CN112661886B - Styrene polymerization system and polymerization method and obtained polystyrene - Google Patents
Styrene polymerization system and polymerization method and obtained polystyrene Download PDFInfo
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Abstract
The invention relates to a styrene polymerization system, a polymerization method and polystyrene obtained by the polymerization system. Wherein the molar ratio of the naphthoxy-metallocene transition metal compound to the alkyl aluminoxane is 1 (50-20000), and the concentration of the naphthoxy-metallocene transition metal compound in a polymerization system is 1x10 ‑8 Mol/liter-1 x10 ‑3 Mol/l. The polymerization system adopts a naphthoxy single metallocene transition metal compound with a special structure as a main catalyst, and syndiotactic polystyrene can be obtained by utilizing the polymerization system, and the obtained polystyrene has the advantages of high molecular weight, narrow molecular weight distribution and the like.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to preparation of styrene, especially syndiotactic styrene, in particular to preparation of styrene by adopting a polymerization system containing naphthoxy-single metallocene transition metal compound.
Background
Metallocene catalysts for olefin polymerization have been the focus of research in metallorganic chemistry, catalytic chemistry, polymer chemistry and materials science for decades. By using the metallocene catalyst, an olefin polymer with uniform molecular weight distribution and chemical composition distribution can be obtained; meanwhile, the molecular structure and molecular weight of the polymer can be highly controllable by adjusting the structure of the catalyst; in addition, by using metallocene catalysts, olefin polymers which cannot be obtained by conventional Ziegler-Natta catalysts can also be obtained.
Styrene polymers can be classified into atactic polystyrene, isotactic polystyrene and syndiotactic polystyrene. Syndiotactic Polystyrene (SPS) is a crystalline styrene polymer in which phenyl groups are regularly and alternately arranged on both sides of a macromolecular carbon-carbon main chain, and is a new polystyrene variety developed in recent years. The melting point of SPS is high (270 ℃), the crystallization speed is high, the density is low, the elastic modulus is high, the moisture absorption rate is low, and the dielectric constant is small; is a high-electrical-insulation engineering plastic with strong resistance to organic solvents and chemical reagents. The excellent performance makes it have wide application prospect in automobile industry, electronic industry and industrial package.
The synthesis of SPS was reported as early as 1962, but the synthesis conditions are very harsh and can be obtained at-62 ℃ (J.Am.chem.Soc.1962, 84, 1488). In 1986, ishihara reported the synthesis of SPS under mild conditions; cpTiCl therefor 3 Forming a catalytic system with a cocatalyst MAO. The melting point of SPS is 270 ℃, and the melting point of SPS is 40 ℃ higher than that of isotactic polystyrene; weight average molecular weight (M) of SPS w ) 82000 (Macromolecules 1986,19,2465; EP210615, 1987). Chien and Rausch et al use IndCl 3 As a catalyst, syndiotactic polymerization of styrene was studied; with CpTiCl 3 Compared with IndclI 3 The activity of catalyzing syndiotactic polymerization of styrene is higher, and the SPS accounts for a higher proportion in the polymer (Macromolecules 1993,26, 5822). In addition, they reported five Cp' Ti (O) i Pr) 3 The catalysts are used for the catalytic syndiotactic polymerization of styrene, as a result of which it has been found that the structure of the catalyst has a significant influence on the polymerization activity, the proportion of SPS in the product and also on the molecular weight of SPS (Organometallics 1993,12, 3075). The Single metallocene Complex Cp' TiCl for Xu 3 The activity of the catalyst can reach 27.0 multiplied by 10 when the catalyst is used for catalyzing the syndiotactic polymerization of styrene 4 g-SPS/mol-Ti/h, the weight-average molecular weight of the polymer can reach 74 ten thousand (Macromolecules 2000,33 2825).
Kaminsky studied the catalytic syndiotactic polymerization of styrene using a fluorine-containing single metallocene catalyst and found that Cp'TiF 3 Polymerization activity ratio Cp' TiCl 3 Tens or even hundreds times higher. Using MeCpTiF 3 SPS with a molecular weight of 142 ten thousand can be obtained as a catalyst (Macromolecules 1997,30, 7647). Ruckenstein uses Ind' TiF 3 Syndiotactic polymerization of styrene was carried out and it was found that the catalytic activity of the fluorine-containing catalyst was much higher than that of the chlorine-containing catalyst, and the molecular weight of the resulting polymer was also higher than that obtained using the chlorine-containing catalyst (J.Polym.Sci.Polym.Chem., 1999,37, 2481). In addition, patent CN02117938 also discloses a fluorinated metallocene catalyst.
Monometallocene complex Cp' TiX 3 The catalyst can effectively catalyze the syndiotactic polymerization of styrene, and the polymerization activity and the polymer molecular weight of the catalyst are influenced by not only Cp ligands but also X ligands. In order to obtain more satisfactory polymerization results, the researchers have modified the catalyst structure by using a mono-metallocene complex Cp' TiCl with an electron-donating ligand 2 L (L = electron donor ligand) is of particular interest.
Other mono-metallocenes containing chelating ligands are also used for the syndiotactic polymerization of styrene. Do et al, using titanocene as shown in the following formula 1 as a catalyst for syndiotactic polymerization of styrene, found that the polymerization activity was relatively high but the molecular weight of the polymer was relatively low (Organometallics 1999,18,36, organometallics 2002,21, 1127). Li employs titanocenes of the following formulas 2 and 3 for syndiotactic polymerization of styrene, in which all catalysts increase in activity with an increase in polymerization temperature and the molecular weight of the polymer decreases (J.Polym.Sci., part A: polym.Chem.2005,43,1562, J.mol.Catal.Chem.2005,232,1 CN 200310115936.
Chinese patents disclose a number of compositions based on Cp' Ti (OR) 3 Studies on the catalysis of syndiotactic styrene polymerizations, such as CN101205261A, CN1611518A, CN1450093A, CN1450089A, CN1467213A, CN1467214A, CN1467232A, CN1459461A, CN1508157A, CN1490344A, CN1340551A, CN1295084A, CN1235986A, CN1235976A, CN1210109ACN1210108A, CN1210107A and CN1150154A.
In view of the above, studies on syndiotactic styrene polymerization have been developed, but the development of novel polymerization catalysts is still the main subject of research in this field in order to reduce the cost and improve the material properties.
Disclosure of Invention
The present inventors have conducted extensive experimental studies to provide a styrene polymerization system comprising a naphthoxy-monocyclopentadienyl transition metal compound having a structure containing a Cp' ligand and a naphthoxy group. Syndiotactic polystyrene with high molecular weight and narrow molecular weight distribution can be obtained when styrene is prepared.
One of the objectives of the present invention is to provide a styrene polymerization system, comprising a naphthoxy-metallocene transition metal compound, alkylaluminoxane and styrene, wherein the structure of the naphthoxy-metallocene transition metal compound comprises a naphthoxy group, a Cp 'ligand and a transition metal, and the naphthoxy group and the Cp' ligand are respectively connected to the transition metal to form the naphthoxy-metallocene transition metal compound.
In a preferred embodiment, the naphthoxymetallocene transition metal compound has the structure of formula (I) or formula (II):
in the formulae (I) and (II), X 1 And X 2 Each independently selected from an alkoxy, aryloxy, alkyl, aryl or halogen atom, cp' is a cyclopentadienyl, indenyl or fluorenyl group substituted or unsubstituted with a hydrocarbyl group, R is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom, a halogen atom or a substituent containing 1 to 18 carbon atoms.
It is explained herein that said cyclopentadienyl, indenyl or fluorenyl substituted or unsubstituted with a hydrocarbyl group means a cyclopentadienyl substituted or unsubstituted with a hydrocarbyl group, an indenyl substituted or unsubstituted with a hydrocarbyl group, or a fluorenyl substituted or unsubstituted with a hydrocarbyl group, described directly as: cyclopentadienyl, indenyl or fluorenyl, substituted or unsubstituted with a hydrocarbyl group, may also be described as cyclopentadienyl, indenyl, fluorenyl or their hydrocarbyl substituted derivatives.
In the invention, the single metallocene compound contains condensed heterocyclic aryloxy, and compared with common aryloxy (such as monocyclic or linked rings), the condensed ring electron donor ligand has larger steric hindrance, and can effectively inhibit chain transfer reaction in polymerization, thereby obtaining a polymer with higher molecular weight.
In the present invention, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 The nitro group capable of coordinating with the central atom is not involved, the nitro group is a strong electron-withdrawing group, the electron cloud density of the central metal atom can be rapidly reduced, the active center is electropositive, the active center is unstable and easy to decompose, the catalytic activity can be seriously reduced, and meanwhile, the strong nucleophilic reagent of the cocatalyst can be added with the nitro group to damage the catalyst structure and increase the consumption of the cocatalyst.
In a preferred embodiment, in formula (I) and formula (II), X 1 And X 2 Each independently selected from C 1 ～C 5 Alkoxy group of (C) 6 ～C 9 Aryloxy group of (A), C 1 ～C 5 Alkyl of (C) 6 ～C 9 An aryl group or a halogen atom of (a); and/or Cp' is selected from C 1 ～C 3 Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; and/or, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom, a halogen atom, C 6 ～C 9 Aryl of (C) 1 ～C 5 Alkyl or C of 1 ～C 5 Substituted alkyl groups of (2).
In a further preferred embodiment, in formula (I) and formula (II), X 1 And X 2 Each independently selected from a chlorine atom, a methoxy group, a phenoxy group, a methyl group, a phenyl group or a benzyl group; and/or Cp' is selected from pentamethylcyclopentadienyl, cyclopentadienyl or indenyl; and/or, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen atom, C 1 ～C 3 Alkyl of (C) 1 ～C 3 Halogen-substituted alkyl groups or halogen atoms.
In a further preferred embodiment, in formula (I) and formula (II), X 1 And X 2 Each independently selected from a chlorine atom or a methoxy group; and/or Cp' is selected from pentamethylcyclopentadienyl or cyclopentadienyl; and/or, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom or a chlorine atom.
In a preferred embodiment, the alkylaluminoxane is selected from compounds of formula (i) and/or formula (ii).
In the formulae (i) and (ii), R represents an alkyl group, preferably C 1 ～C 6 More preferably methyl; n represents an integer of 4 to 30, preferably an integer of 10 to 30.
In a preferred embodiment, the molar ratio of the naphthoxy-metallocene transition metal compound to the alkylaluminoxane is 1 (50 to 20000) in terms of the molar amounts of the Ti element and the Al element, respectively.
In a further preferred embodiment, the molar ratio of said naphthoxy-metallocene transition metal compound to said alkylalumoxane is 1 (200 to 10000) in terms of the molar amount of Ti element and Al element, respectively.
In a still further preferred embodiment, the molar ratio of said naphthoxymetallocene transition metal compound to said alkylaluminoxane is 1 (500 to 3000) in terms of the molar amount of each of the Ti element and the Al element therein.
Most preferably, the molar ratio of the naphthoxy-metallocene transition metal compound to the alkylaluminoxane is 1 (1500 to 2000), wherein the molar amount of the Ti element and the molar amount of the Al element are respectively.
In a preferred embodiment, the polymerization system further comprises an organic solvent, preferably toluene and/or hexane, more preferably toluene.
Wherein, during the styrene polymerization, the alkyl aluminoxane and the naphthoxy metallocene transition metal compound are added into a polymerization vessel together or separately.
In a preferred embodiment, the concentration of the naphthoxymetallocene transition metal compound in the polymerization system is 1X10 -8 mol/liter-1X 10 -2 Mol/l, preferably 1X10 -7 mol/l-1X 10 -3 Mol/l.
Most preferably, the concentration of the naphthoxymetallocene transition metal compound in the polymerization system is (1 to 5). Times.10 -4 Mol/l.
In a preferred embodiment, the polymerization system is conducted at a polymerization temperature of from-50 ℃ to 200 ℃, preferably from-20 ℃ to 150 ℃, more preferably from 0 ℃ to 100 ℃, e.g., from 50 ℃ to 90 ℃ in the preparation of syndiotactic polystyrene.
In a preferred preparation method, the preparation method of the naphthoxy-single metallocene transition metal compound comprises the step of preparing the compound shown in the formula (IV) and/or the compound shown in the formula (V) and the compound shown in the formula (III) as raw materials.
Wherein, in the formula (III), X 1 、X 2 And X 3 Each independently selected from an alkoxy group, an aryloxy group, an alkyl group, an aryl group or a halogen atom, cp' is a cyclopentadienyl group, an indenyl group or a fluorenyl group, substituted or unsubstituted with a hydrocarbon group; in the formulae (IV) and (V), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom, a halogen atom or a substituent containing 1 to 18 carbon atoms.
In the present invention, the compounds represented by the formulae (IV) and (III), the compounds represented by the formulae (V) and (III), or a mixture of the compounds represented by the formulae (IV) and (V) and the compound represented by the formula (III) may be used as the starting materials.
In a preferred embodiment, in formula (III), X 1 、X 2 And X 3 Each independently selected from C 1 ～C 5 Alkoxy group of (1), C 6 ～C 9 Aryloxy group of (A), C 1 ～C 5 Alkyl of (C) 6 ～C 9 An aryl group or a halogen atom of (a); and/or Cp' is selected from C 1 ～C 3 Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; and/or, in the formulae (IV) and (V), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom, a halogen atom, C 6 ～C 9 Aryl of (C) 1 ～C 5 Alkyl or C of 1 ～C 5 Substituted alkyl groups of (2).
In a further preferred embodiment, in formula (III), X 1 、X 2 And X 3 Each independently selected from a chlorine atom, a methoxy group, a phenoxy group, a methyl group, a phenyl group or a benzyl group; and/or Cp' is selected from pentamethylcyclopentadienyl, cyclopentadienyl or indenyl; and/or, in the formulae (IV) and (V), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom, a halogen atom, C 1 ～C 3 Alkyl of (C) 1 ～C 3 Halogen-substituted alkyl of (1).
In a still further preferred embodiment, in formula (III), X 1 、X 2 And X 3 Each independently selected from a chlorine atom or a methoxy group; and/or Cp' is selected from pentamethylcyclopentadienyl or cyclopentadienyl; and/or, in the formulae (IV) and (V), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom or a chlorine atom.
In a preferred embodiment, the method for preparing the naphthoxymetallocene transition metal compound comprises the steps of:
step 1, mixing a compound shown as a formula (III) with a solvent under a protective atmosphere to obtain a solution I;
step 2, mixing the compound shown in the formula (IV) or the compound shown in the formula (V) with a solvent to obtain a solution II;
and 3, dropwise adding the solution II into the solution I, optionally stirring, and reacting to obtain the naphthoxy-metallocene transition metal compound.
Wherein the protective atmosphere is preferably nitrogen.
In a preferred embodiment, in step 1 and step 2, the solvent is an organic solvent comprising dichloromethane, toluene and tetrahydrofuran, preferably dichloromethane.
In a preferred embodiment, in step 3, the reaction is carried out at room temperature or at 60 to 140 ℃ under reflux, preferably at room temperature of 20 to 30 ℃. The heating reflux is carried out at a temperature at which the solvent can be refluxed.
Wherein the process is carried out with or without heating, e.g. when X 1 、X 2 And X 3 When the halogen atom is selected, the reaction is carried out at room temperature without heating; when X is present 1 、X 2 And X 3 Is selected from C 1 ～C 5 Alkoxy group of (1), C 6 ～C 9 Aryloxy group of (1), C 1 ～C 5 Alkyl of (C) 6 ～C 9 The aryl group of (2) is subjected to a reflux reaction under heating.
In a further preferred embodiment, in step 3, the reaction is carried out for 2 to 30h.
In a further preferred embodiment, the reaction is carried out for 20 to 28h, for example 24h, when carried out at room temperature; when the reaction is carried out under reflux at 60-140 deg.C, the reaction is carried out for 2-6 h, such as 4h.
In a preferred embodiment, the reaction of step 3 is followed by a work-up comprising, in order, desolvation, extraction, filtration and crystallization.
In a further preferred embodiment, the post-treatment is carried out as follows: removing solvent under vacuum, extracting with toluene, filtering with diatomite filter aid, and freeze crystallizing the filtrate at-10 deg.C or lower (preferably-25 deg.C or lower).
In a still further preferred embodiment, the mother liquor is removed after crystallization and the remaining solid is dried under vacuum to obtain the naphthoxymonocyclopentadienyl transition metal compound.
In a preferred embodiment, the molar ratio of the compound of formula (IV) or the compound of formula (V) to the compound of formula (III) is independently 1.
The above means: the molar use ratio of the compound represented by the formula (IV) to the compound represented by the formula (III) is 1.
The naphthoxy single metallocene transition metal compound has the advantages of simple synthesis and safe and environment-friendly process, does not need to adopt malodorous triethylamine, and simultaneously avoids the use of dangerous NaH.
The second object of the present invention is to provide a styrene polymerization process using the styrene polymerization system of the first object of the present invention.
In a preferred embodiment, the polymerization temperature is from-50 ℃ to 200 ℃, preferably from 0 ℃ to 100 ℃.
In a preferred embodiment, the alkylaluminoxane and the naphthoxymetallocene transition metal compound in the polymerization system are added together or separately to the polymerization vessel.
It is a third object of the present invention to provide a polystyrene, preferably a syndiotactic polystyrene, obtainable by the polymerization process described above for the second object of the present invention.
Compared with the prior art, the invention has the following beneficial effects: the polymerization system adopts the naphthoxy-single metallocene transition metal compound with a special structure, the raw materials for preparing the polymerization system are cheap, the preparation is simple, safe and efficient, and meanwhile, the syndiotactic polystyrene can be obtained by utilizing the polymerization system, and the obtained syndiotactic polystyrene has the advantages of high molecular weight, narrow molecular weight distribution and the like.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the polymer obtained in example 5.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
The starting materials for the examples and comparative examples of the invention are either commercially available or can be prepared by themselves according to the methods disclosed in the prior art.
Example 1 Synthesis of pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride
Putting the magnetons into a dry three-mouth bottle of 250 ml, and placing the reaction bottle into a magnetic stirring device; the three-necked flask was evacuated and then flushed with nitrogen repeatedly three times. And adding 0.63 g of pentamethylcyclopentadienyl-titanium trichloride into the mixture under the nitrogen atmosphere, adding 20 ml of dried dichloromethane into the mixture for dissolving, dissolving 0.31 g of 1-naphthol into 20 ml of dried dichloromethane, slowly adding the mixture into the three-necked flask at the room temperature, and reacting for 24 hours at the room temperature under stirring. The solvent was removed in vacuo at room temperature to give a dark red solid, which was extracted with dry toluene and filtered using celite as a filter aid to give a dark red toluene solution which was freeze-crystallized at-25 ℃ to give 0.71 g of dark red crystals. Namely pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride, the molar yield is 83 percent.
1 H-NMR(CDCl 3 ,25℃):δ＝1.75(Cp*,15H),6.29(1H),7.4～7.5(1H),7.6～7.8(3H),8.2～8.4(2H)。
Example 2 Synthesis of cyclopentadienyl-1-naphthoxy-titanium dichloride
Putting the magnetons into a dry three-mouth bottle of 250 ml, and placing the reaction bottle into a magnetic stirring device; the three-necked flask was evacuated and flushed with nitrogen repeatedly three times. And adding 0.41 g of cyclopentadienyl-titanium trichloride into the flask under the nitrogen atmosphere, adding 20 ml of dried dichloromethane for dissolution, dissolving 0.27 g of 1-naphthol into 20 ml of dried dichloromethane, slowly adding the mixture into the three-neck flask at room temperature, and reacting at room temperature for 24 hours under stirring. The solvent was removed in vacuo at room temperature to give a black solid, which was extracted with dry toluene and filtered using celite filter aid to give a toluene solution which was freeze-crystallized at-25 ℃ to give 0.55 g of black red crystals. Namely cyclopentadienyl-1-naphthoxy-titanium dichloride, the molar yield of which is 90 percent.
1 H-NMR(CDCl 3 ,25℃):δ＝6.29(1H),6.58(5H,Cp),7.4～7.5(1H),7.6～7.8(3H),8.2～8.4(2H)。
EXAMPLE 3 Synthesis of cyclopentadienyl- (2, 4-dichloro-1-naphthyloxy) -titanium dichloride
Putting the magnetons into a dry three-mouth bottle of 250 ml, and placing the reaction bottle into a magnetic stirring device; the three-necked flask was evacuated and then flushed with nitrogen repeatedly three times. And adding 0.54 g of cyclopentadienyl-titanium trichloride into the nitrogen atmosphere, adding 20 ml of dried dichloromethane for dissolution, dissolving 0.53 g of 2, 4-dichloro-1-naphthol into 20 ml of dried dichloromethane, slowly adding the mixture into the three-necked flask at room temperature, and reacting at room temperature for 24 hours under stirring. The solvent was removed in vacuo at room temperature to give a dark red solid, which was extracted with dry toluene, filtered using celite as a filter aid to give a toluene solution, which was freeze-crystallized at-25 ℃ to give 0.90 g of wine red crystals. Namely cyclopentadienyl- (2, 4-dichloro-1-naphthoxy) -titanium dichloride with the molar yield of 93 percent.
1 H-NMR(CDCl 3 ,25℃):δ＝6.57(5H,Cp),7.30(1H),7.4～7.6(2H),8.1～8.3(2H)。
EXAMPLE 4 Synthesis of cyclopentadienyl- (2-naphthoxy) -titanium dichloride
Putting the magnetons into a dry 250 ml three-mouth bottle, and putting the reaction bottle into a magnetic stirring device; the three-necked flask was evacuated and then flushed with nitrogen repeatedly three times. And adding 1.30 g of cyclopentadienyl-titanium trichloride into the nitrogen atmosphere, adding 20 ml of dried dichloromethane for dissolution, dissolving 0.85 g of 2-naphthol into 20 ml of dried dichloromethane, slowly adding the mixture into the three-necked flask at room temperature, and reacting at room temperature for 24 hours under stirring. The solvent was removed in vacuo at room temperature to give a dark red solid, which was extracted with dry toluene and filtered using celite as a filter aid to give a toluene solution which was freeze-crystallized at-25 ℃ to give 1.70 g of dark red crystals. Namely cyclopentadienyl- (2, 4-dichloro-1-naphthoxy) -titanium dichloride, the molar yield of which is 88 percent.
1 H-NMR(CDCl 3 ,25℃):δ＝6.61(5H,Cp),7.1～7.2(1H),7.3～7.5(3H),7.7～7.9(3H)。
Example 5 polymerization of styrene Using pentamethylcyclopentadienyl-1-naphthyloxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 75 ℃, 9.5 ml of toluene, 5.0 ml of styrene, 4.5 ml of methylaluminoxane toluene solution (containing 7.5 mmol), and 1.0 ml of pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of catalyst) in example 1 were sequentially added to start a timer. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.43 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.41 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.68x10 5 g/mol, MWD =1.61, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum is shown in FIG. 1.
Example 6 polymerization of styrene Using pentamethylcyclopentadienyl-1-naphthyloxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 75 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of catalyst) in example 1 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.66 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was vacuum-dried at 60 ℃ for 24 hours to give 0.64 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.83x10 5 g/mol, MWD =1.64, and melting point of polymer is 269 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 7 polymerization of styrene Using pentamethylcyclopentadienyl-1-naphthyloxy-titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 75 deg.C, 6.5 ml of toluene, 5.0 ml of styrene, 7.5 ml of a toluene solution of methylaluminoxane (containing 12.5 mmol of methylaluminoxane), and 1.0 ml of a toluene solution of pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride as a catalyst (containing 5. Mu. Mol of the catalyst) in example 1 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.84 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.82 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.94x10 5 g/mol, molecular weight distribution MWD =1.59, and melting point of polymer detected by differential scanning calorimetry is 272 ℃. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 8 polymerization of styrene Using pentamethylcyclopentadienyl-1-Naphthyloxy-titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 75 ℃,5 ml of toluene, 5.0 ml of styrene, 9 ml of a methylaluminoxane toluene solution (containing 15 mmol of methylaluminoxane), and 1.0 ml of a pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of catalyst) in example 1 were sequentially added to start a timer. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.85 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.82 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.65x10 5 g/mol, MWD =1.58, and the melting point of the polymer is 271 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 9 polymerization of styrene Using pentamethylcyclopentadienyl-1-Naphthyloxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 90 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a toluene solution of methylaluminoxane (containing 10 mmol of methylaluminoxane), and 1.0 ml of a toluene solution of a catalyst (containing 5. Mu. Mol of catalyst) of pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride in example 1 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.62 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.60 g of SPS polymer.
Gel permeation chromatography detection of weight average molecular weight Mw =1.23x10 of polymer 5 g/mol, MWD =1.68, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 10 polymerization of styrene Using pentamethylcyclopentadienyl-1-Naphthyloxy-titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 60 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of catalyst) in example 1 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, vacuum-drying a filter cake at 60 ℃ for 24 hours, and weighing to obtain 0.08 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.07 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =9.78x10 4 g/mol, molecular weight distribution MWD =1.94, and melting point of polymer detected by differential scanning calorimetry is 268 ℃. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 11 polymerization of styrene Using pentamethylcyclopentadienyl-1-naphthyloxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 45 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a pentamethylcyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of catalyst) in example 1 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.10 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.09 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.56x10 5 g/mol, MWD =1.97, and melting point of polymer is 270 ℃ by differential scanning calorimetry. Nuclear magnetic spectrum of the product andfigure 1 is an approximation.
Example 12 polymerization of styrene Using cyclopentadienyl-1-naphthoxy-titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 75 deg.C, 9.5 ml of toluene, 5.0 ml of styrene, 4.5 ml of a toluene solution of methylaluminoxane (containing 7.5 mmol of methylaluminoxane), and 1.0 ml of a toluene solution of a catalyst of cyclopentadienyl-1-naphthoxy-titanium dichloride (containing 5. Mu. Mol of the catalyst) obtained in example 2 were sequentially added to start a timer. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.33 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.31 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =2.65x10 4 g/mol, MWD =1.82, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 13 polymerization of styrene Using cyclopentadienyl-1-naphthoxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 75 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of the catalyst) in example 2 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.43 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.40 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =2.72x10 4 g/mol, molecular weight distribution MWD =1.76, and the melting point of the polymer is 271 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 14 polymerization of styrene Using cyclopentadienyl-1-naphthoxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 75 ℃, 6.5 ml of toluene, 5.0 ml of styrene, 7.5 ml of methylaluminoxane toluene solution (containing 12.5 mmol of methylaluminoxane), and 1.0 ml of cyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of catalyst) in example 2 were sequentially added to start a timer. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.54 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.52 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =3.61x10 4 g/mol, molecular weight distribution MWD =2.23, and melting point of polymer is 270 ℃ detected by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 15 polymerization of styrene Using cyclopentadienyl-1-naphthoxy-titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 75 ℃,5 ml of toluene, 5.0 ml of styrene, 9 ml of a methylaluminoxane toluene solution (containing 15 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of the catalyst) in example 2 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.63 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.61 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =2.53x10 4 g/mol, MWD =1.77, and the melting point of the polymer is 271 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 16 polymerization of styrene Using cyclopentadienyl-1-naphthoxy-titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 90 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of the catalyst) in example 2 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.55 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.53 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.90x10 4 g/mol, MWD =1.77, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 17 polymerization of styrene Using cyclopentadienyl-1-naphthoxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 60 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of the catalyst) in example 2 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.22 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.20 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =3.65x10 4 g/mol, MWD =1.79, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 18 polymerization of styrene Using cyclopentadienyl-1-naphthoxy-titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 45 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl-1-naphthoxy-titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of the catalyst) in example 2 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, vacuum-drying a filter cake at 60 ℃ for 24 hours, and weighing to obtain 0.16 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.15 g of SPS polymer.
Gel permeation chromatography detection of weight average molecular weight Mw =4.03x10 of polymer 4 g/mol, MWD =1.84, and the melting point of the polymer is 271 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 19 polymerization of styrene Using cyclopentadienyl- (2, 4-dichloro-1-naphthyloxy) -titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 45 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl- (2, 4-dichloro-1-naphthoxy) -titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of the catalyst) in example 3 were sequentially added to start a timer. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.25 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was vacuum-dried at 60 ℃ for 24 hours to give 0.24 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =5.58x10 4 g/mol, MWD =1.82, and the melting point of the polymer is 271 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 20 polymerization of styrene Using cyclopentadienyl- (2, 4-dichloro-1-naphthyloxy) -titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 60 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a toluene solution of methylaluminoxane (containing 10 mmol of methylaluminoxane), and 1.0 ml of a toluene solution of cyclopentadienyl- (2, 4-dichloro-1-naphthoxy) -titanium dichloride catalyst (containing 5. Mu. Mol of the catalyst) in example 3 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.57 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.55 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =5.82x10 4 g/mol, MWD =1.68, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 21 polymerization of styrene Using cyclopentadienyl- (2, 4-dichloro-1-naphthyloxy) -titanium dichloride as a catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 75 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a toluene solution of methylaluminoxane (containing 10 mmol of methylaluminoxane), and 1.0 ml of a toluene solution of a catalyst containing cyclopentadienyl- (2, 4-dichloro-1-naphthoxy) -titanium dichloride (containing 5. Mu. Mol of the catalyst) obtained in example 3 were sequentially added to start a timer. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.58 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.56 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =3.73x10 4 g/mol, molecular weight distribution MWD =1.74, and melting point of polymer is 269 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 22 polymerization of styrene Using cyclopentadienyl- (2, 4-dichloro-1-naphthyloxy) -titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 90 ℃ 8 ml of toluene, 5.0 ml of styrene, 6 ml of a toluene solution of methylaluminoxane (containing 10 mmol of methylaluminoxane), and 1.0 ml of a toluene solution of a catalyst containing cyclopentadienyl- (2, 4-dichloro-1-naphthoxy) -titanium dichloride (containing 5. Mu. Mol of the catalyst) obtained in example 3 were sequentially added to start a timer. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.59 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.56 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.73x10 4 g/mol, MWD =1.58, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 23 polymerization of styrene Using cyclopentadienyl- (2-naphthoxy) -titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 45 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl- (2-naphthoxy) -titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of a catalyst) in example 4 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, vacuum-drying a filter cake for 24 hours at 60 ℃, and weighing to obtain 0.18 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.16 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =4.85x10 4 g/mol, MWD =1.75, and the melting point of the polymer is 271 ℃ as measured by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 24 polymerization of styrene Using cyclopentadienyl- (2-naphthoxy) -titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 60 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl- (2-naphthoxy) -titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of a catalyst) in example 4 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.52 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.50 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =5.02x10 4 g/mol, molecular weight distribution MWD =1.78, melting point of polymer is 270 ℃ detected by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 25 polymerization of styrene Using cyclopentadienyl- (2-naphthoxy) -titanium dichloride as catalyst
The dried polymerization bottle is vacuumized and repeatedly flushed with nitrogen for three times; at a polymerization temperature of 75 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a methylaluminoxane toluene solution (containing 10 mmol of methylaluminoxane), and 1.0 ml of a cyclopentadienyl- (2-naphthoxy) -titanium dichloride catalyst toluene solution (containing 5. Mu. Mol of a catalyst) in example 4 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.40 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.37 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =3.74x10 4 g/mol, molecular weight distribution MWD =1.69, and melting point of the polymer is 269 ℃ as measured by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Example 26 polymerization of styrene Using cyclopentadienyl- (2-naphthoxy) -titanium dichloride as catalyst
Vacuumizing the dried polymerization bottle, and repeatedly flushing the polymerization bottle with nitrogen for three times; at a polymerization temperature of 90 ℃,8 ml of toluene, 5.0 ml of styrene, 6 ml of a toluene solution of methylaluminoxane (containing 10 mmol of methylaluminoxane), and 1.0 ml of a toluene solution of a catalyst containing cyclopentadienyl- (2-naphthoxy) -titanium dichloride (containing 5. Mu. Mol of the catalyst) obtained in example 4 were sequentially added to start timing. After the polymerization time is 30 minutes, carefully pouring the reaction solution into a beaker, adding acidified ethanol, stirring for more than 6 hours, filtering to obtain a polymer, drying a filter cake at 60 ℃ for 24 hours in vacuum, and weighing to obtain 0.48 g of the polymer; the polymer was refluxed in boiling acetone for 2 hours, filtered while hot to give a solid polymer, which was dried under vacuum at 60 ℃ for 24 hours to give 0.44 g of SPS polymer.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =1.81x10 4 g/mol, MWD =1.68, and melting point of polymer is 270 ℃ by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.
Comparative example 1 Synthesis of pentamethylcyclopentadienyl-phenoxy-titanium dichloride
The procedure of example 1 was repeated except that phenol was used in place of 1-naphthol. To obtain pentamethylcyclopentadienyl-phenoxy-titanium dichloride with the yield of 92 percent, 1 H-NMR(CDCl 3 ,25℃):δ＝6.59(5H,Cp),6.80(2H),6.89(1H),7.21(2H)。
comparative example 2 polymerization of styrene Using pentamethylcyclopentadienyl-phenoxy-titanium dichloride as catalyst
The procedure of example 5 was repeated except that pentamethylcyclopentadienyl-phenoxy-dimethoxytitanium obtained in comparative example 1 was used in place of pentamethylcyclopentadienyl-4-naphthyloxy-dimethoxytitanium.
Gel permeation chromatography detection of polymer weight average molecular weight Mw =6.2x10 4 g/mol, MWD =2.02, and melting point of polymer is 270 ℃ by differential scanning calorimetry.
Comparing this comparative example 2 with example 5, it can be seen that example 5, using the catalyst polymerization system of the present invention, yields polystyrene having a higher molecular weight and a narrower molecular weight distribution.
Claims (12)
1. A styrene polymerization system comprising a naphthoxy-metallocene transition metal compound, an alkylaluminoxane and styrene,
the naphthoxy-single metallocene transition metal compound is shown as a formula (I) or a formula (II):
in the formulae (I) and (II), X 1 And X 2 Each independently selected from an alkoxy, aryloxy, alkyl, aryl or halogen atom, cp' is a cyclopentadienyl, indenyl or fluorenyl group substituted or unsubstituted with a hydrocarbon radical, R is a substituted or unsubstituted alkyl group 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom or a halogen atom;
in the polymerization system, the concentration of the naphthoxymetallocene transition metal compound is 1x10 -7 Mol/l-1 x10 -3 Mol/l.
2. Styrene polymerization system according to claim 1, characterized in that, in formula (I) and formula (II),
X 1 and X 2 Each independently selected from C 1 ～C 5 Alkoxy group of (C) 6 ～C 9 Aryloxy group of (A), C 1 ～C 5 Alkyl of (C) 6 ～C 9 An aryl group or a halogen atom of (a); and/or
Cp' is selected from C 1 ～C 3 Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; and/or
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom or a halogen atom.
3. The styrene polymerization system according to claim 2, wherein, in the formula (I) and the formula (II),
X 1 and X 2 Each independently selected from a chlorine atom, a methoxy group, a phenoxy group, a methyl group, a phenyl group or a benzyl group; and/or
Cp' is selected from pentamethylcyclopentadienyl, cyclopentadienyl or indenyl; and/or
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from a hydrogen atom or a halogen atom.
4. Styrene polymerization system according to claim 1, wherein the alkylalumoxane is selected from compounds of formula (i) and/or (ii):
in formulae (i) and (ii), R represents an alkyl group; n represents an integer of 4 to 30.
5. The method of claim 4Styrene polymerization system, characterized in that R is C 1 ～C 6 Alkyl groups of (a); n is an integer of 10 to 30.
6. The styrene polymerization system according to claim 1, wherein the molar ratio of the naphthoxy-metallocene transition metal compound to the alkylaluminoxane is 1 (50 to 20000); wherein, the molar amounts of Ti element and Al element are respectively calculated.
7. The styrene polymerization system according to claim 6, wherein the molar ratio of the naphthoxy-metallocene transition metal compound to the alkylaluminoxane is 1 (200 to 10000); wherein, the molar amounts of Ti element and Al element are respectively counted.
8. The styrene polymerization system of claim 1, wherein the polymerization system further comprises an organic solvent.
9. Styrene polymerization system according to claim 8, characterized in that the organic solvent is toluene and/or hexane.
10. A styrene polymerization process carried out using the styrene polymerization system according to any one of claims 1 to 9.
11. The styrene polymerization process according to claim 10, wherein the polymerization temperature is from-50 ℃ to 200 ℃.
12. The styrene polymerization process of claim 10, wherein the polymerization temperature is from 0 ℃ to 100 ℃.
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