阅读说明：本技术 一种苯乙烯聚合体系及聚合方法与得到的聚苯乙烯 (Styrene polymerization system and polymerization method and obtained polystyrene ) 是由 王伟 曲树璋 陈珺娴 张韬毅 侯莉萍 郑刚 于 2019-10-15 设计创作，主要内容包括：本发明涉及一种苯乙烯聚合体系及聚合方法与得到的聚苯乙烯,所述催化聚合体系包括萘氧基单茂过渡金属化合物、烷基铝氧烷和苯乙烯,所述萘氧基单茂过渡金属化合物的结构中含有萘氧基、Cp’配体和过渡金属,所述萘氧基和Cp’配体分别与过渡金属相连,形成萘氧基单茂过渡金属化合物。其中,所述萘氧基单茂过渡金属化合物与烷基铝氧烷的摩尔比为1:(50～20000),萘氧基单茂过渡金属化合物在聚合体系中的浓度为1x10～(-8)摩尔/升～1x10～(-3)摩尔/升。本发明所述聚合体系采用了具有特殊结构的萘氧基单茂过渡金属化合物为主催化剂,利用所述聚合体系可得到间规聚苯乙烯,并且,得到的聚苯乙烯具有高分子量、窄分子量分布等优点。(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/l-1 x10 ‑3 Mol/l. The polymerization system of the invention adopts naphthoxy-single metallocene transition metal compound with special structure as a main catalyst, and utilizes the polymerizationSyndiotactic polystyrene can be obtained from the combined system, and the obtained polystyrene has the advantages of high molecular weight, narrow molecular weight distribution and the like.)

1. A styrene polymerization system comprises a naphthoxy-metallocene transition metal compound, alkylaluminoxane and styrene, wherein the structure of the naphthoxy-metallocene transition metal compound contains naphthoxy, Cp 'ligands and transition metal, and the naphthoxy and the Cp' ligands are respectively connected with the transition metal to form the naphthoxy-metallocene transition metal compound.

2. The styrene polymerization system of claim 1, wherein the naphthoxy-metallocene transition metal compound is represented by formula (I) or formula (II):

in the formulae (I) and (II), X₁And X₂Each 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 group¹、R²、R³、R⁴、R⁵、R⁶Each independently selected from a hydrogen atom, a halogen atom or a substituent containing 1 to 18 carbon atoms.

3. The styrene polymerization system according to claim 2, wherein, in the formula (I) and the formula (II),

X₁and X₂Each independently selected from C₁～C₅Alkoxy group of (C)₆～C₉Aryloxy group of (A), C₁～C₅Alkyl of (C)₆～C₉An aryl group or a halogen atom of (a); and/or

Cp' is selected from C₁～C₃Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; and/or

R¹、R²、R³、R⁴、R⁵、R⁶Each independently selected from a hydrogen atom, a halogen atom, C₆～C₉Aryl of (C)₁～C₅Alkyl or C₁～C₅Substituted alkyl groups of (1).

4. The styrene polymerization system according to claim 3, wherein, in the formula (I) and the formula (II),

X₁and X₂Each 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

R¹、R²、R³、R⁴、R⁵、R⁶Each independently selected from hydrogen atom, C₁～C₃Alkyl of (C)₁～C₃Halogen-substituted alkyl groups or halogen atoms.

5. Styrene polymerization system according to claim 1, wherein the alkylalumoxane is selected from compounds of formula (i) and/or (ii):

in the formulae (i) and (ii), R represents an alkyl group, preferably C₁～C₆More preferably methyl; n represents an integer of 4 to 30, preferably 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), preferably 1 (200 to 10000), more preferably 1 (500 to 3000); wherein, the molar amounts of Ti element and Al element are respectively calculated.

7. Styrene polymerization system according to claim 1, characterized in that the polymerization system further comprises an organic solvent, preferably toluene and/or hexane, more preferably toluene.

8. Styrene polymerization according to any one of claims 1 to 7A system characterized in that the concentration of the naphthoxymonocyclopentadienyl transition metal compound in the polymerization system is 1x10^-8Mol/l-1 x10^-2Mol/l, preferably 1X10^-7Mol/l-1 x10^-3Mol/l.

9. A styrene polymerization method, which is carried out by using the styrene polymerization system of any one of claims 1 to 8, preferably, the polymerization temperature is from-50 ℃ to 200 ℃, preferably from 0 ℃ to 100 ℃.

10. Polystyrene obtainable by the polymerization process according to claim 9, preferably syndiotactic polystyrene.

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, the 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 a metallocene catalyst, 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 therefor₃Forming 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 19)86,19, 2465; EP210615,1987). Chien and Rausch et al use IndCl₃As a catalyst, syndiotactic polymerization of styrene was studied; with CpTiCl₃Compared with IndclI₃The activity of catalyzing the 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)ⁱPr)₃The 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 Xu₃The activity of the catalyst can reach 27.0 multiplied by 10 when the catalyst is used for catalyzing the syndiotactic polymerization of styrene⁴g-SPS/mol-Ti/h, the weight average molecular weight of the polymer can reach 74 ten thousand (Macromolecules 2000,332825).

Kaminsky studied the syndiotactic polymerization of styrene using a fluorine-containing metallocene catalyst and found that Cp' TiF was used₃Polymerization activity ratio Cp' TiCl₃Tens or even hundreds of times higher. Using MeCpTiF₃SPS with a molecular weight of 142 ten thousand can be obtained as a catalyst (Macromolecules 1997,30, 7647). Ruckenstein uses Ind' TiF₃Syndiotactic 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' TiX₃The 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 ligand₂L (L ═ electron donor ligands) 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 uses titanocenes of the following formulas 2 and 3 for syndiotactic polymerization of styrene, in which all the 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 patents identified with Cp' Ti (OR)₃Studies on the catalysis of syndiotactic polymerization of styrene, for example, CN101205261A, CN1611518A, CN1450093A, CN1450089A, CN1467213A, CN1467214A, CN1467232A, CN1459461A, CN1508157A, CN1490344A, CN1340551A, CN1295084A, CN1235986A, CN1235976A, CN1210109A, CN1210108A, CN1210107A and CN 1150154A.

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), X₁And X₂Each 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 group¹、R²、R³、R⁴、R⁵、R⁶Each 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, R¹、R²、R³、R⁴、R⁵、R⁶The nitro group capable of being coordinated 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, and the active center is electropositive, so that 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 destroy the catalyst structure and increase the consumption of the cocatalyst.

In a preferred embodiment, in formula (I) and formula (II), X₁And X₂Each independently selected from C₁～C₅Alkoxy group of、C₆～C₉Aryloxy group of (A), C₁～C₅Alkyl of (C)₆～C₉An aryl group or a halogen atom of (a); and/or Cp' is selected from C₁～C₃Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; and/or, R¹、R²、R³、R⁴、R⁵、R⁶Each independently selected from a hydrogen atom, a halogen atom, C₆～C₉Aryl of (C)₁～C₅Alkyl or C₁～C₅Substituted alkyl groups of (1).

In a further preferred embodiment, in formula (I) and formula (II), X₁And X₂Each 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, R¹、R²、R³、R⁴、R⁵、R⁶Each independently selected from hydrogen atom, C₁～C₃Alkyl of (C)₁～C₃Halogen-substituted alkyl groups or halogen atoms.

In a further preferred embodiment, in formula (I) and formula (II), X₁And X₂Each independently selected from a chlorine atom or a methoxy group; and/or Cp' is selected from pentamethylcyclopentadienyl or cyclopentadienyl; and/or, R¹、R²、R³、R⁴、R⁵、R⁶Each 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 C₁～C₆More 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), wherein the molar amounts of the Ti element and the Al element are respectively calculated.

In a further preferred embodiment, the molar ratio of the naphthoxy-metallocene transition metal compound to the alkylaluminoxane is 1 (200 to 10000) in terms of the molar amount of the Ti element and the Al element, respectively.

In a further preferred embodiment, the molar ratio of the naphthoxy-metallocene transition metal compound to the alkylaluminoxane is 1 (500 to 3000) based on the molar amount of the Ti element and the Al element, respectively.

Most preferably, the molar ratio of the naphthoxy-single metallocene transition metal compound to the alkylaluminoxane is 1 (1500-2000), wherein the molar amounts of the Ti element and the Al element are respectively calculated.

In a preferred embodiment, the polymerization system further comprises an organic solvent, preferably toluene and/or hexane, more preferably toluene.

Wherein, during styrene polymerization, the alkyl aluminoxane and the naphthoxy-single 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^-8mol/l-1X 10^-2Mol/l, preferably 1X10^-7mol/l-1X 10^-3Mol/l.

Most preferably, the concentration of the naphthoxymetallocene transition metal compound in the polymerization system is (1-5). times.10^-4Mol/l.

In a preferred embodiment, the polymerization system is used for the preparation of syndiotactic polystyrene at a polymerization temperature of from-50 ℃ to 200 ℃, preferably from-20 ℃ to 150 ℃, more preferably from 0 ℃ to 100 ℃, for example from 50 ℃ to 90 ℃.

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), X₁、X₂And X₃Each 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), R¹、R²、R³、R⁴、R⁵、R⁶Each 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), X₁、X₂And X₃Each independently selected from C₁～C₅Alkoxy group of (C)₆～C₉Aryloxy group of (A), C₁～C₅Alkyl of (C)₆～C₉An aryl group or a halogen atom of (a); and/or Cp' is selected from C₁～C₃Alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl; and/or, in the formulae (IV) and (V), R¹、R²、R³、R⁴、R⁵、R⁶Each independently selected from a hydrogen atom, a halogen atom, C₆～C₉Aryl of (C)₁～C₅Alkyl or C₁～C₅Substituted alkyl groups of (1).

In a further preferred embodiment, in formula (III), X₁、X₂And X₃Each 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), R¹、R²、R³、R⁴、R⁵、R⁶Each independently selected from a hydrogen atom, a halogen atom, C₁～C₃Alkyl of (C)₁～C₃Halogen-substituted alkyl of (1).

In a still further preferred embodiment, in formula (III), X₁、X₂And X₃Each 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), R¹、R²、R³、R⁴、R⁵、R⁶Each 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 performed 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 X₁、X₂And X₃When the halogen atom is selected, the reaction is carried out at room temperature without heating; when X is present₁、X₂And X₃Is selected from C₁～C₅Alkoxy of (2)Base, C₆～C₉Aryloxy group of (A), C₁～C₅Alkyl of (C)₆～C₉The 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 30 hours.

In a further preferred embodiment, the reaction is carried out for 20 to 28 hours, for example 24 hours, when the reaction is carried out at room temperature; when the reaction is performed under reflux at 60-140 ℃, the reaction is performed for 2-6 hours, such as 4 hours.

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: 1.

The above means: the molar use ratio of the compound shown in the formula (IV) to the compound shown in the formula (III) is 1:1, or the molar use ratio of the compound shown in the formula (V) to the compound shown in the formula (III) is 1: 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 250 ml three-mouth bottle, and putting the reaction bottle into a magnetic stirring device; the three-necked flask was evacuated and 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.

¹H-NMR(CDCl₃,25℃):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 250 ml three-mouth bottle, and putting 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.

¹H-NMR(CDCl₃,25℃):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 250 ml three-mouth bottle, and putting the reaction bottle into a magnetic stirring device; the three-necked flask was evacuated and 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 and filtered using celite 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, the molar yield of which is 93 percent.

¹H-NMR(CDCl₃,25℃):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 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.

¹H-NMR(CDCl₃,25℃):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 weight average molecular weight Mw of polymer 1.68x10⁵g/mol, MWD of 1.61, and melting point of polymer of 270 deg.C 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 dried under vacuum at 60 ℃ for 24 hours to give 0.64 g of SPS polymer.

Gel permeation chromatography detection of weight average molecular weight Mw of polymer 1.83x10⁵g/mol, MWD of 1.64, and melting point of 269 deg.C 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

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 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 0.84 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 weight average molecular weight Mw of polymer 1.94x10⁵g/mol, MWD of 1.59, and melting point of polymer 272 deg.C by differential scanning calorimetry. 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

The dried polymerization bottle is vacuumized and repeatedly flushed 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 weight average molecular weight Mw of polymer 1.65x10⁵g/mol, MWD of 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 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 0.62 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 of polymer 1.23x10⁵g/mol, MWD of 1.68, and melting point of polymer is 270 deg.C 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

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 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 weight average molecular weight Mw of polymer 9.78x10⁴g/mol, MWD of 1.94, melting point of polymer 268 ℃ detected by differential scanning calorimetry. 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, vacuum-drying a filter cake for 24 hours at 60 ℃, 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 weight average molecular weight Mw of polymer 1.56x10⁵g/mol, MWD of 1.97, and melting point of polymer of 270 deg.C by differential scanning calorimetry. The nuclear magnetic spectrum of the product is similar to that of figure 1.

Example 12 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 ℃, 9.5 ml of toluene, 5.0 ml of styrene, 4.5 ml of methylaluminoxane toluene solution (containing 7.5 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 0.33 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 weight average molecular weight Mw of polymer 2.65x10⁴g/mol, MWD of 1.82, melting point of polymer is 270 degree centigrade 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 weight average molecular weight Mw of polymer 2.72x10⁴g/mol, MWD of 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 weight average molecular weight Mw of polymer 3.61x10⁴g/mol, MWD of 2.23, and melting point of polymer 270 deg.C by differential scanning calorimetry. Nuclear magnetic spectrum and graph of the product1 approximation.

Example 15 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 ℃,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 weight average molecular weight Mw of polymer 2.53x10⁴g/mol, MWD of 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

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 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 for 24 hours at 60 ℃, 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 weight average molecular weight Mw of polymer 1.90x10⁴g/mol, moleculeThe MWD is 1.77, and the melting point of the 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 weight average molecular weight Mw of polymer 3.65x10⁴g/mol, MWD of 1.79, and melting point of polymer of 270 ℃ detected 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 of polymer 4.03x10⁴g/mol, MWD of 1.84, and 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 dried under vacuum at 60 ℃ for 24 hours to give 0.24 g of SPS polymer.

Gel permeation chromatography detection of weight average molecular weight Mw of polymer 5.58x10⁴g/mol, MWD of 1.82, and melting point of polymer 271 deg.C 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

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, 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 0.57 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 weight average molecular weight Mw of polymer 5.82x10⁴g/mol, MWD of 1.68, and melting point of polymer is 270 deg.C 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 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, 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 0.58 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 weight average molecular weight Mw of polymer 3.73x10⁴g/mol, MWD 1.74, and melting point 269 deg.C as measured 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 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 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 0.59 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 weight average molecular weight Mw of polymer 1.73x10⁴g/mol, MWD of 1.58, and melting point of polymer of 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 weight average molecular weight Mw of polymer 4.85x10⁴g/mol, MWD of 1.75, and 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 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 weight average molecular weight Mw of polymer 5.02x10⁴g/mol, MWD of 1.78, and melting point of polymer of 270 deg.C 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 weight average molecular weight Mw of polymer 3.74x10⁴g/mol, MWD 1.69, and melting point 269 deg.C 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

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 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 0.48 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 weight average molecular weight Mw of polymer 1.81x10⁴g/mol, MWD of 1.68, and melting point of polymer is 270 deg.C 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,¹H-NMR(CDCl₃,25℃):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 weight average molecular weight Mw of polymer 6.2x10⁴g/mol, MWD of 2.02, and melting point of polymer of 270 deg.C 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.