CN114853964B - Cyclic olefin block copolymer and preparation method thereof - Google Patents
Cyclic olefin block copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a cycloolefin segmented copolymer and a preparation method thereof, wherein the preparation method comprises the following steps: norbornene and alpha-olefin are used as raw materials, a metallocene catalyst and an alpha-diimine catalyst are used as composite catalysts, and the cycloolefin block copolymer is obtained through polymerization under the action of diethyl zinc and a cocatalyst. The two different catalysts are mutually cooperated, the molecular weight distribution of the copolymer obtained by co-catalysis is wider, and the chain structure is different from that of the norbornene copolymer prepared by any single catalyst; under the action of diethyl zinc, a chain shuttling reaction occurs, so that two polymer chains with different norbornene contents form a block polymer. The use of the composite catalyst can ensure the high catalytic activity and good stability of the catalyst, and the prepared norbornene segmented copolymer has wide molecular weight distribution compared with the norbornene copolymer prepared by any single catalyst, so that the catalyst has better processability.
Description
Technical Field
The invention relates to a cycloolefin block copolymer, which is prepared by catalyzing ethylene (or propylene) and norbornene to copolymerize under the action of diethyl zinc and a cocatalyst, and belongs to the field of olefin polymerization.
Background
The block copolymer is a special polymer prepared by connecting two or more polymer chain segments with different properties, and can combine the excellent properties of a plurality of polymers to obtain a functional polymer material with superior performance. The polymer has controllable molecular weight, and designable molecular structure and composition, and is one of the most significant and challenging research works in the field of high molecular research. The block copolymers can be synthesized by a variety of methods, such as by interaction of functional end groups between different homopolymers, control of the order of monomer addition in living polymerization, and condensation reactions, special initiators, and mechanical forces. Literature (Macromolecules 2007, 40, 7061) studies have found that polyethylene-b-poly (ethylene-co-octene) is efficiently prepared by chain shuttling polymerization and coordination chain transfer polymerization. Cycloolefin copolymers are attracting attention because of their advantages of high transparency, extremely low dielectric constant, excellent moisture barrier properties, high chemical resistance, high glass transition temperature, and the like. Is widely used in the manufacture of various optical lenses, automotive lamp heads, LCD components, electronic and electrical parts, pharmaceutical and food packaging materials, and the like. The cycloolefin copolymer is a high-added value thermoplastic engineering plastic formed by addition copolymerization of cycloolefin and alpha-olefin, and the catalyst for preparing the cycloolefin copolymer is a metallocene catalyst, and the metallocene catalyst can control the molecular weight, the stereoregularity and the comonomer reactivity to a great extent according to the structures of the catalyst and the ligand. Chinese patent CN101125901 relates to a method for preparing cycloolefin copolymer with narrow composition distribution by using metallocene catalyst; chinese patent CN102702433a provides a method for preparing high molecular weight ethylene and norbornene copolymers using half metallocene catalysts; chinese patent CN201110127385.4 provides a method for preparing a high transparent cyclic olefin copolymer with low cyclic olefin content using a metallocene catalyst; chinese patent CN200910100771.7 provides a method for preparing cyclic olefin copolymer with polar group using metallocene catalyst. In addition, non-metallocene catalysts may also catalyze the production of cycloolefin copolymers. Hu reports that bis (benzoin) titanium complex has higher activity for copolymerization of ethylene and norbornene under activation of Methylaluminoxane (MAO), resulting in high molecular weight ethylene-norbornene copolymer (Polymer, 2008, 49, 4552). Late transition metal catalysts have attracted considerable attention from Brookhart et al since the discovery that complexes containing the alpha-diimine ligands Ni (II) and Pa (II) can polymerize alpha-olefins to high molecular weight polymers. Because the late transition metal catalyst has the remarkable characteristics of weak electrophilicity of central metal atoms and strong heteroatom-resistant capability, the catalyst can be used for the homogeneous polymerization of ethylene and the copolymerization of olefin, polar monomer and cycloolefin, thereby producing the functionalized polyolefin material with excellent performance. Chinese patent CN104926686a reports the synthesis of a class of α -diimine catalysts which catalyze the homopolymerization of norbornene and the copolymerization of ethylene norbornene. However, compared with the general metallocene ethylene-cycloolefin copolymer, the polymerization activity of the catalyst is relatively low, and the obtained ethylene-cycloolefin copolymer has higher norbornene content and slightly poorer processability. And the content of norbornene in the cycloolefin copolymer prepared by the metallocene catalyst is low. The present invention therefore combines two catalyst systems, and a chain shuttling polymerization technique, to synthesize a block copolymer of cycloolefins.
Kaminsky W，Arndt M，Beulich I.New materials&kinetic aspects by copolymerization of cyclic olefins with metallocene catalysts[J].Polymeric Materials Science and Engineering，1997，76：18-19、Tritto Incoronata，Boggioni Laura，Ferro Dino R.Metallocene catalyzed ethene-and propene co-norbornene polymerization：Mechanisms from a detailed microstructural analysis[J].Coordination Chemistry Reviews，2006，250(1-2)：212-241、Boggioni Laura，Zampa Cristina，Ravasio Andrea，et al.Propene-norbornene copolymers by C 2 -symmetric metallocene rac-Et(Ind) 2 ZrCl 2 ：Influence of reaction conditions on reactivity and copolymer properties[J]Macromolecules,2008, 41 (14): 5107-5115 the copolymerization of norbornene and ethylene or propylene is catalyzed by metallocene catalyst. Shiono T, sugimoto M, hasan T, et al random copolymer-merization of norbornene with higher l-alkone with anasa-fluorenyl amidodimethyltitanium catalyst [ J]Macromolecules,2008, 41 (22): 8292-8294 uses metallocene catalyst to catalyze the copolymerization of norbornene and long chain alpha-olefin. Nagncopolymerization of Ethylene with Cycloolefins or Cyclodiolefins by a Constrained-Geometry Catalyst[J]Journal of Polymer Science, part a: polymer Chemistry,2005, 43 (6), 1285-1291. Copolymerization of cycloolefins and ethylene is catalyzed with metallocene catalysts having a defined geometry. Yonkin Todd R, connor Eric F, henderson Jason I, et al Neutral, single-component nickel (II) polyolefin catalysts that tolerate heteroatoms [ J ]].Science，2000，287(5452)：460-462、Yang H，Sun WH，Chang F，et al.Vinyl-polymerization of norbornene catalyzed by bis-[N-(substituted methyl)-salicylideneiminato]nickel/MAO system[J]Applied Catalysis, a: general,2003, 252 (2): 261-267, the addition polymerization of cycloolefins or the copolymerization with ethylene is catalyzed by means of late transition metal nickel catalysts. Zhao CT, ribeiro Maria do R, portela M F.addition polymerisation of-vinyl-2-norbornene with nickel bis (acrylic-acrylate-e)/methylaluminoxane system [ J]Journal of Molecular Catalysis A: chemical,2002, 185 (1-2): 81-85, the homopolymerization of cycloolefins is catalyzed by means of the late transition metal nickel. Mi X, ma Z, wang L Y, et al, homo-and copolymerization of norbornene and styrene with Pd-and Ni-based novel bridged dinuclear diimine complexes andMAO [ J ]Macromolecular Chemistry and Physics,2003, 204 (5/6): 868-876 employs late transition metal nickel, palladium to catalyze the copolymerization of norbornene and styrene. Li Y F, gao M L, wu Q.Vinyl polymerization of norbornene by Nickel (II) complex bearing beta-diketiminate ligands [ J].Applied Organometallic Chemistry，2007，21(11)：965-969、Li Y F，Gao M，Gao H Y，et al.Synthesis and structural characterization of ethylene-norbornene copolymer with high norbornene content catalyzed by β-diketiminato nickel/methylaluminoxane[J]European Polymer Journal,2011, 47 (10), 1964-1969 the homo-polymerization of cycloolefins or copolymerization with ethylene is catalyzed by the late transition metal catalyst beta-diimine nickel. Pelastini F, peruch F, lutz P J, et al polymerization of norbornene with CoCl 2 and pyridine bisimine cobalt(II)complexes activated with MAO[J].Macromolecular Rapid Communications，2003，24(13)：768-771. The homo-polymerization of cycloolefins is catalyzed by means of cobalt late transition metals. Mi X, xu D M, yan W D, et al preparation of polynorbornene with beta-diketonate titanium/MAO catalysts [ J ]]Polymer Bulletin,2002, 47 (6), 521-527 catalyzes norbornene homopolymerization with a beta-diketone titanium catalyst, and copolymerization with alpha-olefins or other cycloolefins is not mentioned. Scollard J D, mcConville D H.Living Polymerization of alpha-Olefins by Chelating Diamide Complexes of Titanium [ J ]]Journal of the American Chemical Society 1996, 118 (41), 10008-10009. Active polymerization of alpha-olefins is catalyzed with diamine titanium chelates. Hong M, pan L, li BX, et al Synthesis of novel poly (ethylene-ter-1-hexene-ter-dicyclohexylentadiene) susing bis (. Beta. -enamino-keyalto) titanium catalysts and their applications in preparing polyolefin-graft-poly (epsilon-polycaprolactone) [ J) ]Polymer,2010, 51 (16), 3636-3643 is used to prepare graft copolymers of polyolefins with polycaprolactone by copolymerizing dicyclopentadiene with ethylene and alpha-olefins using a titanium beta-diketonate amine with an N-O ligand to synthesize an elastomer. Mi X, ma Z, wang L Y, et al homo-and copolymerization of ethylene and norbornene with bis (. Beta. -diketiminao) titanium complexes activated with methylaluminoxane [ J]Macromolecular Chemistry and Physics,2008, 46 (5/6): 93-101. The homo-polymerization and copolymerization of norbornene and ethylene are catalyzed by a beta-diimine titanium catalyst, and no researches on copolymerization with other alpha-olefins or copolymerization with other cycloolefins are mentioned.
The polymer obtained by the method has narrow molecular weight distribution, poor processability and needs improvement.
Disclosure of Invention
The main purpose of the invention is to provide a cycloolefin block copolymer and a preparation method thereof, which are used for overcoming the defects of narrow molecular weight distribution and poor processability of cycloolefin and alpha-olefin addition copolymerization products in the prior art.
In order to achieve the above object, the present invention provides a process for preparing a cycloolefin block copolymer, comprising: norbornene and alpha-olefin are used as raw materials, a metallocene catalyst and an alpha-diimine catalyst are used as composite catalysts, and the cycloolefin block copolymer is obtained through polymerization under the action of diethyl zinc and a cocatalyst.
The preparation method of the cycloolefin block copolymer provided by the invention comprises the following steps of:
wherein X is methylene, ethylene or Me 2 Si or Me 2 C, R is H, me, et or Pr.
The preparation method of the cycloolefin block copolymer comprises the step of preparing a metallocene catalyst, wherein the metallocene catalyst is one of ethyl bridged bis (indenyl) zirconium dichloride, dimethyl silicon bridged bis (indenyl) zirconium dichloride, dimethyl carbon bridged bis (tetrahydroindenyl) zirconium dichloride, dimethyl silicon bridged bis [ 1-methyl, 4-phenylindene ] zirconium dichloride and ethylene bridged bis [1,4, 7-trimethylindene ] zirconium dichloride.
The invention relates to a preparation method of a cycloolefin segmented copolymer, wherein the alpha-diimine catalyst is prepared by reacting an alpha-diimine compound with a post-transition metal salt, wherein the post-transition metal salt is one of nickel salt and palladium salt; the alpha-diimine compound has the following structure:
wherein R is 1 Is C 6 -C 60 Aromatic hydrocarbon radical, C 6 -C 60 Is one of heterocyclic aromatic hydrocarbon groups; r is R 2 Is C 6 -C 60 Aromatic hydrocarbon radical, C 6 -C 60 Is one of heterocyclic aromatic hydrocarbon groups; and R is 1 And R is 2 The same or different;
ar has the following structure:
Wherein n=1, 2, 3, 4, 5, 6 or 7.
The preparation method of the cycloolefin block copolymer provided by the invention is characterized in that the alpha-diimine compound has the following structure:
wherein R is a 、R b Is hydrogen, C 1 -C 20 Alkyl, C 6 -C 20 Phenyl, C 6 -C 20 Is one of halogen atom substituted phenyl groups, R a 、R b The same or different; r is R c Is hydrogen, fluorine, chlorine, bromine, C 1 -C 20 C substituted by alkanyl, fluorine 1 -C 20 Alkyl and C 1 -C 20 Is one of the alkoxy groups of (a).
The invention relates to a preparation method of a cycloolefin block copolymer, wherein the post-transition metal salt is (DME) NiBr 2 、(DME)NiCl 2 、(COD)PdClCH 3 、(PhCN) 2 PdCl 2 Or (COD) PdMe (NCMe).
The preparation method of the cycloolefin block copolymer provided by the invention, wherein the alpha-diimine catalyst is one of 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis (2, 6-diisopropyl) benzene imine nickel bromide, 5- (4-hydroxymethyl phenoxy) acenaphthoquinone bis (2, 6-diisopropyl) benzene imine nickel bromide, 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis [2, 6-di (benzhydryl) -4-methyl ] benzene imine nickel bromide and 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis [2, 6-di (benzhydryl) -4-methyl ] benzene imine palladium bromide.
The invention relates to a preparation method of a cycloolefin block copolymer, wherein in the composite catalyst, the molar ratio of a metallocene catalyst to an alpha-diimine catalyst is 1-10:1.
The invention relates to a preparation method of a cycloolefin block copolymer, wherein the mol ratio of norbornene to alpha-olefin is 3-30:1; the saidThe mol ratio of the cocatalyst to the composite catalyst is 100-4000:1; the mol ratio of the diethyl zinc to the composite catalyst is 10-1000:1; the molar concentration of the composite catalyst in the polymerization system is 1 multiplied by 10 -5 -1×10 - 3 mol/L。
The invention relates to a preparation method of a cycloolefin block copolymer, wherein the alpha-olefin is ethylene or propylene; the cocatalyst is MAO, EAO, MMAO, alEt 2 Cl、Al 2 Et 3 Cl 3 、AlEt 3 、Al(i-Bu) 3 、B(C 6 F 5 ) 4 And B (C) 6 H 3 (CF 3 ) 2 ) 4 One of the following; the polymerization temperature is 40-100 ℃; the monomer pressure of the alpha-olefin is 0.1-5MPa.
In order to achieve the above object, the present invention also provides a cycloolefin block copolymer prepared by the above method.
The invention has the beneficial effects that:
the invention provides a preparation method of a cycloolefin segmented copolymer, which is a composite catalyst consisting of an alpha-diimine catalyst and a metallocene catalyst, and adopts a chain shuttling polymerization technology to catalyze ethylene (or propylene) and norbornene to carry out polymerization reaction under the action of diethyl zinc and a cocatalyst. The two different catalysts cooperate with each other, the molecular weight distribution of the copolymer obtained by co-catalysis is wider, and the chain structure is different from that of the norbornene copolymer prepared by any single catalyst.
Under the action of diethyl zinc, a chain shuttling reaction occurs, so that two polymer chains with different norbornene contents form a block polymer. In addition, the number and the proportion of the two active centers can be regulated by regulating the proportion of the metallocene catalyst and the alpha-diimine catalyst, so that the polymerization products with different performances can be obtained. The use of the composite catalyst can ensure the high catalytic activity and good stability of the catalyst, and the prepared norbornene segmented copolymer has wide molecular weight distribution compared with the norbornene copolymer prepared by any single catalyst, so that the catalyst has better processability.
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 preparation method of a cycloolefin block copolymer, which comprises the following steps: norbornene and alpha-olefin are used as raw materials, a metallocene catalyst and an alpha-diimine catalyst are used as composite catalysts, and the cycloolefin block copolymer is obtained through polymerization under the action of diethyl zinc and a cocatalyst.
The invention combines the alpha-diimine catalyst and the metallocene catalyst into a composite catalyst, and under the action of diethyl zinc and a cocatalyst, ethylene (or propylene) and norbornene are catalyzed to be copolymerized, the chain structure of a copolymer obtained by catalyzing the two different catalysts is different from that of a copolymer obtained by catalyzing the single catalyst, and in addition, under the action of diethyl zinc, a chain shuttling reaction can occur between polymer chains, so that two sections of polymer chains with different structures form a block polymer. Therefore, the cycloolefin copolymer prepared by the method has a unique structure and a wide molecular weight distribution, and is beneficial to processing.
In one embodiment, the metallocene catalyst has the following structure:
wherein X is methylene (CH) 2 ) Ethylene (CHCH) 3 )、Me 2 Si or Me 2 C, R is H, me, et or Pr.
In another embodiment, the metallocene catalyst is one of ethyl bridged bis-indenyl zirconium dichloride, dimethyl silicon bridged bis-indenyl zirconium dichloride, dimethyl carbon bridged bis-indenyl zirconium dichloride, ethylene bridged bis (tetrahydroindene) zirconium dichloride, dimethyl silicon bridged bis [ 1-methyl, 4-phenylindene ] zirconium dichloride, and ethylene bridged bis [1,4, 7-trimethylindene ] zirconium dichloride.
In one embodiment, the alpha-diimine catalyst is prepared by reacting an alpha-diimine compound with a late transition metal salt, wherein the late transition metal salt is one of nickel salt and palladium salt; the α -diimine compound has the following structure:
wherein R is 1 Is C 6 -C 60 Aromatic hydrocarbon radical, C 6 -C 60 Is one of heterocyclic aromatic hydrocarbon groups; r is R 2 Is C 6 -C 60 Aromatic hydrocarbon radical, C 6 -C 60 Is one of heterocyclic aromatic hydrocarbon groups; and R is 1 And R is 2 The same or different;
ar has the following structure:
wherein n=1, 2, 3, 4, 5, 6 or 7.
In another embodiment, the α -diimine compound has the structure:
wherein R is a 、R b Is hydrogen, C 1 -C 20 Alkyl, C 6 -C 20 Phenyl, C 6 -C 20 Is one of halogen atom substituted phenyl groups, R a 、R b The same or different; r is R c Is hydrogen, fluorine, chlorine, bromine, C 1 -C 20 C substituted by alkanyl, fluorine 1 -C 20 Alkyl and C 1 -C 20 Is one of the alkoxy groups of (a).
In one embodiment, the late transition metal salt is (DME) NiBr 2 、(DME)NiCl 2 、(COD)PdClCH 3 、(PhCN) 2 PdCl 2 Or (COD) PdMe (NCMe).
In one embodiment, the α -diimine catalyst is one of nickel 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis (2, 6-diisopropyl) benzene imine bromide, nickel 5- (4-hydroxymethyl phenoxy) acenaphthoquinone bis (2, 6-diisopropyl) benzene imine bromide, nickel 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis [2, 6-di (benzhydryl) -4-methyl ] benzene imine bromide, and palladium 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis [2, 6-di (benzhydryl) -4-methyl ] benzene imine bromide.
In one embodiment, the molar ratio of metallocene catalyst to alpha-diimine catalyst in the composite catalyst of the present invention is 1-10:1. The mole ratio of norbornene to alpha-olefin is 3-30:1; the mol ratio of the cocatalyst to the composite catalyst is 100-4000:1; the mol ratio of the diethyl zinc to the composite catalyst is 10-1000:1; the molar concentration of the composite catalyst in the polymerization system is 1X 10 -5 -1×10 -3 mol/L. The α -olefin is ethylene or propylene, and the present invention is not particularly limited. The promoter is MAO, EAO, MMAO, alEt 2 Cl、Al 2 Et 3 Cl 3 、AlEt 3 、Al(i-Bu) 3 、B(C 6 F 5 ) 4 And B (C) 6 H 3 (CF 3 ) 2 ) 4 One of the following; the polymerization temperature is 40-100 ℃; the monomer pressure of the alpha-olefin is 0.1-5MPa.
As an exemplary embodiment, the cycloolefin block copolymer according to the invention can be prepared as follows: adding an organic solvent (such as anhydrous toluene) into a reaction kettle which is filled with ethylene (or propylene) after being replaced by nitrogen for a plurality of times, heating to a certain temperature and keeping the temperature constant, respectively adding norbornene, the composite catalyst, a cocatalyst and diethyl zinc, stirring and introducing ethylene (or propylene) to keep constant pressure in the reactor, polymerizing for 0.5-2 hours, then adding 10mL of acidified ethanol with the volume percentage concentration of 10% until the reaction is ended, filtering out a polymer, washing with water and ethanol, and drying in a vacuum drying oven at 60 ℃ until the weight is constant to obtain a solid polymer product; wherein the mole ratio of norbornene to ethylene 3-30:1; the molar concentration of the composite catalyst in the polymerization system is 1X 10 -5 -1×10 -3 mol/L; the mol ratio of the cocatalyst to the composite catalyst is 100-4000:1; the mol ratio of the diethyl zinc to the composite catalyst is 10-1000:1; the polymerization temperature is 40-100 ℃; the olefin monomer pressure is 0.1-5MPa.
The technical scheme of the invention is further described in detail through specific examples.
In the following examples, the content of norbornene in the polymer was measured by a nuclear magnetic resonance apparatus, and the polymer was dissolved in deuterated chloroform at a measurement temperature of 120 ℃. The number average molecular weight, weight average molecular weight and molecular weight distribution index of the polymer were determined using high temperature gel permeation chromatography (HT-GPC).
Example 1
In a 100ml kettle reactor, 21g of refined norbornene is dissolved in 50ml of refined toluene to prepare a solution, the solution is added into a reactor which is filled with ethylene after being replaced by nitrogen for three times in advance, a cocatalyst and a composite catalyst are added, polymerization reaction is carried out under the conditions of maintaining the polymerization temperature at 70 ℃ and the ethylene pressure at 0.2MPa and stirring, and the composite catalyst is 7 mu mol of ethyl bridged diindenyl zirconium dichloride and 2 mu mol of 5- [4- (2-hydroxyethyl) phenyl group ]The mole ratio of the promoter (MAO) to the composite catalyst is 200, the mole ratio of the diethyl zinc to the composite catalyst is 800:1, the mole ratio of the norbornene to the ethylene is 30, and the reaction time is 0.5h. After 0.5h of reaction, the reaction is stopped, the reaction solution is poured into 10mL of 10 percent by volume of acidified ethanol to stop the reaction, the polymer is filtered out, and is washed by water and ethanol and then dried to constant weight in a vacuum drying oven at 60 ℃ to obtain 2.34 g of solid polymer product with the catalyst activity of 5.2 multiplied by 10 5 g·mol -1 ·h -1 The norbornene content of the polymer product was 50% by nuclear magnetic resonance measurement, the weight average molecular weight was 75400 by GPC measurement, and the molecular weight distribution was 7.01.
Example 2
In a 100ml kettle reactor, the refined norbornene is dissolved in 50ml refined toluene to prepare a solution, and the solution is then usedThe solution was added to a reactor, which was purged three times with nitrogen and then refilled with ethylene, and the cocatalyst and the composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 40 ℃, the ethylene pressure was 0.2MPa, the ethylene pressure was 8. Mu. Mol of ethyl bridged bis indenyl zirconium dichloride and 2. Mu. Mol of 5- (4-hydroxymethylphenyl) acenaphthoquinone bis (2, 6-diisopropyl) phenylimine nickel bromide were combined, the molar ratio of cocatalyst (MAO) to combined catalyst was 3900, the molar ratio of diethyl zinc to combined catalyst was 600:1, the molar ratio of norbornene to ethylene was 3, and the reaction time was 2h. A solid polymer product of 22.29 g and a catalyst activity of 1.15X10 was obtained 6 g·mol -1 ·h -1 The norbornene content was 33%, the weight average molecular weight was 65700, and the molecular weight distribution was 7.44.
Example 3
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 70℃and ethylene pressure 0.3MPa, 6. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 2. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]The molar ratio of the cocatalyst (EAO) to the composite catalyst is 1500, the molar ratio of the diethyl zinc to the composite catalyst is 100:1, the molar ratio of the norbornene to the ethylene is 15, and the reaction time is 0.5h. 9.96 g of a solid polymer product was obtained, and the catalyst activity was 2.49X 10 6 g·mol -1 ·h -1 The norbornene content was 48%, the weight average molecular weight was 69600, and the molecular weight distribution was 6.45.
Example 4
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature of 80 ℃ and ethylene pressure of 2.0MPa and stirring condition 6. Mu. Mol of ethylene-bridged bis (tetrahydroindene) zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]The mole ratio of the cocatalyst (MMAO) to the composite catalyst is 1500, the mole ratio of diethyl zinc to the composite catalyst is 200:1, the mole ratio of norbornene to ethylene is 15, and the reaction time is 0.5h. 11.04 g of solid polymer product was obtained, and the catalyst activity was 2.76X10 6 g·mol -1 ·h -1 The norbornene content was 28%, the weight average molecular weight was 162600, and the molecular weight distribution was 7.33.
Example 5
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 70 ℃, the ethylene pressure was 5.0MPa, 8. Mu. Mol of dimethylcarbon bridged bis indenyl zirconium dichloride, and 1. Mu. Mol of 5- (4-hydroxymethylphenyl) acenaphthoquinone bis (2, 6-diisopropyl) phenylimine nickel bromide were combined, the molar ratio of cocatalyst (MMAO) to combined catalyst was 2000, the molar ratio of diethyl zinc to combined catalyst was 300:1, the molar ratio of norbornene to ethylene was 20, the control pressure was 5.0MPa, and the reaction time was 0.5h. 11.67 g of solid polymer product was obtained, and the catalyst activity was 2.60X 10 6 g·mol -1 ·h -1 The norbornene content was 54%, the weight average molecular weight was 186700, and the molecular weight distribution was 7.32.
Example 6
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 70 ℃ and ethylene pressure 0.5MPa,7 mu mol of dimethyl silicon bridged bis [ 1-methyl, 4-phenylindene]Zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]]Composite catalyst of acenaphthoquinone bis (2, 6-diisopropyl) phenylimine nickel bromide, cocatalyst (AlEt) 2 Cl) and the composite catalyst were 1500, the molar ratio of diethyl zinc and the composite catalyst was 100:1, the molar ratio of norbornene and ethylene was 5, and the reaction time was 0.5h. 11.57 g of solid polymer product was obtained, and the catalyst activity was 2.89X 10 5 g·mol -1 ·h -1 The norbornene content was 36%, the weight average molecular weight was 82900, and the molecular weight distribution was 8.47.
Example 7
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 60℃and ethylene pressure 1.5MPa, 7. Mu. Mol ethylene-bridged bis [1,4, 7-trimethylindene ]Zirconium yl dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Composite catalyst of acenaphthoquinone bis (2, 6-diisopropyl) phenylimine nickel bromide, cocatalyst (AlEt) 2 Cl) and the composite catalyst were 1500, the molar ratio of diethyl zinc and the composite catalyst was 80:1, the molar ratio of norbornene and ethylene was 25, and the reaction time was 0.5h. 9.25 g of solid polymer product was obtained, and the catalyst activity was 2.31X10 6 g·mol -1 ·h -1 Norbornene content was 58%, weight average molecular weight was 179500, molecular weight distribution was 7.72.
Example 8
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 100℃and the ethylene pressure was 1.0MPa, 7. Mu. Mol of ethylene-bridged bis [1,4, 7-trimethylindene]Zirconium yl dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of nickel phenylimine bromide, cocatalyst (AlEt 3 ) The mol ratio of the catalyst to the composite catalyst is 500, the mol ratio of diethyl zinc to the composite catalyst is 200:1, the mol ratio of norbornene to ethylene is 4, and the catalyst is reacted The time was 1h. 10.34 g of solid polymer product was obtained, and the catalyst activity was 1.29X 10 6 g·mol -1 ·h -1 The norbornene content was 29%, the weight average molecular weight was 153700, and the molecular weight distribution was 7.45.
Example 9
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which propylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 70℃and the propylene pressure was 1.0MPa, 7. Mu. Mol of ethylene-bridged bis [1,4, 7-trimethylindene]Zirconium yl dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]The molar ratio of the cocatalyst (MAO) to the composite catalyst is 500, the molar ratio of the diethyl zinc to the composite catalyst is 600:1, the molar ratio of the norbornene to the propylene is 4, and the reaction time is 0.5h. 10.02 g of solid polymer product and 2.51X10 g of catalyst activity were obtained 6 g·mol -1 ·h -1 The norbornene content was 22%, the weight average molecular weight was 223200, and the molecular weight distribution was 6.24.
Example 10
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 100℃and ethylene pressure 0.5MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 500, the mol ratio of diethyl zinc to the composite catalyst is 500:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. 11.72 g of solid polymer product was obtained, and the catalyst activity was 2.93X 10 6 g·mol -1 ·h -1 Norbornene content50% by weight, 96800 by weight and 7.43 by weight.
Example 11
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 100℃and the ethylene pressure was 0.5MPa, 7. Mu. Mol of ethylene-bridged bis [1,4, 7-trimethylindene]Zirconium yl dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 H 3 (CF 3 ) 2 ) 4 ) The molar ratio of the catalyst to the composite catalyst is 500, the molar ratio of the diethyl zinc to the composite catalyst is 200:1, the molar ratio of the norbornene to the ethylene is 10, and the reaction time is 0.5h. 10.57 g of solid polymer product was obtained, and the catalyst activity was 2.64X 10 6 g·mol -1 ·h -1 The norbornene content was 44%, the weight average molecular weight was 93800, and the molecular weight distribution was 7.84.
Example 12
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 100 ℃, ethylene pressure 0.5MPa,7 mu mol of dimethyl silicon bridged bis [ 1-methyl, 4-phenylindene]Zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 800, the mol ratio of diethyl zinc to the composite catalyst is 800:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 14.34 g was obtained, the catalyst activity was 3.56X10 6 g·mol -1 ·h -1 Norbornene content of 47%, weight average molecular weight of 84700, molecular weight distribution of7.40。
Example 13
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 80℃and ethylene pressure 0.5MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]The molar ratio of the cocatalyst (MMAO) to the composite catalyst is 800, the molar ratio of the diethyl zinc to the composite catalyst is 300:1, the molar ratio of the norbornene to the ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 14.24 g was obtained, the catalyst activity was 3.56X10 6 g·mol -1 ·h -1 The norbornene content was 50%, the weight average molecular weight was 90400, and the molecular weight distribution was 7.63.
Example 14
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 100℃and ethylene pressure 0.4MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 800, the mol ratio of diethyl zinc to the composite catalyst is 800:1, the mol ratio of norbornene to ethylene is 21, and the reaction time is 0.5h. A solid polymer product of 13.44 g was obtained, the catalyst activity being 3.36X 10 6 g·mol -1 ·h -1 The norbornene content was 57%, the weight average molecular weight was 102100, and the molecular weight distribution was 7.50.
Example 15
In a 100ml kettle reactor, the refined norbornene is dissolved in 50ml refined toluene to prepareThe solution is added into a reactor which is filled with ethylene after being replaced by nitrogen three times in advance, and the cocatalyst and the composite catalyst are added under the condition of stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 50 ℃ and ethylene pressure 4.0MPa,7 mu mol of dimethyl silicon bridged bis [ 1-methyl, 4-phenylindene]Zirconium dichloride and 2. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 800, the mol ratio of diethyl zinc to the composite catalyst is 500:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 1.0h. A solid polymer product of 22.94 g was obtained, the catalyst activity was 2.55X10 6 g·mol -1 ·h -1 The norbornene content was 47%, the weight average molecular weight was 98300, and the molecular weight distribution was 6.26.
Example 16
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: composite catalyst of dimethyl carbon bridged diindenyl zirconium dichloride and 1. Mu. Mol of 5- (4-hydroxymethylphenyl) acenaphthoquinone bis (2, 6-diisopropyl) phenyliminium nickel bromide with polymerization temperature 100℃and ethylene pressure 0.5MPa, cocatalyst (AlEt) 2 Cl) and the composite catalyst are in a molar ratio of 1000, the mol ratio of diethyl zinc and the composite catalyst is 1000:1, the mol ratio of norbornene and ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 14.05 g was obtained, the catalyst activity was 3.51X10 6 g·mol -1 ·h -1 The norbornene content was 50%, the weight average molecular weight was 91500, and the molecular weight distribution was 7.35.
Example 17
Dissolving refined norbornene in 50ml refined toluene in 100ml kettle reactor to obtain solution, adding the solution into reactor with propylene replaced by nitrogen three times, adding cocatalyst and composite catalyst under stirringAnd (3) a chemical agent. Wherein, the polymerization conditions are as follows: polymerization temperature 70℃and propylene pressure 2.0MPa, 8. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of nickel phenylimine bromide, promoter (Al 2 Et 3 Cl 3 ) The mol ratio of the catalyst to the composite catalyst is 1500, the mol ratio of diethyl zinc to the composite catalyst is 800:1, the mol ratio of norbornene to propylene is 15, and the reaction time is 0.5h. A solid polymer product of 19.94 g was obtained with a catalyst activity of 4.43X10 6 g·mol -1 ·h -1 The norbornene content was 50%, the weight average molecular weight was 98700, and the molecular weight distribution was 7.21.
Example 18
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 80℃and ethylene pressure 0.5MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 H 3 (CF 3 ) 2 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 1000, the mol ratio of diethyl zinc to the composite catalyst is 50:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. 17.82 g of solid polymer product was obtained, and the catalyst activity was 4.45X10 6 g·mol -1 ·h -1 The norbornene content was 41%, the weight average molecular weight was 115300, and the molecular weight distribution was 7.10.
Example 19
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 100℃and the ethylene pressure was 0.5MPa, 7. Mu. Mol of ethylene Bridged bis (tetrahydroindene) zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 H 3 (CF 3 ) 2 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 2000, the mol ratio of diethyl zinc to the composite catalyst is 200:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. 21.14 g of solid polymer product was obtained, and the catalyst activity was 5.28X10 6 g·mol -1 ·h -1 The norbornene content was 49%, the weight average molecular weight was 91100, and the molecular weight distribution was 6.13.
Example 20
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 70℃and ethylene pressure 0.5MPa, 5. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Composite catalyst of acenaphthoquinone bis (2, 6-diisopropyl) phenylimine nickel bromide, cocatalyst (AlEt) 3 ) The mol ratio of the catalyst to the composite catalyst is 800, the mol ratio of diethyl zinc to the composite catalyst is 500:1, the mol ratio of norbornene to ethylene is 18, and the reaction time is 0.5h. A solid polymer product of 12.21 g was obtained, the catalyst activity being 4.07X 10 6 g·mol -1 ·h -1 The norbornene content was 55%, the weight average molecular weight was 98200, and the molecular weight distribution was 8.94.
Example 21
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 100℃and ethylene pressure 3.0MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 2. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite of phenylimine palladium bromideCatalyst, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 1000, the mol ratio of diethyl zinc to the composite catalyst is 300:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 19.64 g was obtained with a catalyst activity of 4.36X 10 6 g·mol -1 ·h -1 The norbornene content was 45%, the weight average molecular weight was 99800, and the molecular weight distribution was 7.15.
Example 22
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 60℃and ethylene pressure 1.0MPa, 7. Mu. Mol of dimethylsilyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 2000, the mol ratio of diethyl zinc to the composite catalyst is 700:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. 21.99 g of a solid polymer product was obtained, and the catalyst activity was 5.49X 10 6 g·mol -1 ·h -1 The norbornene content was 49%, the weight average molecular weight was 90800, and the molecular weight distribution was 6.17.
Example 23
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 100℃and ethylene pressure 0.5MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 H 3 (CF 3 ) 2 ) 4 ) Molar ratio to composite catalystThe value is 800, the mol ratio of diethyl zinc to the composite catalyst is 500:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 15.94 g and a catalyst activity of 3.98X10 were obtained 6 g·mol -1 ·h -1 The norbornene content was 47%, the weight average molecular weight was 98400, and the molecular weight distribution was 7.52.
Example 24
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 80℃and ethylene pressure 1.0MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 1300, the mol ratio of diethyl zinc to the composite catalyst is 200:1, the mol ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 16.89 g was obtained, the catalyst activity was 4.22X 10 6 g·mol -1 ·h -1 The norbornene content was 50%, the weight average molecular weight was 90400, and the molecular weight distribution was 7.98.
Example 25
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which propylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 90℃and propylene pressure 1.5MPa, 7. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 2. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of nickel phenylimine bromide, cocatalyst (Al (i-Bu) 3 ) The mol ratio of the catalyst to the composite catalyst is 800, the mol ratio of diethyl zinc to the composite catalyst is 80:1, the mol ratio of norbornene to propylene is 10, and the reaction time is 0.5h. Obtaining a solid polymer product14.85 g and a catalyst activity of 3.30X10 6 g·mol -1 ·h -1 The norbornene content was 46%, the weight average molecular weight was 91100, and the molecular weight distribution was 7.92.
Example 26
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 70 ℃ and ethylene pressure 1.5MPa,3 mu mol of dimethyl silicon bridged bis [ 1-methyl, 4-phenylindene]A composite catalyst of zirconium dichloride and 3 mu mol of 5- (4-hydroxymethyl phenyl) acenaphthoquinone bis (2, 6-diisopropyl) phenylimine nickel bromide, the molar ratio of a cocatalyst (EAO) to the composite catalyst is 1000, the molar ratio of diethyl zinc to the composite catalyst is 200:1, the molar ratio of norbornene to ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 13.94 g was obtained, the catalyst activity was 3.49X 10 6 g·mol -1 ·h -1 The norbornene content was 44%, the weight average molecular weight was 98400, and the molecular weight distribution was 7.67.
Example 28
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which ethylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 70℃and ethylene pressure 0.5MPa, 6. Mu. Mol of dimethylsilyl-bridged bis-indenyl zirconium dichloride and 2. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]The molar ratio of the cocatalyst (MAO) to the composite catalyst is 1500, the molar ratio of the diethyl zinc to the composite catalyst is 50:1, the molar ratio of the norbornene to the ethylene is 10, and the reaction time is 0.5h. A solid polymer product of 12.24 g was obtained, the catalyst activity 3.06X10 6 g·mol -1 ·h -1 The norbornene content was 43%, the weight average molecular weight was 100500, and the molecular weight distribution was 6.41.
Example 29
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which propylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 90℃and propylene pressure 0.2MPa, 5. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 1. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl ]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]The molar ratio of the cocatalyst (MAO) to the composite catalyst is 800, the molar ratio of the diethyl zinc to the composite catalyst is 1000:1, the molar ratio of the norbornene to the propylene is 25, and the reaction time is 1.0h. 17.74 g of a solid polymer product was obtained, and the catalyst activity was 2.96X 10 6 g·mol -1 ·h -1 The norbornene content was 59%, the weight average molecular weight was 99800, and the molecular weight distribution was 8.89.
Example 30
In a 100ml kettle reactor, refined norbornene was dissolved in 50ml of refined toluene to prepare a solution, and the solution was added to a reactor in which propylene was charged after three times of nitrogen substitution in advance, and a cocatalyst and a composite catalyst were added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 70 ℃, the propylene pressure was 0.5MPa, 7. Mu. Mol of a composite catalyst of dimethyl carbon bridged bis indenyl zirconium dichloride and 1 mol of 5- (4-hydroxymethylphenyl) acenaphthoquinone bis (2, 6-diisopropyl) phenylimine nickel bromide, the molar ratio of cocatalyst (MAO) to composite catalyst was 2000, the molar ratio of diethyl zinc to composite catalyst was 500:1, the molar ratio of norbornene to propylene was 10, and the reaction time was 0.5h. A solid polymer product of 12.84 g was obtained, the catalyst activity was 3.21X 10 6 g·mol -1 ·h -1 The norbornene content was 45%, the weight average molecular weight was 90200, and the molecular weight distribution was 7.78.
Example 31
In a 100ml kettle reactor, dissolving refined norbornene in 50ml refined toluene to prepare a solution, adding the solution into a reactor which is replaced by nitrogen three times in advance and then is filled with propylene,adding the cocatalyst and the composite catalyst under stirring. Wherein, the polymerization conditions are as follows: polymerization temperature 80℃and propylene pressure 1.0MPa, 2. Mu. Mol of ethyl-bridged bis-indenyl zirconium dichloride and 2. Mu. Mol of 5- [4- (2-hydroxyethyl) phenyl]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Composite catalyst of palladium bromide of phenylimine, cocatalyst (B (C) 6 F 5 ) 4 ) The mol ratio of the catalyst to the composite catalyst is 1000, the mol ratio of diethyl zinc to the composite catalyst is 50:1, the mol ratio of norbornene to propylene is 18, and the reaction time is 0.5h. A solid polymer product of 19.34 g was obtained with a catalyst activity of 4.84X10 6 g·mol -1 ·h -1 The norbornene content was 50%, the weight average molecular weight was 105300, and the molecular weight distribution was 6.44.
Comparative example 1
In a 100ml kettle reactor, refined norbornene is dissolved in 50ml refined toluene to prepare a solution, the solution is added into a reactor which is replaced three times by nitrogen in advance and then is filled with ethylene, and a cocatalyst and a main catalyst are added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 70℃and the ethylene pressure was 0.3MPa, 6. Mu. Mol of ethyl bridged diindenyl zirconium dichloride, the molar ratio of cocatalyst EAO to the main catalyst was 1500, the molar ratio of norbornene to ethylene was 15, and the reaction time was 0.5h. 11.4 g of solid polymer product and 3.80×10 catalyst activity were obtained 6 g·mol -1 ·h -1 The norbornene content was 37%, the weight average molecular weight was 90200, and the molecular weight distribution was 2.25. The tensile strength was 40.1MPa, and the elongation at break was 1.9%.
Comparative example 2
In a 100ml kettle reactor, refined norbornene is dissolved in 50ml refined toluene to prepare a solution, the solution is added into a reactor which is replaced three times by nitrogen in advance and then is filled with ethylene, and a cocatalyst and a main catalyst are added under stirring. Wherein, the polymerization conditions are as follows: the polymerization temperature was 70℃and the ethylene pressure was 0.3MPa, and the main catalyst was 2. Mu. Mol of 5- [4- (2-hydroxyethyl) phenoxy]Acenaphthoquinone bis [2, 6-bis (benzhydryl) -4-methyl]Nickel bromide of benzene imine, molar ratio of catalyst promoter EAO to main catalyst is1500, the molar ratio of norbornene to ethylene was 15 and the reaction time was 0.5h. A solid polymer product of 1.25 g and a catalyst activity of 1.2X10 were obtained 5 g·mol -1 ·h -1 The norbornene content was 58%, the weight average molecular weight was 55200, and the molecular weight distribution was 2.60. The tensile strength was 60.2MPa, and the elongation at break was 1.2%.
Comparative example 3
The polymers obtained in comparative example 1 and comparative example 2 were mixed in a mass ratio of 3:1, and the norbornene content of the obtained mixture was 42%, the tensile strength was 38.0MPa, and the elongation at break was 1.4%.
In comparative example 3, the polymers obtained by catalytic polymerization of the two catalysts were physically mixed again, and the obtained mixture was not uniformly mixed, and the mechanical properties were also poor. The polymer obtained in example 3 had a tensile strength of 58.0MPa and an elongation at break of 1.7%. The polymer obtained by catalyzing the composite catalyst under the action of the chain shuttling agent diethyl zinc has two chain segment structures with different norbornene proportions on a macromolecular chain segment, is a block copolymer, can integrate the advantages of two different polymers, and has mechanical properties better than those of a mixture of the two polymers.
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 (9)
1. A preparation method of a cycloolefin block copolymer is characterized by comprising the following steps: using norbornene and alpha-olefin as raw materials, using a metallocene catalyst and an alpha-diimine catalyst as composite catalysts, and polymerizing under the action of diethyl zinc and a cocatalyst to obtain a cycloolefin block copolymer;
Wherein the metallocene catalyst has the following structure:
wherein X is methylene, ethylene or Me 2 Si or Me 2 C, R is H, me, et or Pr;
the alpha-diimine catalyst is prepared by reacting an alpha-diimine compound with a late transition metal salt, wherein the late transition metal salt is one of nickel salt and palladium salt; the alpha-diimine compound has the following structure:
wherein R is 1 Is C 6 -C 60 Aromatic hydrocarbon radical, C 6 -C 60 Is one of heterocyclic aromatic hydrocarbon groups; r is R 2 Is C 6 -C 60 Aromatic hydrocarbon radical, C 6 -C 60 Is one of heterocyclic aromatic hydrocarbon groups; and R is 1 And R is 2 The same or different;
ar has the following structure:
wherein n=1, 2, 3, 4, 5, 6 or 7.
2. The method for preparing a cycloolefin block copolymer according to claim 1, wherein the metallocene catalyst is one of ethyl bridged bis-indenyl zirconium dichloride, dimethylsilicon bridged bis-indenyl zirconium dichloride, dimethylcarbonyl bridged bis-indenyl zirconium dichloride, ethylene bridged bis (tetrahydroindenyl) zirconium dichloride, dimethylsilicon bridged bis [ 1-methyl, 4-phenylindene ] zirconium dichloride and ethylene bridged bis [1,4, 7-trimethylindene ] zirconium dichloride.
3. The method for producing a cycloolefin block copolymer according to claim 1, characterized in that the α -diimine compound has the following structure:
Wherein R is a 、R b Is hydrogen, C 1 -C 20 Alkyl, C 6 -C 20 Phenyl, C 6 -C 20 Is one of halogen atom substituted phenyl groups, R a 、R b The same or different; r is R c Is hydrogen, fluorine, chlorine, bromine, C 1 -C 20 C substituted by alkanyl, fluorine 1 -C 20 Alkyl and C 1 -C 20 Is one of the alkoxy groups of (a).
4. The process for producing a cycloolefin block copolymer according to claim 3, characterized in that the late transition metal salt is (DME) NiBr 2 、(DME)NiCl 2 、(COD)PdClCH 3 、(PhCN) 2 PdCl 2 Or (COD) PdMe (NCMe).
5. The method for preparing a cycloolefin block copolymer according to claim 4, wherein the α -diimine catalyst is one of nickel 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis (2, 6-diisopropyl) benzene imine bromide, nickel 5- (4-hydroxymethyl phenoxy) acenaphthoquinone bis (2, 6-diisopropyl) benzene imine bromide, nickel 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis [2, 6-di (benzhydryl) -4-methyl ] benzene imine bromide, and palladium 5- [4- (2-hydroxyethyl) phenoxy ] acenaphthoquinone bis [2, 6-di (benzhydryl) -4-methyl ] benzene imine bromide.
6. The method for producing a cycloolefin block copolymer according to claim 1, characterized in that the molar ratio of the metallocene catalyst to the α -diimine catalyst in the composite catalyst is 1 to 10:1; the cocatalyst is one or more of alkyl aluminum, alkyl aluminoxane and boride.
7. According to the weightsThe process for preparing a cycloolefin block copolymer according to claim 1, characterized in that the molar ratio of norbornene to α -olefin is 3 to 30:1; the mol ratio of the cocatalyst to the composite catalyst is 100-4000:1; the mol ratio of the diethyl zinc to the composite catalyst is 10-1000:1; the molar concentration of the composite catalyst in the polymerization system is 1 multiplied by 10 -5 -1×10 -3 mol/L。
8. The method for producing a cycloolefin block copolymer according to claim 1, characterized in that the α -olefin is ethylene or propylene; the cocatalyst is MAO, EAO, MMAO, alEt 2 Cl、Al 2 Et 3 Cl 3 、AlEt 3 、Al(i-Bu) 3 、B(C 6 F 5 ) 4 And B (C) 6 H 3 (CF 3 ) 2 ) 4 One of the following; the polymerization temperature is 40-100 ℃; the monomer pressure of the alpha-olefin is 0.1-5MPa.
9. A cyclic olefin block copolymer prepared by the process of any one of claims 1-8.
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