CN116410359A - Non-metallocene catalyst and preparation method and application thereof - Google Patents

Non-metallocene catalyst and preparation method and application thereof Download PDF

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CN116410359A
CN116410359A CN202111681460.1A CN202111681460A CN116410359A CN 116410359 A CN116410359 A CN 116410359A CN 202111681460 A CN202111681460 A CN 202111681460A CN 116410359 A CN116410359 A CN 116410359A
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metallocene catalyst
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黄付玲
米普科
马鸿钰
王斯晗
蒋岩
王力搏
霍宏亮
牟玉强
王亚丽
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East China University of Science and Technology
Petrochina Co Ltd
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Petrochina Co Ltd
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Abstract

The invention discloses a non-metallocene catalyst, a preparation method and application thereof, wherein the non-metallocene catalyst has a structure as shown in the following formula I:
Figure DDA0003453370150000011
wherein M is selected from IVB transition metal atoms; l is a halogen atom; x is selected from one of O, NH and S; r is R 1 、R 2 And R is 3 Independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon group having 1-12 carbons, substituted or unsubstituted aromatic hydrocarbon group having 6-12 carbons, oxygen-containing group, sulfur-containing group or halogen atom, R 2 And R is 3 May also be selected from nitrogen-containing groups; alternatively, R 3 Selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups with 1-12 carbons, substituted or unsubstituted substituted hydrocarbon groups with 1-12 carbonsAn aromatic hydrocarbon group having 6 to 12 carbon atoms, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a halogen atom, R 1 And R is 2 Form a cyclic structure, being substituted or unsubstituted C 4 ～C 8 Conjugated olefinic groups of (2); n is 1 to 3. The non-metallocene catalyst has high polymerization activity when being applied to olefin polymerization, and can prepare low-molecular-weight polyethylene.

Description

Non-metallocene catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a non-metallocene catalyst and a preparation method and application thereof.
Background
In the development of olefin polymerization catalysts, non-metallocene catalysts developed in the nineties of the twentieth century have been greatly developed and paid attention to. Since non-metallocene catalysts occur after metallocene catalysts, they are also referred to as "post-metallocene" olefin polymerization catalysts. It has the characteristics similar to metallocene catalyst, can customize polymer according to the requirement, and has lower cost. The central atoms of non-metallocene catalysts include almost all transition metal elements, which in some properties have reached, even exceeded, the metallocene catalysts, becoming a new generation of olefin polymerization catalysts subsequent to Ziegler-Natta and metallocene catalysts.
Depending on the central atom of the main catalyst, it is further distinguished into non-metallocene front-transition metal (group IIIB, IVB, VB, VIB, VIIB) catalysts and non-metallocene rear-transition metal (group VIII) catalysts. Polyolefin products made from such catalysts have excellent properties and low manufacturing costs. The non-metallocene catalyst coordination atoms are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadienyl groups or derivative groups thereof, such as indenyl groups, fluorenyl groups and the like, and the non-metallocene catalyst coordination atoms are characterized in that the central ion has stronger electrophilicity, has a cis-alkyl or halogen metal central structure, is easy to insert olefin, is easy to alkylate central metal, and is favorable for generating cation active centers; the complexes formed have defined geometric configurations, stereoselectivity, electronegativity and chiral adjustability. In addition, the formed metal-carbon bond is easy to polarize, which is more beneficial to the polymerization and copolymerization of olefin. Thus, a higher polymerization activity can be obtained at the polymerization temperature. In particular, the group IV transition metal complex (EP 0874005, W00155231) containing a phenoxy-imine ligand has a high activity of catalyzing olefin polymerization, and can give a polyolefin resin having functional characteristics.
Patents ZL01126323.7, ZL02151294.9 and ZL02110844.7 and WO 03/010207 disclose olefin homo/copolymerization catalysts or catalytic systems which have wide olefin homo/copolymerization performance, but the catalysts or catalytic systems disclosed in the patents require higher cocatalyst dosage during olefin polymerization to obtain proper olefin polymerization activity, and the phenomena of short activity duration, polymer sticking to a kettle and the like exist in the polymerization process. Patent CN102295714 discloses an ethylene polymerization catalyst, and the molecular weight of polyethylene obtained by the catalysis of the catalyst is more than 100 ten thousand.
Thus, there is still a need in the art for further research into non-metallocene catalysts.
Disclosure of Invention
The invention mainly aims to provide a non-metallocene catalyst, a preparation method and application thereof, so as to overcome the defects of high cocatalyst consumption, low activity of the non-metallocene catalyst and the like in the olefin polymerization process in the prior art.
In order to achieve the above object, the present invention provides a non-metallocene catalyst having the structure of formula I:
Figure BDA0003453370130000021
wherein M is selected from IVB transition metal atoms;
l is a halogen atom;
x is selected from one of O, NH and S;
R 1 selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups or halogen atoms, R 2 And R is 3 Independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or halogen atoms; alternatively, R 3 Selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or halogen atoms, R 1 And R is 2 Form a cyclic structure, being substituted or unsubstituted C 4 ～C 8 Conjugated olefinic groups of (2);
n is 1 to 3.
The non-metallocene catalysts of the present invention, in one embodiment, R 1 、R 2 And R is 3 Not both hydrogen.
In one embodiment of the non-metallocene catalyst described herein, M is Ti, zr or Hf; l is Cl or Br; n is 2; r is R 1 Selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons or halogen atoms, R 2 And R is 3 Independently selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbonsA group, alkylthio group having 1 to 12 carbons, alkylamine having 1 to 12 carbons, nitro group or halogen atom; alternatively, R 3 Selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, alkylamine groups having 1 to 12 carbons, nitro groups or halogen atoms, R 1 And R is 2 Form a cyclic structure, which is unsubstituted C 4 ～C 8 Or C containing an alkoxy substituent or an alkylthio substituent 4 ～C 8 Is a conjugated olefin group of (C).
In one embodiment, the non-metallocene catalyst of the present invention has one of the following structures:
1、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝H，R 3 ＝CH 3 ；
2、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝R 3 ＝H；
3、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝t-Bu,R 2 ＝H,R 3 ＝OCH 3 ；
4、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝i-OPr，R 2 ＝R 3 ＝H；
5、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝n-OBu,R 2 ＝R 3 ＝H；
6、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Br,R 2 ＝H,R 3 ＝Cl；
7、M＝Ti,X＝O,n＝2,L＝Br,R 1 ＝t-Bu,R 2 ＝H,R 3 ＝OCH 3 ；
8、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝R 3 ＝H；
9、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝SCH 3 ,R 2 ＝R 3 ＝H；
10、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 ＝-OBu，R 2 ＝R 3 ＝H；
11、M＝Ti,X＝O,n＝2,L＝Cl,R 1 and R is 2 Is cyclic and is-ch=ch-, R 3 ＝H；
12、M＝Ti,X＝O,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )-CH＝CH-, R 3 ＝H；
13、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-, R 3 ＝H；
14、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-C (OCH) 3 )＝CH-,R 3 ＝H；
15、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Cl,R 2 ＝R 3 ＝H；
16、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Cl,R 2 ＝H,R 3 ＝CH 3 ；
17、M＝Ti,X＝S,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-, R 3 ＝H；
18、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )- C(OCH 3 )＝CH-,R 3 ＝H；
19、M＝Ti,X＝O,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )- C(OCH 3 )＝CH-,R 3 ＝H。
In order to achieve the above object, the present invention also provides a method for preparing a non-metallocene catalyst, comprising the steps of:
step 1, mixing a transition metal compound and an aryl ligand, and reacting at 50-120 ℃;
step 2, cooling the mixture obtained in the step 1 to 0-30 ℃, and continuing to react in an inert gas environment;
step 3, carrying out post-treatment and drying on the mixture obtained in the step 2 to obtain a non-metallocene catalyst;
wherein the transition metal compound is a compound of IV B transition metal, and the aryl ligand is aryl phenol, aryl sulfur or aryl amine containing or not containing substituent groups.
In one embodiment, the transition metal compound is a compound of Ti, zr or Hf, and the substituent is selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon group with 1-12 carbons, substituted or unsubstituted aromatic hydrocarbon group with 6-12 carbons, oxygen-containing group, sulfur-containing group or halogen atom.
In one embodiment, the transition metal compound is a chloride of Ti, zr or Hf, and the substituent is selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons or halogen atoms.
In one embodiment, the aryl ligand contains at least two substituents on adjacent carbons of the aromatic ligand, and the at least two substituents form a cyclic structure, which is a substituted or unsubstituted C 4 ～C 8 Is a conjugated olefin group of (C).
In one embodiment, the at least two substituents form a cyclic structure, which is unsubstituted C 4 ～C 8 Or C containing an alkoxy substituent, alkylthio substituent or halogen substituent 4 ～C 8 Conjugated olefins of (a).
In one embodiment, the transition metal compound and the aryl ligand are dissolved in organic solvent, and the organic solvent is selected from C 4 ～C 10 Alkanes, halogenated C 1 ～C 10 Alkanes, C 6 ～C 10 Cycloalkane or C 6 ～C 20 Aromatic hydrocarbons.
In order to achieve the above-mentioned object, the present invention further provides a method for polymerizing olefins, wherein the above-mentioned non-metallocene catalyst is used as a main catalyst.
In one embodiment of the olefin polymerization process of the present invention, the olefin polymerization process uses an organoaluminum as a cocatalyst.
The invention has the beneficial effects that:
the non-metallocene catalyst of the invention can be used for olefin polymerization, and has higher catalytic activity under the condition of smaller consumption of the cocatalyst, and the catalytic activity can reach 3-6 KgPE (g.cat.h) -1 Thus, low molecular weight polyethylene, for example, a viscosity average molecular weight of 8675-12586 g/mol, can be obtained, and the polymer obtained has good morphology, a crystallinity of 59-78% and a molecular weight distribution of 2-5.
The non-metallocene catalyst has the advantages of easily available raw materials, low cost, simple preparation process and convenient operation, and is suitable for industrial production.
Drawings
FIG. 1 is a chart of nuclear magnetic resonance carbon spectrum of catalyst CAT-1 of example 1 of the present invention;
FIG. 2 is a chart of the nuclear magnetic resonance spectrum of catalyst CAT-4 of example 4 of the present invention;
FIG. 3 is a chart of the nuclear magnetic resonance spectrum of catalyst CAT-7 of example 7 of the present invention;
FIG. 4 is a chart showing the nuclear magnetic resonance spectrum of catalyst CAT-10 of example 10 of the present invention.
Detailed Description
The following describes the present invention in detail, and the present examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
The invention provides a non-metallocene catalyst, which has a structure shown in the following formula I:
Figure BDA0003453370130000061
in the formula I, n is as followsShowing the group attached to M
Figure BDA0003453370130000062
For example, n is 2, then two +.>
Figure BDA0003453370130000063
The radicals are each bonded to M; similarly, 4-n represents the number of groups L attached to M, e.g., n is 2, and then represents that two L groups are each bonded to M, thus giving the following formula II:
Figure BDA0003453370130000064
wherein M is selected from group III to group XI transition metal atoms, preferably group IVB transition metal atoms;
l is a halogen atom;
x is selected from one of O, NH and S;
R 1 、R 2 and R is 3 Independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon group having 1-12 carbons, substituted or unsubstituted aromatic hydrocarbon group having 6-12 carbons, oxygen-containing group, sulfur-containing group or halogen atom, R 2 、R 3 May also be a nitrogen-containing group; alternatively, R 3 Selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or halogen atoms, R 1 And R is 2 Form a cyclic structure, being substituted or unsubstituted C 4 ～C 8 Conjugated olefinic groups of (2);
n is 1 to 3.
In one embodiment, M is Ti, zr or Hf; l is Cl or Br; n is 2; r is R 1 、R 2 And R is 3 Not both hydrogen. In another embodiment, R 1 、R 2 And R is 3 Independently selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, or halogen atoms, wherein，R 2 And R is 3 May be a nitrogen-containing group such as an alkylamine having 1 to 12 carbons, a nitro group, or the like; alternatively, R 3 Selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, alkylamine groups having 1 to 12 carbons, nitro groups or halogen atoms, R 1 And R is 2 Form a cyclic structure, which is unsubstituted C 4 ～C 8 Or C containing an alkoxy substituent or an alkylthio substituent 4 ～C 8 Is a conjugated olefin group of (C).
In another embodiment, the non-metallocene catalyst has one of the following structures:
1、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝H，R 3 ＝CH 3 ；
2、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝R 3 ＝H；
3、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝t-Bu,R 2 ＝H,R 3 ＝OCH 3 ；
4、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝i-OPr，R 2 ＝R 3 ＝H；
5、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝n-OBu,R 2 ＝R 3 ＝H；
6、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Br,R 2 ＝H,R 3 ＝Cl；
7、M＝Ti,X＝O,n＝2,L＝Br,R 1 ＝t-Bu,R 2 ＝H,R 3 ＝OCH 3 ；
8、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝R 3 ＝H；
9、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝SCH 3 ,R 2 ＝R 3 ＝H；
10、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 ＝-OBu，R 2 ＝R 3 ＝H；
11、M＝Ti,X＝O,n＝2,L＝Cl,R 1 and R is 2 Is cyclic and is-ch=ch-, R 3 =h, where R 1 And R is 2 Forming a naphthalene ring structure with the benzene ring in the formula I;
12、M＝Ti,X＝O,n＝2,L＝Cl,R 1 and R is 2 Is cyclic and is-ch=c (OCH) 3 )-CH＝CH-, R 3 ＝H；
13、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-, R 3 ＝H；
14、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-C (OCH) 3 )＝CH-,R 3 ＝H；
15、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Cl,R 2 ＝R 3 ＝H；
16、M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Cl,R 2 ＝H,R 3 ＝CH 3 ；
17、M＝Ti,X＝S,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-, R 3 ＝H；
18、M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )- C(OCH 3 )＝CH-,R 3 ＝H；
19、M＝Ti,X＝O,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )- C(OCH 3 )＝CH-,R 3 ＝H。
The invention also provides a preparation method of the non-metallocene catalyst, which comprises the following steps:
step 1, mixing a transition metal compound and an aryl ligand, and reacting at 50-120 ℃;
step 2, cooling the mixture obtained in the step 1 to 0-30 ℃, and continuing to react in an inert gas environment;
step 3, carrying out post-treatment and drying on the mixture obtained in the step 2 to obtain a non-metallocene catalyst;
wherein the transition metal compound is a compound of IV B transition metal, and the aryl ligand is aryl phenol, aryl sulfur or aryl amine containing or not containing substituent groups.
In one embodiment, the above-described non-metallocene catalysts of the present invention can be prepared according to the preparation method.
In another embodiment, the transition metal compound is a compound of Ti, zr or Hf, and in yet another embodiment, the transition metal compound is a chloride of Ti, zr or Hf, such as a tetrachloride of Ti, zr or Hf.
In another embodiment, the aryl ligand contains a substituent selected from the group consisting of hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbons, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbons, an oxygen-containing group, a sulfur-containing group, or a halogen atom. In yet another embodiment, the substituents of the aryl ligand are selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, or halogen atoms. In yet another embodiment, the aryl ligand contains at least two substituents, located on adjacent carbons of the aromatic ligand, and the at least two substituents form a cyclic structure, either substituted or unsubstituted C 4 ～C 8 Is a conjugated olefin group of (C). In yet another embodiment, the at least two substituents form a cyclic structure, which is unsubstituted C 4 ～C 8 Or C containing an alkoxy substituent, alkylthio substituent or halogen substituent 4 ～C 8 Conjugated olefinic groups of (2); further, substituted C 4 ～C 8 The substituent in the conjugated olefin group of (a) may be an alkoxy group having 1 to 12 carbons, an alkylthio group having 1 to 12 carbons or a halogen atom. In yet another embodiment, the aryl groups in the aryl ligands of the present invention are phenyl, naphthyl, and the like.
In one embodiment, the transition metal compound and the aryl ligand of the present invention are dissolved in an organic solvent selected from C 4 ～C 10 Alkanes, halogenated C 1 ～C 10 Alkanes, C 6 ～C 10 Cycloalkanes or cycloalkanesC 6 ～C 20 Aromatic hydrocarbons. In another embodiment, the organic solvent is selected from butane, pentane, hexane, heptane, octane, nonane, decane, methylene chloride, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, xylene or other organic solvents, with n-hexane, n-heptane and toluene being preferred, toluene being most preferred.
In one embodiment, the molar ratio of transition metal compound to aryl ligand is 1:2.
In one embodiment, the method for preparing the non-metallocene catalyst comprises the following steps:
step 1, slowly dripping a transition metal compound solution dissolved in an organic solvent into an aryl-containing ligand solution at the temperature of 0-50 ℃ under the stirring state, and refluxing for 1-4 hours at the constant temperature of 50-120 ℃;
step 2, in the inert gas environment, the reaction system is reduced to 0-30 ℃ and stirred for reaction for 12-48 hours;
and step 3, distilling the liquid in the reaction system under reduced pressure to obtain a viscous solid, taking a certain amount of hexane solvent for washing, press-filtering for multiple times, and drying to obtain a powdery solid catalyst.
The inert gas is not particularly limited in the present invention, and is, for example, nitrogen, argon, or the like.
In another embodiment, the process for preparing the non-metallocene catalyst of the present invention comprises the steps of:
step 1, dissolving 0.2-2mmol of aryl ligand in a certain amount of organic solvent, and stirring until the aryl ligand is dissolved to obtain a component A solution;
(2) Dissolving 0.2-1.5mmol of transition metal compound in a certain amount of organic solvent, and fully stirring to obtain a component B solution;
(3) Slowly dripping the component B solution into the component A solution at the temperature of between 0 and 50 ℃ under the stirring state, and refluxing for 1 to 4 hours at the constant temperature of between 50 and 120 ℃;
(4) In the inert gas environment, the reaction system is reduced to 0 ℃ to 30 ℃ and stirred for reaction for 12h to 48h;
(5) And (3) distilling the liquid in the reaction system under reduced pressure to obtain a viscous solid, taking a certain amount of hexane solvent for washing, press-filtering for 3 times, and drying to obtain a powdery solid catalyst.
The invention also provides application of the non-metallocene catalyst in olefin polymerization, namely, the non-metallocene catalyst is used as a main catalyst, and organic aluminum is used as a cocatalyst to catalyze olefin homopolymerization or copolymerization.
In one embodiment, the olefin polymerization is carried out by a solution polymerization process, wherein ethylene homo-polymerization or ethylene and a catalyst selected from C are carried out by using the non-metallocene catalyst as a main catalyst and an organoaluminum as a cocatalyst 3 ～C 12 The alpha-olefin of (a) is copolymerized to produce an olefin polymer.
In one embodiment, the organoaluminum cocatalyst of the present invention is MAO (methylaluminoxane). To reduce the production costs, organoaluminum cocatalysts may be used as aluminum alkyls, the general formula of which may be represented by the following chemical formula: alR (AlR) 3 . Wherein the radicals R may be identical or different and are each selected from C 1 ～C 8 Alkyl groups, in particular, may be selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, triisohexylaluminum, diethylmethylaluminum, dimethylethylaluminum or other alkylaluminum, with trimethylaluminum, triethylaluminum and triisobutylaluminum being preferred, trimethylaluminum and triethylaluminum being further preferred, and triethylaluminum being most preferred.
In another embodiment, the organoaluminum cocatalysts of the present invention are haloalkylaluminum compounds of the general formula: alR (AlR) n X (3-n) . Wherein the radicals R may be identical or different and are each selected from C 1 ～C 8 An alkyl group; the group X is halogen, preferably chlorine; n is 1-2. Specifically, the catalyst is selected from dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, dipropylaluminum chloride, propylaluminum dichloride, di-n-butylaluminum chloride, n-butylaluminum dichloride, propylaluminum chloride, di-n-butylaluminum chloride, di-n-pentylaluminum chloride, n-pentylaluminum dichloride, diisopentylaluminum chloride, isoamylaluminum dichloride, and monoaluminum chlorideDi-n-hexylaluminum chloride, n-hexylaluminum dichloride, diisohexylaluminum chloride, isohexylaluminum dichloride, chloromethylethylaluminum, chloromethylpropylaluminum, chloromethyl n-butylaluminum, chloromethylisobutylaluminum, chloroethylaluminum n-butylaluminum, chloromethylisobutylaluminum, sesquihexylaluminum or other chloroalkylaluminum, of which monoethylaluminum chloride and sesquihexylaluminum are preferred, and sesquihexylaluminum is most preferred.
In one embodiment, the solvent for olefin polymerization may be selected from C 4 ～C 10 Alkanes, halogenated C 1 ～C 10 Alkanes, C 6 ～C 10 Cycloalkane or C 6 ～C 20 Aromatic hydrocarbons; in particular, it may be selected from butane, pentane, hexane, heptane, octane, nonane, decane, dichloromethane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, xylene or other organic solvents, of which n-hexane, n-heptane and toluene are preferred, toluene being most preferred.
The technical scheme of the present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited to the following examples.
Example 1
Under nitrogen atmosphere, 124mg of 2-methoxyphenol is weighed, added into a Schlenk bottle with 100ml, added with 30ml of toluene, and stirred for 5-10 min until the mixture is completely dissolved to form an anhydrous transparent solution A; taking 104mg of titanium tetrachloride under the nitrogen atmosphere, adding 20ml of toluene into a 50ml round-bottom flask, and stirring for 5-10 min until the titanium tetrachloride is completely dissolved to obtain anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 60 ℃, and stirring and refluxing for 3h; then cooling to room temperature, stirring and reacting for 24 hours, decompressing and distilling to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-1.
The nuclear magnetic resonance measurement is carried out on CAT-1 for structural analysis, and the obtained carbon spectrum is shown in FIG. 1. Wherein, 9 peaks appear in the nuclear magnetic resonance carbon spectrum chart, corresponding to the carbon atoms of 9 different chemical environments, and the chemical structure of CAT-1 can be obtained by further analysis.
Figure BDA0003453370130000111
Example 2
Under nitrogen atmosphere, 124.1mg of 4-methoxyphenol is weighed, added into a Schlenk bottle with 100ml, added with 30ml of toluene, and stirred for 5-10 min until the 4-methoxyphenol and the toluene are completely dissolved to form an anhydrous transparent solution A; under nitrogen atmosphere, taking 102mg of zirconium tetrachloride, adding 20ml of toluene into a 50ml round-bottom flask, and stirring for 5-10 min until the zirconium tetrachloride is completely dissolved to obtain anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 80 ℃, and stirring and refluxing for 2h; then cooling to 30 ℃ and stirring for reaction for 12 hours, distilling under reduced pressure to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-2.
Example 3
Under nitrogen atmosphere, 138.1mg of 2-methoxy-4-methylphenol is weighed, added into a Schlenk bottle with 100ml, added with 30ml of toluene, and stirred for 5-10 min until the mixture is completely dissolved to form anhydrous transparent solution A; under nitrogen atmosphere, 99mg of titanium tetrachloride is taken and added into a 50ml round-bottom flask, 20ml of toluene is added, and stirring is carried out for 5-10 min until the titanium tetrachloride is completely dissolved to obtain anhydrous transparent solution B; slowly dripping the solution B into the solution A at 50 ℃ under stirring, stirring for 10min until the solution B is completely dissolved, heating to 80 ℃, and stirring and refluxing for 2h; then cooling to 0 ℃ and stirring for reaction for 48 hours, distilling under reduced pressure to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-3.
Example 4
Under nitrogen atmosphere, 165.2mg of 2-tertiary butyl-4 methylphenol is weighed, added into a Schlenk bottle with 100ml, added with 30ml of toluene, and stirred for 5-10 min until the mixture is completely dissolved to form anhydrous transparent solution A; under the nitrogen atmosphere, 162mg of hafnium tetrachloride is taken and added into a 50ml round bottom flask, 20ml of normal hexane is added, and the mixture is stirred for 5 to 10 minutes until the mixture is completely dissolved to form anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 120 ℃, and stirring and refluxing for reaction for 1h; then cooling to room temperature, stirring and reacting for 24 hours, decompressing and distilling to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-4.
The nuclear magnetic resonance measurement is carried out on CAT-4 for structural analysis, and the obtained nuclear magnetic resonance carbon spectrum is shown in figure 2. Wherein, 7 peaks appear in the nuclear magnetic resonance carbon spectrum spectrogram, corresponding to 7 carbon atoms in different chemical environments, and the chemical structure of CAT-4 can be obtained by further analysis:
Figure BDA0003453370130000131
example 5
Under nitrogen atmosphere, 152.1mg of 2-propoxyphenol is weighed, added into a Schlenk bottle with 100ml, added with 30ml of toluene, and stirred for 5-10 min until the mixture is completely dissolved to form an anhydrous transparent solution A; under nitrogen atmosphere, adding 95.8mg of titanium tetrachloride into a 50ml round-bottom flask, adding 20ml of dimethylbenzene, and stirring for 5-10 min until the titanium tetrachloride is completely dissolved to obtain anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 60 ℃, and stirring and refluxing for 3h; then cooling to room temperature, stirring and reacting for 16h, distilling under reduced pressure to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-5.
Example 6
Under nitrogen atmosphere, 207.5mg of 2-bromo-4-chlorophenol is weighed and added into a Schlenk bottle with 100ml, 30ml of toluene is added, and stirring is carried out for 5-10 min until complete dissolution, thus obtaining anhydrous transparent solution A; under nitrogen atmosphere, 97.2mg of titanium tetrachloride is taken and added into a 50ml round-bottom flask, 20ml of toluene is added, and stirring is carried out for 5-10 min until complete compatibility is achieved, thus obtaining anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 60 ℃, and stirring and refluxing for 3h; then cooling to room temperature, stirring and reacting for 24 hours, decompressing and distilling to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-6.
Example 7
Under nitrogen atmosphere, weighing 157.1mg of 3-fluoro-4-nitrophenol, adding into a Schlenk bottle with 100ml, adding 30ml of toluene, and stirring for 5-10 min until the 3-fluoro-4-nitrophenol is completely dissolved to obtain an anhydrous transparent solution A; taking 105mg of titanium tetrachloride under the nitrogen atmosphere, adding 20ml of toluene into a 50ml round-bottom flask, and stirring for 5-10 min until the titanium tetrachloride is completely dissolved to obtain anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 60 ℃, and stirring and refluxing for 3h; then cooling to room temperature, stirring and reacting for 24 hours, decompressing and distilling to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-7.
The nuclear magnetic resonance measurement is carried out on CAT-7 for structural analysis, and the obtained magnetic resonance carbon spectrum is shown in figure 3. Wherein, 9 peaks appear in the nuclear magnetic resonance carbon spectrum spectrogram, corresponding to the carbon atoms of 9 different chemical environments, and the chemical structure of CAT-7 can be obtained by further analysis as follows:
Figure BDA0003453370130000141
example 8
Under the nitrogen atmosphere, 174.2mg of 6-methoxy naphthol is weighed, a 100ml Schlenk bottle is added, 30ml toluene is added, and stirring is carried out for 5-10 min until complete compatibility is achieved, thus obtaining anhydrous transparent solution A; under nitrogen atmosphere, 96.3mg of titanium tetrachloride is taken and added into a 50ml round-bottom flask, 20ml of toluene is added, and stirring is carried out for 5-10 min until the titanium tetrachloride is completely dissolved, thus obtaining anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 100 ℃, and stirring and refluxing for 3h; then cooling to room temperature, stirring and reacting for 36h, distilling under reduced pressure to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-8.
Example 9
Under nitrogen atmosphere, 356.1mg of 2,2' -thio (4, 6-dichlorophenol) is weighed, added into a Schlenk bottle with 100ml, added with 30ml of toluene, and stirred for 5-10 min until the mixture is completely dissolved to form anhydrous transparent solution A; taking 104mg of titanium tetrachloride under the nitrogen atmosphere, adding 20ml of toluene into a 50ml round-bottom flask, and stirring for 5-10 min until the titanium tetrachloride is completely dissolved to obtain anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 80 ℃, and stirring and refluxing for 3h; then cooling to room temperature, stirring and reacting for 18h, distilling under reduced pressure to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-9.
Example 10
Under nitrogen atmosphere, weighing 123.2mg of 4-methoxyaniline, adding into a Schlenk bottle with 100ml, adding 30ml of toluene, and stirring for 5-10 min until the mixture is completely dissolved to obtain an anhydrous transparent solution A; under nitrogen atmosphere, 97.2mg of titanium tetrachloride is taken and added into a 50ml round-bottom flask, 20ml of toluene is added, and stirring is carried out for 5-10 min until complete compatibility is achieved, thus obtaining anhydrous transparent solution B; slowly dripping the solution B into the solution A at the temperature of 0 ℃ under the stirring state, stirring for 10min until the solution B is completely dissolved, heating to 100 ℃, and stirring and refluxing for 3h; then cooling to room temperature, stirring and reacting for 24 hours, decompressing and distilling to remove the solvent, separating out the product, washing the product with n-hexane for 3 times, and pumping to obtain the orange solid powder catalyst.
The non-metallocene catalyst was designated CAT-10.
The nuclear magnetic resonance measurement is carried out on CAT-10 for structural analysis, and the obtained nuclear magnetic resonance carbon spectrum is shown in FIG. 4. Wherein, 10 peaks appear in the nuclear magnetic resonance carbon spectrum chart, corresponding to 10 carbon atoms in different chemical environments, and the chemical structure of CAT-10 can be obtained by further analysis as follows:
Figure BDA0003453370130000161
examples 11 to 20
Examples 11 to 20 are olefin polymerization applications of catalysts CAT1 to 10.
The polymerization experiment process is as follows:
in a 250ml stainless steel autoclave, each of which was replaced three times with nitrogen and ethylene, was warmed to 100℃and then 50ml of toluene solvent was added with a feeder, 10ml of MAO (10% toluene solution) as a cocatalyst, 2.0mg of the main catalyst (non-metallocene catalyst of examples 1 to 10) was weighed, washed with 50ml of toluene solvent, and the reaction solution in the feeder was added to the high-pressure polymer, and the pressure was raised to and maintained at 2.0MPa and 80℃for 0.5 hours. After the polymerization reaction was completed, it was cooled and degassed, and then acidic methanol (5%, v/v) was slowly poured to precipitate a polymer. The polymer powder produced was filtered, washed and finally dried at 80 ℃. The specific polymerization results are shown in Table 1.
TABLE 1 catalytic ethylene polymerization results
Figure BDA0003453370130000162
Figure BDA0003453370130000171
Comparative examples
Comparative example polymerization conditions were the same as those of examples 1-10 except that titanium 2- (hydroxy, diphenyl-methyl) phenolate was used as the catalyst, designated catalyst CAT-11. The polymerization results are shown in Table 2.
TABLE 2 catalyst 8 and catalyst 11 ethylene polymerization results
Figure BDA0003453370130000172
As shown in Table 2, the molecular weight of the polyethylene obtained by the CAT-11 catalytic polymerization exceeds 100 ten thousand, and is unsuitable for preparing low molecular weight polyethylene, so that polyethylene wax cannot be prepared by using the catalyst.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (12)

1. A non-metallocene catalyst characterized in that the non-metallocene catalyst has the structure of formula i:
Figure FDA0003453370120000011
wherein M is selected from IVB transition metal atoms;
l is a halogen atom;
x is selected from one of O, NH and S;
R 1 selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups or halogen atoms, R 2 And R is 3 Independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or halogen atoms; alternatively, R 3 Selected from hydrogen, substituted orUnsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, oxygen-containing group, sulfur-containing group, nitrogen-containing group or halogen atom, R 1 And R is 2 Form a cyclic structure, being substituted or unsubstituted C 4 ～C 8 Conjugated olefinic groups of (2);
n is 1 to 3.
2. The non-metallocene catalyst according to claim 1, characterized in that R 1 、R 2 And R is 3 Not both hydrogen.
3. The non-metallocene catalyst according to claim 1, wherein M is Ti, zr or Hf; l is Cl or Br; n is 2; r is R 1 Selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons or halogen atoms, R 2 And R is 3 Independently selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, alkylamine groups having 1 to 12 carbons, nitro groups, or halogen atoms; alternatively, R 3 Selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, alkylamine groups having 1 to 12 carbons, nitro groups or halogen atoms, R 1 And R is 2 Form a cyclic structure, which is unsubstituted C 4 ～C 8 Or C containing an alkoxy substituent or an alkylthio substituent 4 ～C 8 Is a conjugated olefin group of (C).
4. The non-metallocene catalyst according to claim 1, characterized in that it has one of the following structures:
(1)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝H，R 3 ＝CH 3 ；
(2)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝R 3 ＝H；
(3)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝t-Bu,R 2 ＝H,R 3 ＝OCH 3 ；
(4)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝i-OPr，R 2 ＝R 3 ＝H；
(5)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝n-OBu,R 2 ＝R 3 ＝H；
(6)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Br,R 2 ＝H,R 3 ＝Cl；
(7)M＝Ti,X＝O,n＝2,L＝Br,R 1 ＝t-Bu,R 2 ＝H,R 3 ＝OCH 3 ；
(8)M＝Ti,X＝NH,n＝2,L＝Cl,R 1 ＝OCH 3 ,R 2 ＝R 3 ＝H；
(9)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝SCH 3 ,R 2 ＝R 3 ＝H；
(10)M＝Ti,X＝NH,n＝2,L＝Cl,R 1 ＝-OBu，R 2 ＝R 3 ＝H；
(11)M＝Ti,X＝O,n＝2,L＝Cl,R 1 and R is 2 Is cyclic and is-ch=ch-, R 3 ＝H；
(12)M＝Ti,X＝O,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )-CH＝CH-,R 3 ＝H；
(13)M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-, R 3 ＝H；
(14)M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=ch-C (OCH) 3 )＝CH-,R 3 ＝H；
(15)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Cl,R 2 ＝R 3 ＝H；
(16)M＝Ti,X＝O,n＝2,L＝Cl,R 1 ＝Cl,R 2 ＝H,R 3 ＝CH 3 ；
(17)M＝Ti,X＝S,n＝2,L＝Cl,R 1 And R is 2 The ring is formed,and is-ch=ch-, R 3 ＝H；
(18)M＝Ti,X＝NH,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )-C(OCH 3 )＝CH-,R 3 ＝H；
(19)M＝Ti,X＝O,n＝2,L＝Cl,R 1 And R is 2 Is cyclic and is-ch=c (OCH) 3 )-C(OCH 3 )＝CH-,R 3 ＝H。
5. A method for preparing a non-metallocene catalyst, comprising the steps of:
step 1, mixing a transition metal compound and an aryl ligand, and reacting at 50-120 ℃;
step 2, cooling the mixture obtained in the step 1 to 0-30 ℃, and continuing to react in an inert gas environment;
step 3, carrying out post-treatment and drying on the mixture obtained in the step 2 to obtain a non-metallocene catalyst;
wherein the transition metal compound is a compound of IV B transition metal, and the aryl ligand is aryl phenol, aryl sulfur or aryl amine containing or not containing substituent groups.
6. The method for producing a non-metallocene catalyst according to claim 5, wherein the transition metal compound is a compound of Ti, zr or Hf, and the substituent is selected from hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbons, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbons, an oxygen-containing group, a sulfur-containing group or a halogen atom.
7. The method for producing a non-metallocene catalyst according to claim 6, wherein the transition metal compound is a chloride of Ti, zr or Hf, and the substituent is selected from an aliphatic hydrocarbon group having 1 to 12 carbons, an aromatic hydrocarbon group having 6 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkylthio group having 1 to 12 carbons or a halogen atom.
8. The process for preparing a non-metallocene catalyst according to claim 5, wherein the aryl ligand has at least two substituents which are located on adjacent carbons of the aromatic ligand and form a cyclic structure, which is a substituted or unsubstituted C 4 ～C 8 Is a conjugated olefin group of (C).
9. The process for preparing a non-metallocene catalyst according to claim 8, wherein the at least two substituents form a cyclic structure, which is unsubstituted C 4 ～C 8 Or C containing an alkoxy substituent, alkylthio substituent or halogen substituent 4 ～C 8 Conjugated olefins of (a).
10. The method for preparing a non-metallocene catalyst according to claim 5, wherein the transition metal compound and the aryl ligand are dissolved in an organic solvent selected from the group consisting of C, respectively, and then mixed 4 ～C 10 Alkanes, halogenated C 1 ～C 10 Alkanes, C 6 ～C 10 Cycloalkane or C 6 ～C 20 Aromatic hydrocarbons.
11. A process for the polymerization of olefins, wherein the non-metallocene catalyst according to any one of claims 1 to 4 is used as a main catalyst.
12. The process for the polymerization of olefins according to claim 11, wherein the process for the polymerization of olefins uses an organoaluminum as a cocatalyst.
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