, C
6～C
12Alkaryl or C
1～C
3Perfluoroalkyl, more preferably methyl, ethyl, propyl group, sec.-propyl, butyl, phenyl, benzyl or naphthalene benzyl.A among the formula RA is a halogen, preferred iodine or bromine.Preferred halohydrocarbon is methyl iodide, iodoethane, iodopropane, butyl iodide, phenyl-iodide, bromobenzyl.
Used transition metal halide MX of (2) step in above-mentioned two kinds of methods
4Preferred titanium tetrachloride, this step reaction is for using 3-R-beta-diketonate ligand and transition metal halide MX
4The reaction synthetic catalyst, synthetic method is with 3-R-beta-diketonate ligand and transition metal halide MX preferably
4Make diethyl ether solution respectively, then the diethyl ether solution of two kinds of materials is mixed, be heated to reflux temperature reaction 1～2 hour, filter or remove and desolvate, wash to filtrate colourlessly with ether, promptly obtain 3-R-beta diketone titanium compound.
Catalyzer provided by the invention is used for the Primary Catalysts of synthesis of syndiotactic polystyrene, also need add aikyiaiurnirsoxan beta or aluminum alkyls during polymerization is promotor, make styrene monomer at 10～100 ℃, preferably carry out polymerization under 20～80 ℃, the Al/Ti mol ratio is 200～2000 during reaction, is preferably 500～1000.
The promotor that uses during polymerization is selected from aikyiaiurnirsoxan beta or aluminum alkyls, as methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium.Described aikyiaiurnirsoxan beta can be linear or cyclic, and preferred aikyiaiurnirsoxan beta is a methylaluminoxane.
The present invention carries out modification owing to introduce electron donating group on 3 carbon of beta-diketone compound to the existing catalyzer that contains beta-diketonate ligand, makes activity of such catalysts improve, and can improve the gained syndiotactic polystyrene between normality and molecular weight.
Further specify the present invention below by embodiment, but the present invention is not limited to this.
Embodiment 1
This examples preparation two (3-methyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation 3-methyl-diphenylpropane-1,3-dione(DPPO).
(Shanghai chemical reagent work) is dissolved in 15 milliliters of tetrahydrofuran (THF)s with 0.1 mole diphenylpropane-1,3-dione(DPPO), 0.1 the tetraethyl-fluoride amine of mole is dissolved in 15 milliliters of deionized waters, two kinds of solution are mixed, at room temperature stirred 20 minutes, 90 ℃ of pressure reducing and steaming water and tetrahydrofuran (THF), wash residuum with ether, suction filtration obtains solid.In solid, add the 10ml chloroform and make it dissolving, the methyl iodide that adds 0.1 mole, reflux temperature stirred 1 hour down, with ether washing reaction thing, removed by filter unreacted reactant, filtrate is distilled, remove ether and chloroform, add 15 milliliters of dehydrated alcohol recrystallizations, obtain crystal, crystal carries out recrystallization once more with 15 milliliters of dehydrated alcohols, obtains 3-methyl-diphenylpropane-1,3-dione(DPPO) 2.1 grams.Productive rate is 91 heavy %.Carbon wherein, hydrogen richness analyses.Ultimate analysis: measured value (calculated value): C 80.48% (80.65%), H5.85% (5.92%).
(2) 3-methyl-diphenylpropane-1,3-dione(DPPO) of 0.2 mole is dissolved in 15 milliliters of ether, 0.1 mole TiCl
4Be dissolved in 20 milliliters of ether and make solution, two kinds of solution are added in the encloses container, be heated with stirring to reflux temperature, reacted 1 hour, filter, solid makes two (3-methyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride with ether washing 3 times.Ultimate analysis: measured value (calculated value): C 64.59% (64.78%), H4.28% (4.42%).
Embodiment 2
This examples preparation two (3-ethyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation 3-ethyl-diphenylpropane-1,3-dione(DPPO).
Be prepared by (1) step synthetic method in the example 1, different is replaces methyl iodide to react reacting reflux time 2 hours with 0.1 mole iodoethane.Productive rate is 90 heavy %.
Ultimate analysis: measured value (calculated value): C 80.87% (80.93%), H 6.36% (6.39%).
(2) 3-ethyl-diphenylpropane-1,3-dione(DPPO) of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-ethyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
Ultimate analysis: measured value (calculated value): C 65.61% (65.72%), H 4.69% (4.87%).
Embodiment 3
This examples preparation two (3-propyl group-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation 3-propyl group-diphenylpropane-1,3-dione(DPPO).
Be prepared by (1) step synthetic method in the example 1, different is replaces methyl iodide to react with 0.1 mole iodopropane.Productive rate is 90 heavy %.
Ultimate analysis: measured value (calculated value): C 81.09% (81.17%), H 6.79% (6.81%).
(2) 3-propyl group-diphenylpropane-1,3-dione(DPPO) of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-propyl group-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
Ultimate analysis: measured value (calculated value): C 66.42% (66.57%), H 5.13% (5.28%).
Embodiment 4
This examples preparation two (3-butyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation 3-butyl-diphenylpropane-1,3-dione(DPPO).
Be prepared by (1) step synthetic method in the example 1, different is replaces methyl iodide to react with 0.1 mole butyl iodide.Productive rate 82 heavy %.
Ultimate analysis: measured value (calculated value): C 81.53% (81.40%), H 7.05% (7.19%).
(2) 3-butyl-diphenylpropane-1,3-dione(DPPO) of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-butyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
Ultimate analysis: measured value (calculated value): C 67.12% (67.38%), H 5.58% (5.65%).
Embodiment 5
This examples preparation two (3-phenyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation 3-phenyl-diphenylpropane-1,3-dione(DPPO).
Be prepared by (1) step synthetic method in the example 1, different is 0.1 mole replace methyl iodide to react with phenyl-iodide.Productive rate 76 heavy %.
Ultimate analysis: measured value (calculated value): C 83.76% (83.98%), H 5.18% (5.37%).
(2) 3-phenyl-diphenylpropane-1,3-dione(DPPO) of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-phenyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
Ultimate analysis: measured value (calculated value): C 70.15% (70.31%), H 4.09% (4.21%).
Embodiment 6
This examples preparation two (3-benzyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation 3-benzyl-diphenylpropane-1,3-dione(DPPO).
Be prepared by (1) step synthetic method in the example 1, different is replaces methyl iodide to react with 0.1 mole bromobenzyl.Productive rate is 85 heavy %.
Ultimate analysis: measured value (calculated value): C 83.76% (83.98%), H 5.18% (5.37%).
(2) 3-benzyl-diphenylpropane-1,3-dione(DPPO) of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-benzyl-diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
Ultimate analysis: measured value (calculated value): C 70.77% (70.89%), H 4.51% (4.60%).
Embodiment 7
This examples preparation two (3-methyl-methyl ethyl diketone) titanium dichloride.
(1) preparation 3-methyl-methyl ethyl diketone.
(Shanghai chemical reagent work) is dissolved in 15 milliliters of tetrahydrofuran (THF)s with 0.1 mole of methyl ethyl diketone, 0.1 mole tetraethyl-fluoride amine is dissolved in 15 milliliters of deionized waters, two kinds of solution are mixed, stirred 20 minutes under the room temperature, 90 ℃ of pressure reducing and steaming water and tetrahydrofuran (THF), residuum washs and filters with ether, in solid, add 10 milliliters of chloroforms and make it dissolving, the methyl iodide that adds 0.1 mole, reflux temperature stirred 1 hour down, reactant distills the filtrate that obtains to remove ether and chloroform with ether washing and filtration, and 80 ℃ of following underpressure distillation can obtain 3-methyl-methyl ethyl diketone 1.1 grams then.Productive rate is 95 heavy %.
Ultimate analysis: measured value (calculated value): C 63.26% (63.13%), H 8.36% (8.30%).
(2) 3-methyl-methyl ethyl diketone of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-methyl-methyl ethyl diketone) titanium dichloride.
Ultimate analysis: measured value (calculated value): C 41.53% (41.77%), H 5.09% (5.26%).
Embodiment 8
This examples preparation two (3-butyl-methyl ethyl diketone) titanium dichloride.
(1) preparation 3-butyl-methyl ethyl diketone.
Be prepared by (1) step synthetic method in the example 7, different is replaces methyl iodide to react with 0.1 mole butyl iodide.Productive rate 85 heavy %.
Ultimate analysis: measured value (calculated value): C 83.76% (83.98%), H 5.18% (5.37%).
(2) 3-butyl-methyl ethyl diketone of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-butyl-methyl ethyl diketone) titanium dichloride.
Ultimate analysis: measured value (calculated value): C 50.21% (50.37%), H 6.95% (7.04%).
Embodiment 9
This examples preparation (3-butyl-diphenylpropane-1,3-dione(DPPO)) titanous chloride.
3-butyl-diphenylpropane-1,3-dione(DPPO) of 0.1 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make (3-butyl-diphenylpropane-1,3-dione(DPPO)) titanous chloride.
Ultimate analysis: measured value (calculated value): C 52.61% (52.65%), H 4.35% (4.42%).
Embodiment 10
This examples preparation three (3-butyl-methyl ethyl diketone) monochlor(in)ate titanium.
3-butyl-methyl ethyl diketone of 0.3 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make three (3-butyl-methyl ethyl diketone) monochlor(in)ate titanium.
Ultimate analysis: measured value (calculated value): C 58.96% (59.07%), H 8.13% (8.26%).
Embodiment 11
This examples preparation four (3-butyl-methyl ethyl diketone) titanium.
3-butyl-methyl ethyl diketone of 0.4 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make four (3-butyl-methyl ethyl diketone) titanium.
Ultimate analysis: measured value (calculated value): C 64.49% (64.66%), H 8.89% (9.04%).
Embodiment 12
This example prepares two (3-methyl-methyl ethyl diketone) titanium dichloride with another kind of method provided by the invention.
(1) preparation 3-methyl-methyl ethyl diketone.
(Shanghai chemical reagent work) is dissolved in 20 milliliters of chloroform wiring solution-formings with 0.1 mole of methyl ethyl diketone, the sodium hydride that adds 0.1 mole, at room temperature stirred 20 minutes, reflux is 1 hour then, be chilled to room temperature, the methyl iodide that adds 0.1 mole, stirring and refluxing 1 hour, the [Cu (NH of adding 1.0M in reaction solution
3)
6] SO
460 milliliters of the aqueous solution remove by filter insoluble byproduct of reaction methyl oxidation methyl ethyl diketone, and filtrate is used extracted with diethyl ether three times, merge organic phase, and ether and chloroform are removed in distillation, obtain 3-methyl-methyl ethyl diketone 1.1 grams in 80 ℃ of following underpressure distillation.Productive rate 53 heavy %.
Ultimate analysis: measured value (calculated value): C 63.02% (63.13%), H 8.11% (8.30%).
(2) 3-methyl-methyl ethyl diketone of 0.2 mole is dissolved in 15 milliliters of ether, presses the method and the TiCl of example 1
4Diethyl ether solution reaction, filter, washing, make two (3-methyl-methyl ethyl diketone) titanium dichloride.
Embodiment 13～23
Following example carries out polyreaction, the preparation syndiotactic polystyrene.
With 100 milliliters of reaction flasks that agitator is housed with nitrogen replacement after, add 25 milliliters of exsiccant toluene, be warming up to 60 ℃ under stirring, the concentration that adds 3.3 milliliters of U.S. Albemarle companies productions is that the toluene solutions of the methylaluminoxane (MAO) of 10 heavy % (contain MAO7.5 * 10
-3Mol), stirred 5 minutes, the compound that adds embodiment 1～11 preparation is as catalyzer, and the catalyzer dosage is 1.5 * 10
-5Mol, and be mixed with toluene solution, Al/Ti is 500, adds 10 milliliters of exsiccant styrene monomers at last, isothermal reaction 1 hour adds 10 milliliters of acidifying ethanol that contain 3%HCl and stops polyreaction.Reactant was continued to stir in excess ethyl alcohol 1 hour, filter, use washing with alcohol, 70 ℃ of following vacuum-drying 4 hours must polymkeric substance.Each embodiment polyreaction catalyst system therefor and polymer property see Table 1.
In the table 1 polymkeric substance between normality measure with the acetone extraction process, melting point polymer is measured with the differential scanning method, weight-average molecular weight Mw gel chromatography.
Embodiment 24
Present embodiment is a Comparative Examples.Two (methyl ethyl diketone) titanium dichloride with CN1158859A preparation is a catalyzer, carries out cinnamic polyreaction by the reaction conditions of embodiment 13, and different is that temperature of reaction is 80 ℃.Catalyst activity and polymer property see Table 1.
Embodiment 25
Present embodiment is a Comparative Examples.Two (diphenylpropane-1,3-dione(DPPO)) titanium dichloride with CN1158859A preparation is a catalyzer, carries out cinnamic polyreaction by the reaction conditions of embodiment 13, and different is that temperature of reaction is 80 ℃.Catalyst activity and polymer property see Table 1.
Embodiment 26
Present embodiment also is a Comparative Examples.With USP4, the cyclopentadiene-tri-chlorination zirconiums of 808,680 preparations are catalyzer, carry out cinnamic polyreaction by the reaction conditions of embodiment 13, and different is that temperature of reaction is 80 ℃.Catalyst activity and polymer property see Table 1.
Table 1
| Instance number | Catalyzer | Catalyst activity and polymer property | |||
| Active (gram polymkeric substance/gram catalyzer) | Between normality (%) | Melting temperature (℃) | Mw(10 4) | ||
| 13 | (3-Me-dbm) 2TiCl 2 | 4.68×10 2 | 95.7 | 271.0 | 11.23 |
| 14 | (3-Et-dbm) 2TiCl 2 | 5.13×10 2 | 94.9 | 269.9 | 12.55 |
| 15 | (3-Pr-dbm) 2TiCl 2 | 5.56×10 3 | 93.6 | 271.9 | 16.39 |
| 16 | (3-Bu-dbm) 2TiCl 2 | 6.26×10 3 | 97.4 | 270.1 | 42.28 |
| 17 | (3-Ph-dbm) 2TiCl 2 | 1.02×10 3 | 98.5 | 272.1 | 38.56 |
| 18 | (3-Bz-dbm) 2TiCl 2 | 2.35×10 3 | 98.8 | 272.8 | 32.69 |
| 19 | (3-Me-acac) 2TiCl 2 | 2.59×10 2 | 94.5 | 269.9 | 18.9 |
| 20 | (3-Bu-acac) 2TiCl 2 | 3.89×10 2 | 95.6 | 270.1 | 19.8 |
| 21 | (3-Bu-dbm)TiCl 3 | 4.95×10 2 | 96.4 | 269.9 | 32.08 |
| 22 | (3-Bu-acac) 3TiCl | 3.98×10 2 | 96.3 | 270.1 | 21.08 |
| 23 | (3-Bu-acac) 4Ti | 3.76×10 2 | 95.9 | 269.9 | 20.8 |
| 24 | (acac) 2TiCl 2 | 2.51×10 2 | 91.4 | 267.9 | 16.70 |
| 25 | (dbm) 2TiCl 2 | 4.55×10 2 | 94.9 | 268.9 | 6.38 |
| 26 | CpZrCl 3 | 1.35×10 2 | 60.1 | 205.8 | 1.30 |
* the substituting group of each symbology is in the table 1: ketone group in the dbm-diphenylpropane-1,3-dione(DPPO) base, acac-acetyl, Me-methyl, Et-ethyl, Pr-n-propyl, Bu-normal-butyl, Ph-phenyl, Bz-benzyl.
Claims (15)
1, a kind of catalyzer of synthesis of syndiotactic polystyrene has following general expression:
R ' and R in the formula " identical or inequality, be selected from C respectively
1～C
12Alkyl, C
6～C
10Aryl or C
1～C
12Perfluoroalkyl, wherein said aryl is the phenyl that phenyl or alkyl replace,
R is selected from C
1～C
12Alkyl, C
6～C
14Alkaryl or C
1～C
12Perfluoroalkyl,
M is selected from IVB family metallic element,
X is a halogen,
N is 1～4 integer.
2, according to the described catalyzer of claim 1, it is characterized in that described R ' and R and " be selected from C respectively
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or C
6～C
10Aryl, R is selected from C
1～C
6Alkyl, C
6～C
14Alkaryl, M are titanium, and X is a chlorine.
3, according to the described catalyzer of claim 2, " be selected from methyl or phenyl, R is selected from C to it is characterized in that described R ' and R
1～C
6Alkyl, phenyl, benzyl or naphthalene benzyl.
4, the described Preparation of catalysts method of a kind of claim 1 may further comprise the steps:
(1) beta-diketone compound is dissolved in ether solvent, press 1: 1 mixed of solute mol ratio, stirring with the aqueous solution of tetraethyl-fluoride amine then, remove and anhydrate and ether solvent, the gained solid is dissolved with chloroform or methylene dichloride, by adding expression formula with 1: 1 mol ratio of beta-diketone compound is the halohydrocarbon of RA, stirring reaction under the reflux temperature, remove and desolvate, residue underpressure distillation or recrystallization promptly obtain the 3-R-beta-diketonate ligand, and wherein the general expression that has of beta-diketone compound is R '-C (O)-CH
2-C (O)-R ", described R, R ' and R " implication is with claim 1, and A is a halogen,
(2) in the presence of organic solvent, make MX
4Under reflux temperature, react according to 1: 1～4 mol ratio with the 3-R-beta-diketone compound, filter or remove and desolvate MX
4M is selected from IVB family metallic element in the formula, and X is a halogen.
5, in accordance with the method for claim 4, it is characterized in that the halohydrocarbon in (1) is hydrobromic ether or idohydrocarbon, the MX in (2) step
4Be titanium tetrachloride.
6, in accordance with the method for claim 5, when it is characterized in that the beta-diketone compound described in (1) is selected from diphenylpropane-1,3-dione(DPPO) or trifluoroacetylacetone, residue obtains the 3-R-beta-diketonate ligand with the dehydrated alcohol recrystallization, and the RA that uses in the preparation process is selected from methyl iodide, iodoethane, iodopropane, butyl iodide, phenyl-iodide, bromobenzyl.
7, in accordance with the method for claim 5, when it is characterized in that the beta-diketone compound described in (1) is selected from methyl ethyl diketone, residue under reduced pressure distills and obtains the 3-R-methyl ethyl diketone, and the RA that uses in the preparation process is selected from methyl iodide, iodoethane, iodopropane, butyl iodide, phenyl-iodide, bromobenzyl.
8, according to described any one method of claim 4～7, it is characterized in that described ether solvent is tetrahydrofuran (THF) or ether, organic solvent is ether or methylene dichloride.
9, the described Preparation of catalysts method of a kind of claim 1 may further comprise the steps:
(1) beta-diketone compound is dissolved in chloroform, by adding sodium hydride with 1: 1 mol ratio of beta-diketone compound, stirred at least 20 minutes, be chilled to room temperature after being heated to the reflux temperature reaction, be the halohydrocarbon of RA by adding expression formula again with 1: 1 mol ratio of beta-diketone compound, stirring reaction under the reflux temperature adds [Cu (NH then in reaction solution
3)
6] SO
4The aqueous solution, remove by filter insolubles, filtrate is used extracted with diethyl ether, and organic phase distillation is desolvated to remove, residue under reduced pressure distills or recrystallization promptly obtains the 3-R-beta-diketonate ligand, wherein the general expression that has of beta-diketone compound is R '-C (O)-CH
2-C (O)-R ", described R, R ' and R " implication is with claim 1, and A is a halogen,
(2) in the presence of organic solvent, make MX
4Under reflux temperature, react according to 1: 1～4 mol ratio with the 3-R-beta-diketonate ligand, filter or remove and desolvate MX
4M is selected from IVB family metallic element in the formula, and X is a halogen.
10, in accordance with the method for claim 9, it is characterized in that the halohydrocarbon in (1) is hydrobromic ether or idohydrocarbon, the TiX in (2) step
4Be titanium tetrachloride.
11, in accordance with the method for claim 9, when it is characterized in that the beta-diketone compound described in (1) is selected from diphenylpropane-1,3-dione(DPPO) or trifluoroacetylacetone, residue obtains the 3-R-beta-diketonate ligand with the dehydrated alcohol recrystallization, and the RA that uses in the preparation process is selected from methyl iodide, iodoethane, iodopropane, butyl iodide, phenyl-iodide, bromobenzyl.
12, in accordance with the method for claim 9, when it is characterized in that the beta-diketone compound described in (1) is selected from methyl ethyl diketone, residue under reduced pressure distills the back and obtains the 3-R-methyl ethyl diketone, and the RA that uses in the preparation process is selected from methyl iodide, iodoethane, iodopropane, butyl iodide, phenyl-iodide, bromobenzyl.
13,, it is characterized in that the organic solvent described in (2) is ether or methylene dichloride according to described any one method of claim 9～12.
14, a kind of method of synthesis of syndiotactic polystyrene, it is characterized in that with the described catalyzer of claim 1 be Primary Catalysts, with aikyiaiurnirsoxan beta or aluminum alkyls is promotor, makes styrene monomer 10～100 ℃ of following polyreactions, and the Al/Ti mol ratio is 200～2000 during reaction.
15, in accordance with the method for claim 14, it is characterized in that described aikyiaiurnirsoxan beta is a methylaluminoxane, the Al/Ti mol ratio is 500～1000 during reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158859A (en) * | 1996-03-07 | 1997-09-10 | 中国科学院化学研究所 | Catalyst system for synthesizing syndiotactic polystyrene and its preparation |
| CN1185448A (en) * | 1996-12-17 | 1998-06-24 | 中国科学院化学研究所 | Catalyst system for synthesizing syndiotactic polyphenylacetylene and preparation process thereof |
| CN1215735A (en) * | 1997-10-29 | 1999-05-05 | 中国科学院化学研究所 | Catalyst system for synthesis of syndiotactic polystyrene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158859A (en) * | 1996-03-07 | 1997-09-10 | 中国科学院化学研究所 | Catalyst system for synthesizing syndiotactic polystyrene and its preparation |
| CN1185448A (en) * | 1996-12-17 | 1998-06-24 | 中国科学院化学研究所 | Catalyst system for synthesizing syndiotactic polyphenylacetylene and preparation process thereof |
| CN1215735A (en) * | 1997-10-29 | 1999-05-05 | 中国科学院化学研究所 | Catalyst system for synthesis of syndiotactic polystyrene |
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