CN118373937A - Terpolymer of isoprene, alpha-olefin and cycloolefin compounds and preparation method thereof - Google Patents

Abstract

The invention provides a terpolymer prepared from isoprene, alpha-olefin compounds and cycloolefin compounds, wherein the main chain of the terpolymer comprises cycloolefin units, isoprene units and alpha-olefin units; the content of the cycloolefin unit is more than 3mol% and less than 20mol%, the content of the isoprene unit is more than 10mol% and less than 85mol%, and the content of the alpha-olefin unit is more than 10mol% and less than 85mol% based on the terpolymer main chain. Compared with polyisoprene, the terpolymer provided by the invention has excellent strength and elongation at break, and simultaneously maintains high weather resistance, aging resistance, ozone resistance and crack growth resistance.

Description

Terpolymer of isoprene, alpha-olefin and cycloolefin compounds and preparation method thereof

Technical Field

The invention relates to the technical field of copolymers, in particular to a terpolymer of isoprene, alpha-olefin and cycloolefin compounds and a preparation method thereof.

Background

Elastomeric materials are used in various fields for their excellent mechanical properties. In recent years, the performance requirements for elastomer materials have been increasingly diversified, and elastomer materials having excellent properties such as high tensile strength, high elongation at break, low temperature resistance, and crack growth resistance have been desired.

The ethylene homopolymer is plastic, the polyisoprene is rubber, and the cyclic olefin polymer is transparent resin; while polyethylene molecular chains have large flexibility, strong crystallization capability, higher modulus and strength, good toughness and tear resistance, isoprene rubber molecular chains have excellent flexibility and elasticity, but have low tensile and tear strength. If ethylene, isoprene and cyclic olefin monomer are copolymerized to prepare a novel plastic-rubber, so that the novel plastic-rubber has the elasticity of rubber, the toughness and tearing of plastic, and the performances of wear resistance, fatigue resistance, thermal oxidative aging resistance and the like are improved, and the novel plastic-rubber material is hopeful to become a novel rubber-plastic material with excellent performances.

In the patent documents disclosed heretofore, the conjugated diene monomer in the conjugated diene and non-conjugated olefin copolymer is mostly butadiene, and the non-conjugated diene monomer is ethylene. The conjugated diene in the conjugated diene/non-conjugated diene multipolymer is butadiene, the non-conjugated diene is ethylene, and the third monomer is an aromatic compound (mainly styrene). However, ethylene, conjugated diene and cyclic olefin monomers have different polymerization mechanisms and large polymerization activities, and copolymerization is difficult to achieve, and ethylene, cycloolefin and isoprene terpolymers have not been reported so far.

Disclosure of Invention

The technical problem solved by the invention is to provide a terpolymer of isoprene, alpha-olefin and cyclic olefin compounds, which can realize copolymerization of isoprene, alpha-olefin and cyclic olefin compounds, and the copolymer has higher elongation at break and tensile strength.

In view of this, the present application provides a terpolymer prepared from isoprene, an α -olefin compound and a cycloolefin compound, the terpolymer main chain comprising cycloolefin units, isoprene units and α -olefin units; the content of the cycloolefin unit is more than 3mol% and less than 20mol%, the content of the isoprene unit is more than 10mol% and less than 85mol%, and the content of the alpha-olefin unit is more than 10mol% and less than 85mol% based on the terpolymer main chain.

Preferably, the terpolymer is a random copolymer.

Preferably, the isoprene units consist of 1, 4-structural units and 3, 4-structural units, and the content of 3, 4-structural units is less than 70mol% based on the total amount of isoprene units.

Preferably, the cyclic olefin compound is selected from the group consisting of a compound of the structure of formula I, a compound of the structure of formula II, a compound of the structure of formula III, and a compound of the structure of formula IV:

A formula I; A formula II; formula III; A formula IV;

R in the formula I is selected from a hydrogen atom, a C1-6 hydrocarbon group, a phenyl group, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group or a silicon-containing group;

n in formula III is 0,1 or 2;

r in formula IV is selected from a hydrogen atom, a C1-6 hydrocarbon group, a phenyl group, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a silicon-containing group.

Preferably, the alpha-olefin compound comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene or 1-octene; the cycloolefin compound includes at least one of norbornene, dicyclopentadiene, tricyclopentadiene, tetracyclododecene, vinyl norbornene, cyclohexene and ethylidene norbornene.

Preferably, the glass transition temperature of the terpolymer is-50-20 ℃, and the melting point is below 130 ℃ or does not have the melting point.

Preferably, the number average molecular weight of the terpolymer is 20000 or more, and the molecular weight distribution of the terpolymer is 1 to 10.

The application also provides a preparation method of the terpolymer, which comprises the following steps:

polymerizing alpha-olefin compounds, isoprene and cycloolefin compounds in a reaction medium under the action of a catalytic system to obtain a multipolymer;

the catalyst system comprises an organoboron salt compound, an organoaluminum compound and a rare earth metal complex;

The rare earth metal complex has the structure of formula V:

A formula V;

in the formula V, M is selected from one of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, gadolinium, ytterbium and lutetium;

R ¹、R²、R³、R⁴ and R ⁵ are independently selected from the group consisting of a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 20 carbon atoms, an aralkyl group containing 6 to 20 carbon atoms, a silyl group containing 1 to 14 carbon atoms; or two or more of R ¹ to R ⁵ may be linked to each other to form an alicyclic or aromatic ring;

e is O, S or N, R ₂ is methyl, ethyl, isopropyl, phenyl or substituted phenyl;

X ₁ and X ₂ are monoanionic ligands, X ₁ and X ₂ are independently selected from hydrogen, a linear aliphatic group, a branched aliphatic group or an alicyclic group having 1 to 20 carbon atoms, phenyl, a linear alkyl group, a branched alkyl group, a cyclic aliphatic group or an aromatic group-substituted phenyl group having 1 to 20 carbon atoms, a linear alkoxy group or a branched alkoxy group having 1 to 20 carbon atoms, a linear alkylamino group or a branched alkylamino group having 1 to 20 carbon atoms, a linear arylamino group or a branched arylamino group having 1 to 20 carbon atoms, a linear or branched silyl group having 1 to 20 carbon atoms, a borono group, an allyl derivative or halogen;

L is a neutral Lewis base;

w is an integer of 0 to 3.

Preferably, the reaction medium is selected from one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes.

Preferably, the organoboron salt compound is an ionic compound formed from an organoboron anion and a cation; the organoboron anion is selected from tetraphenylborate ([ BPh ₄]^-), tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C ₆F₅)₄]^-), tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl), phenyl ] borate or undecahydride-7, 8-dicarbaundecaborate, the cation being selected from carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations or ferrocenium cations containing transition metals;

The organoaluminum compound is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum or ethyldi (p-tolylaluminum).

The application provides a terpolymer of isoprene, alpha-olefin and cycloolefin compounds, which is prepared from isoprene, alpha-olefin compounds and cycloolefin compounds, wherein the main chain of the terpolymer comprises cycloolefin units, isoprene units and alpha-olefin units; the content of the cycloolefin unit is more than 3mol% and less than 20mol%, the content of the isoprene unit is more than 10mol% and less than 85mol%, and the content of the alpha-olefin unit is more than 10mol% and less than 85mol% based on the terpolymer main chain; the copolymer provided by the application has three copolymers with adjustable monomer sequence distribution, and can obtain the copolymer with the elongation reaching 1000% and the tensile strength reaching 15MPa according to different monomer contents.

The application also provides a preparation method of the terpolymer, which ensures that alpha-olefin, cycloolefin and isoprene monomers have high catalytic activity by adopting a specific catalyst and changing a polymerization reaction process, realizes the copolymerization of the alpha-olefin, cycloolefin and isoprene with three polymerization reaction mechanisms and polymerization activities with great difference, and obtains the copolymer with different copolymerization unit contents.

Drawings

FIG. 1 is a ¹ H NMR spectrum of a copolymer sample prepared in example 7 of the present invention;

FIG. 2 is a ¹ H NMR spectrum of a copolymer sample prepared in example 8 of the present invention;

FIG. 3 is a ¹ H NMR spectrum of a copolymer sample prepared in example 9 of the present invention;

FIG. 4 is a graph showing the mechanical properties of a copolymer sample prepared in example 5 of the present invention;

FIG. 5 is a graph showing the mechanical properties of a copolymer sample prepared in example 8 of the present invention.

Detailed Description

For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.

In view of the problem that the polymerization mechanism and polymerization activity of cycloolefin compounds, isoprene and alpha-olefin compounds are greatly different and are difficult to copolymerize in the prior art, the application provides a terpolymer and a preparation method thereof, and the specific polymerization system and polymerization process conditions are introduced to ensure that the cycloolefin compounds, isoprene and alpha-olefin compounds have higher catalytic activity, so that copolymers of cycloolefin units, isoprene units and alpha-olefin units with three different contents are obtained, and the elongation at break and the tensile strength of the terpolymer are improved, so that the terpolymer can be completely used as a novel elastic material. Specifically, the application provides a terpolymer prepared from isoprene, an alpha-olefin compound and a cycloolefin compound, wherein the main chain of the terpolymer comprises cycloolefin units, isoprene units and alpha-olefin units; the content of the cycloolefin unit is more than 3mol% and less than 20mol%, the content of the isoprene unit is more than 10mol% and less than 85mol%, and the content of the alpha-olefin unit is more than 10mol% and less than 85mol% based on the terpolymer main chain.

In the present application, the terpolymer is a random copolymer or a multiblock copolymer.

In the present invention, the alpha-olefin is selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene or 1-octene, more preferably from ethylene.

In the present invention, the cycloolefin compound is selected from the group consisting of a compound of the structure of formula I, a compound of the structure of formula II, a compound of the structure of formula III, and a compound of the structure of formula IV:

A formula I; A formula II; formula III; A formula IV;

R in the formula I is selected from a hydrogen atom, a C1-6 hydrocarbon group, a phenyl group, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group or a silicon-containing group;

n in formula III is 0,1 or 2;

r in formula IV is selected from a hydrogen atom, a C1-6 hydrocarbon group, a phenyl group, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a silicon-containing group.

In the present invention, the cycloolefin compound is a cycloolefin compound having 3 or more carbon atoms, preferably at least one selected from norbornene, dicyclopentadiene, tricyclopentadiene, tetracyclododecene, vinylnorbornene, cyclohexene and ethylidenenorbornene, more preferably norbornene, dicyclopentadiene, ethylidenenorbornene, vinylnorbornene or tetracyclododecene.

In the invention, the content of the isoprene unit in the terpolymer is more than 10mol% and less than 85mol%, preferably 15mol% to 80mol%, more preferably 30mol% to 70mol%, and most preferably 50mol% to 60mol%. The content of 1, 4-structural units in the isoprene units is preferably higher than 30mol%, and the content of 3, 4-structural units is preferably lower than 70mol%; specifically, the content of the 1, 4-structural unit is 31-45 mol%.

In the present invention, the cycloolefin unit content is preferably more than 3mol% and less than 20mol%, preferably 5mol% to 18mol%, more preferably 6mol% to 12mol% of the entire terpolymer.

In the present invention, the terpolymer main chain further contains an α -olefin unit, and the α -olefin unit content is preferably more than 10mol% and less than 85mol% of the entire terpolymer, most preferably 20 to 80mol% of the entire terpolymer, still more preferably 30 to 70mol%, and most preferably 50 to 60mol%.

In the present invention, the glass transition temperature of the terpolymer is preferably-60 ℃ to 20 ℃, more preferably-40 ℃ to 20 ℃.

In the present invention, the melting point of the multipolymer is preferably 130 ℃ or less or has no melting point, more preferably 70 ^o to 110 ℃, still more preferably 80 to 100 ℃, and most preferably 90 ℃ or has no melting point.

In the present invention, the number average molecular weight of the multipolymer is preferably 10,000 to 1,000,000, more preferably 50,000 to 1,000,000; the molecular weight distribution of the multipolymer is preferably 1 to 10, more preferably 1 to 4.

The invention provides a preparation method of the terpolymer, which comprises the following steps:

polymerizing alpha-olefin compound, conjugated diene compound and cycloolefin compound in reaction medium under the action of catalytic system to obtain multipolymer;

the catalyst system comprises an organoboron salt compound, an organoaluminum compound and a rare earth metal complex;

The rare earth metal complex has the structure of formula V:

A formula V;

in the formula V, M is selected from one of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, gadolinium, ytterbium and lutetium;

R ¹、R²、R³、R⁴ and R ⁵ are independently selected from the group consisting of a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 20 carbon atoms, an aralkyl group containing 6 to 20 carbon atoms, a silyl group containing 1 to 14 carbon atoms; or two or more of R ¹ to R ⁵ may be linked to each other to form an alicyclic or aromatic ring;

e is O, S or N, R ₂ is methyl, ethyl, isopropyl, phenyl or substituted phenyl;

X ₁ and X ₂ are monoanionic ligands, X ₁ and X ₂ are independently selected from hydrogen, a linear aliphatic group, a branched aliphatic group or an alicyclic group having 1 to 20 carbon atoms, phenyl, a linear alkyl group, a branched alkyl group, a cyclic aliphatic group or an aromatic group-substituted phenyl group having 1 to 20 carbon atoms, a linear alkoxy group or a branched alkoxy group having 1 to 20 carbon atoms, a linear alkylamino group or a branched alkylamino group having 1 to 20 carbon atoms, a linear arylamino group or a branched arylamino group having 1 to 20 carbon atoms, a linear or branched silyl group having 1 to 20 carbon atoms, a borono group, an allyl derivative or halogen;

L is a neutral Lewis base;

w is an integer of 0 to 3.

In the present invention, the types of the α -olefin compound, isoprene and cycloolefin compound are the same as those described in the above technical scheme, and will not be described in detail herein.

In the present invention, the organoboron compound is preferably an ionic compound formed of an organoboron anion and a cation; the organoboron anion is preferably selected from tetraphenyl borate ([ BPh ₄]^-), tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C ₆F₅)₄]^-), tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl), phenyl ] borate or undecahydride-7, 8-dicarbaundecaborate; the cation is preferably selected from a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation or a transition metal containing ferrocenium cation, the carbonium cation preferably comprises a trisubstituted carbonium cation, which may in particular be selected from a triphenylcarbonium cation ([ Ph ₃C]⁺), which may in particular be selected from a tris (tolyl) carbonium cation, or a tris (substituted phenyl) carbonium cation, which may in particular be selected from a tri (tolyl) carbonium cation, the ammonium cation preferably comprises a trialkylammonium cation, an N, N-dialkylanilinium cation or a dialkylammonium cation, which may in particular be selected from a trimethylammonium cation, a triethylammonium cation ([ NEt ₃H]⁺), a tripropylammonium cation or a tributylammonium cation, which N, N-dialkylanilinium cation is in particular selected from N, n-dimethylanilinium cations ([ PhNMe ₂H]⁺), N-diethylanilinium cations, and N, N-2,4, 6-pentamethylanilinium cations, said dialkylammonium cations being selected in particular from diisopropylammonium cations and dicyclohexylammonium cations; the phosphonium cations preferably comprise triarylphosphonium cations, which are selected in particular from triphenylphosphonium cations, tri (tolyl) phosphonium cations or tri (xylyl) phosphonium cations.

In the present invention, the organoboron salt compound is preferably specifically selected from [Ph₃C][B(C₆F₅)₄]、[PhNMe₂H][BPh₄]、[NEt₃H][BPh₄] or [ PhNMe ₂H][B(C₆F₅)₄ ]; organoboron compounds having the same function as organoboron salt compounds, such as B (C ₆F₅)₃, C), may also be used.

In the present invention, the organoaluminum compound is preferably selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum or ethyldi (p-tolylaluminum).

In the present invention, the rare earth metal complex is preferably one of the formulas 1 to 6:

。

The source of the rare earth metal complex is not particularly limited and may be prepared according to methods well known to those skilled in the art, for example, by synthesis according to the method in Organometallics 2015, 34, 455-461; Angew. Chem. Int. Ed. 2017, 56, 6975-6979;Angew. Chem. Int. Ed. 2016, 55, 1–7 or the method disclosed in WO 2015/051569.

The present invention is not particularly limited in the ratio of the amounts of isoprene, α -olefin compounds and cycloolefin compounds, and those skilled in the art can adjust the ratio of the amounts of the respective raw materials according to the content of the respective structural units in the terpolymer to be obtained.

In the invention, the concentration of the isoprene in the polymerization system is preferably lower than 2mol/L, more preferably 0.05-2 mol/L, and still more preferably 0.10-1.0 mol/L; the molar ratio of the α -olefin compound to the conjugated diene compound is preferably (10 to 1): (1-7), more preferably (5-1): (1-3), most preferably (4~2): 2; the molar ratio of the conjugated diene compound to the cycloolefin compound is preferably (10 to 1): 1, more preferably (8~2): 1, more preferably (6~2): 1, most preferably (4~2): 1.

The amount of the catalyst system used in the present invention is not particularly limited, and a person skilled in the art may select a proper amount of catalyst system according to the amount of catalyst used in the polymerization of monomers known in the art, and may ensure that the polymerization reaction proceeds according to the actual situation.

In the present invention, the molar ratio of the organoboron compound to the rare earth metal complex is preferably (0.5 to 10): 1, more preferably (2 to 6): 1, and most preferably (1 to 3): 1.

In the present invention, the molar ratio of the organoaluminum compound to the rare earth metal complex is preferably (2 to 300): 1, more preferably (5 to 250): 1, more preferably (10 to 200): 1, more preferably (50 to 150): 1, more preferably (80 to 100): 1.

In the present invention, the polymerization reaction temperature is preferably-20 to 150 ℃, more preferably-10 to 120 ℃, more preferably 10 to 90 ℃, more preferably 20 to 80 ℃, more preferably 30 to 60 ℃, more preferably 40 to 50 ℃.

In the invention, the alpha-olefin compound used in the reaction process is preferably ethylene, and the pressure of the ethylene in the reaction process is preferably 1-20 atmospheres, more preferably 2-15 atmospheres, and even more preferably 4-10 atmospheres.

The polymerization time of the present invention is not particularly limited, and is selected according to the amount of the catalyst and the size of the reaction system. Wherein the polymerization reaction is carried out by an intermittent kettle, and the reaction time is 1 minute to 10 hours; if the polymerization reaction is carried out in a continuous kettle, the reaction time is 1-10 days.

In the present invention, the reaction medium is preferably one or more selected from aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes, more preferably one or more selected from hexane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and bromobenzene.

The amount of the reaction medium used in the present invention is not particularly limited, and a person skilled in the art may select a suitable amount of the reaction medium according to the actual situation to ensure that the polymerization reaction can be performed.

In the present invention, the method of polymerization preferably comprises:

A mixed solution of a conjugated diene compound and a cycloolefin compound is added to a polymerization reaction system of an alpha-olefin compound (ethylene) saturated solution containing a rare earth metal complex, an organoaluminum compound and an organoboron salt compound. In the present invention, it is preferable to add a mixed solution of the conjugated diene compound and the cycloolefin compound stepwise to a solution containing the α -olefin compound (ethylene), the rare earth metal complex, the organoaluminum compound and the organoboron salt compound. In the present invention, the isoprene compound and the α -olefin compound may be added in a pulsed manner or at a constant rate throughout the polymerization reaction.

In the present invention, the method of polymerization may preferably include:

Mixing rare earth metal complex, organic aluminum compound and organic boron salt compound with alpha-olefin compound, isoprene and cycloolefin monomer to initiate polymerization. In the present invention, the α -olefin compound is preferably continuously introduced at a constant pressure during the polymerization, and isoprene and cycloolefin compounds are preferably added in the form of monomer pulses.

In the present invention, the method of polymerization may preferably further include:

During the polymerization reaction, adding the solution of isoprene monomer into the mixed solution of alpha-olefin compound and cycloolefin compound containing the catalytic system to initiate polymerization; the mixed solution of isoprene monomer and cycloolefin compound monomer may be added in a pulsed manner or at a constant rate.

In the present invention, it is preferable to terminate the reaction by adding a methanolic hydrochloric acid solution after completion of the polymerization reaction.

In the invention, the copolymer prepared by ethanol separation is preferably added after the polymerization reaction is terminated, and then the copolymer is dried; the drying method is preferably vacuum drying; the drying temperature is preferably 30 to 50 ℃, more preferably 35 to 45 ℃, and most preferably 40 ℃.

The invention adopts three kinds of monomer alpha-olefin, isoprene and cyclic olefin with great difference in polymerization mechanism and polymerization activity, improves the polymerization activity of the polymerized monomer by adjusting the catalyst structure, changes the polymerization process to realize the copolymerization of the alpha-olefin, the cycloolefin compound and the isoprene, and obtains the terpolymer, and the elongation at break of the copolymer can reach 1000 percent and the tensile strength can reach 15MPa according to different contents of each component in the copolymer, thus being a novel elastomer material which has not been reported in patents and documents so far.

In order to further understand the present invention, the terpolymer of isoprene, α -olefin and cyclic olefin compounds and the preparation method thereof according to the present invention will be described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.

The raw materials used in the following examples of the present invention are all commercially available.

Example 1

Adding 40 mmol isoprene and 1.2 g (10 mmol) Ethylidene Norbornene (ENB) and 40ml toluene into a 150 ml stainless steel reaction kettle fully purged by nitrogen, and filling 1.0 atm ethylene into the mixture under vigorous stirring to enable the mixture to reach a saturated state in toluene solution to form a polymerization reaction system;

In a glove box, a catalyst solution was prepared by dissolving a complex of the structure of formula 2 (4.7 mg, 10. Mu. Mol), al ⁱBu₃ (0.1 mL, 50. Mu. Mol, 0.5: 0.5 mol/L toluene solvent), and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (9.2 mg, 10. Mu. Mol) in 2mL toluene; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization; three monomers are added according to the reaction progress in the whole polymerization process, and after 5 minutes of reaction, 20 mL methanol hydrochloric acid solution is added immediately to terminate the reaction. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.

Example 2

Adding 40 mmol isoprene and 1.2 g (10 mmol) Ethylidene Norbornene (ENB) and 40ml toluene into a 150 ml stainless steel reaction kettle fully purged by nitrogen, and filling 1.0 atm ethylene into the mixture under vigorous stirring to enable the mixture to reach a saturated state in toluene solution to form a polymerization reaction system;

In a glove box, a catalyst solution was prepared by dissolving a complex of the structure of formula 3 (5.1 mg, 10. Mu. Mol), al ⁱBu₃ (0.1 mL, 50. Mu. Mol, 0.5: 0.5 mol/L toluene solvent), and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (9.2 mg, 10. Mu. Mol) in 2 mL toluene; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization. Three monomers are added according to the reaction progress in the whole polymerization process; after 5 minutes of reaction, the reaction was terminated by adding 20 mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

Example 3

Adding 40 mmol isoprene, 1.2g (10 mmol) Ethylidene Norbornene (ENB) and 40 ml toluene into a 150 ml stainless steel reaction kettle fully purged with nitrogen, and filling 1.0 atm ethylene into the mixture under vigorous stirring to enable the mixture to reach a saturated state in toluene solution to form a polymerization reaction system;

In a glove box, a catalyst solution was prepared by dissolving a complex of the structure of formula 5 (5.9 mg, 10. Mu. Mol), al ⁱBu₃ (0.1 mL, 50. Mu. Mol, 0.5: 0.5 mol/L toluene solvent), and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (9.2 mg, 10. Mu. Mol) in 2 mL toluene; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization; three monomers are added according to the reaction progress in the whole polymerization process; immediately after 5 minutes of reaction, the reaction was terminated by adding 20 mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

Example 4

Adding 40 mmol isoprene and 1.2g (10 mmol) Ethylidene Norbornene (ENB) and 40 ml toluene into a 150 ml stainless steel reaction kettle fully purged with nitrogen, and charging 1.0 atm ethylene into the mixture under vigorous stirring to reach a saturated state in toluene solution to form a polymerization reaction system;

In a glove box, a catalyst solution was prepared by dissolving a complex of the structure of formula 6 (5.3 mg, 10. Mu. Mol), al ⁱBu₃ (0.1 mL, 50. Mu. Mol, 0.5: 0.5 mol/L toluene solvent), and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (9.2 mg, 10. Mu. Mol) in 2 mL toluene; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization; after 5 minutes of reaction, the reaction was terminated by adding 20mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

Example 5

To a 350 ml stainless steel reaction vessel sufficiently purged with nitrogen, 20 mmol (0.25 mol/L) of isoprene and 2.4g (20 mmol) of Ethylidene Norbornene (ENB) and 80 ml of toluene were added, and 1.0 atm of ethylene was charged under vigorous stirring to be saturated in toluene solution to form a polymerization reaction system;

In a glove box, a catalyst solution was prepared by dissolving a complex of the structure of formula 6 (10.6 mg, 20. Mu. Mol), al ⁱBu₃ (0.2 mL, 100. Mu. Mol, 0.5. 0.5 mol/L toluene solvent), and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (18.4 mg, 20. Mu. Mol) in 4mL toluene; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization; after 5 minutes of reaction, the reaction was terminated by adding 20 mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

The mechanical properties of the copolymer prepared in example 5 of the present invention were measured, and the measurement results are shown in FIG. 4.

Example 6

40Mmol (0.5 mol/L) of isoprene and 2.4g (20 mmol) of Ethylidene Norbornene (ENB) and 80 ml of toluene are added into a 350ml stainless steel reaction kettle fully purged with nitrogen, and 1.0 atm of ethylene is filled into the reaction kettle under vigorous stirring to reach a saturated state in toluene solution, so that a polymerization reaction system is formed;

In a glove box, a catalyst solution was prepared by dissolving a complex of the structure of formula 6 (10.6 mg, 20. Mu. Mol), al ⁱBu₃ (0.2 mL, 100. Mu. Mol, 0.5. 0.5 mol/L toluene solvent), and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (18.4 mg, 20. Mu. Mol) in 4mL toluene; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization; after 5 minutes of reaction, the reaction was terminated by adding 20 mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

Example 7

To a 350 ml stainless steel reaction vessel sufficiently purged with nitrogen, 40 mmol (0.5 mol/L) of isoprene and 1.92g (16 mmol) of Ethylidene Norbornene (ENB) and 80 ml of toluene were added, and 1.0 atm of ethylene was charged under vigorous stirring to be saturated in toluene solution to form a polymerization reaction system;

In a glove box, a catalyst solution was prepared by dissolving a complex of the structure of formula 6 (10.6 mg, 20. Mu. Mol), al ⁱBu₃ (0.2 mL, 100. Mu. Mol, 0.5. 0.5 mol/L toluene solvent), and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] 18.4 mg, 20. Mu. Mol) in 4 mL toluene; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization; after 5 minutes of reaction, the reaction was terminated by adding 20 mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

The copolymer prepared in example 7 of the present invention was subjected to nuclear magnetic resonance hydrogen spectrum detection, and the detection result is shown in FIG. 1.

Example 8

40Mmol (0.5 mol/L) of isoprene and 2.4g (20 mmol) of Ethylidene Norbornene (ENB) and 80 ml toluene are added into a 350ml stainless steel reaction kettle fully purged with nitrogen, and 1.0 atm ethylene is filled into the reaction kettle under vigorous stirring to reach a saturated state in toluene solution to form a polymerization reaction system;

In a glove box, a complex of the structure of formula 6 (10.6 mg, 20. Mu. Mol), al ⁱBu₃ (0.2 mL, 100. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (18.4 mg, 20. Mu. Mol) were dissolved in 4mL of toluene to prepare a catalyst solution; thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃and the ethylene pressure was adjusted to 4 atm to initiate polymerization; after 5 minutes of reaction, the reaction was terminated by adding 20mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

The copolymer prepared in example 8 of the present invention was subjected to nuclear magnetic resonance hydrogen spectrum detection, and the detection result is shown in FIG. 2.

The mechanical properties of the copolymer prepared in example 8 of the present invention were measured, and the measurement results are shown in FIG. 5.

Example 9

30Mmol (0.75 mol/L) of isoprene and 1.88 g (10 mmol) of Tricyclopentadiene (TCPD) and 40 ml of toluene are added into a 150 ml stainless steel reaction kettle fully purged by nitrogen, and 1.0 atm of ethylene is charged into the reaction kettle under vigorous stirring to reach a saturated state in toluene solution, so as to form a polymerization reaction system;

In a glove box, a complex of the structure of formula 6 (5.3 mg, 10. Mu. Mol), al ⁱBu₃ (0.1 mL, 50. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ₃C][B(C₆F₅)₄ ] (9.2 mg, 10. Mu. Mol) were dissolved in 2mL of toluene to prepare a catalyst solution; after that, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40 ℃ to initiate polymerization; after 5 minutes of reaction, the reaction was terminated by adding 20mL methanol hydrochloric acid solution, and then a large amount of ethanol was added to isolate the copolymer, and the copolymer was dried under vacuum at 40℃until the weight of the polymer was not changed.

The copolymer prepared in example 9 of the present invention was subjected to nuclear magnetic resonance hydrogen spectrum detection, and the detection result is shown in FIG. 3.

Performance detection

The performance of the terpolymer prepared according to the examples of the present invention was examined as follows:

The contents of ethylene (E), isoprene (IP) and Ethylidene Norbornene (ENB) in the copolymer were calculated from ¹ H NMR spectrum of the copolymer measured at 110℃in C ₆D₄Cl₂, respectively, using the following formulas:

The integral of I _5.07-4.87 is defined as the integral sum of one H of an isoprene 1,4 structure double bond and one H of an ENB trans-ethylene double bond, the integral of I _5.07-4.87 is the integral sum of two H of an isoprene 3,4 structure double bond, the integral sum of one H of cis-ethylene ENB and trans-ethylene ENB 4 tertiary carbon, and the integral sum of H of all methyl, methylene and methine of a polymer main chain and a side chain, wherein I _3.04-2.92 and I _2.73-2.58 are respectively.

f_E=[I_2.55-0.90-3I_5.07-4.87-7(I_5.58-5.29-I_2.73-2.58)-10(I_3.04-2.92+I_2.73-2.58)]/( I_2.55-0.90-3I_2.73-2.58-3I_5.58-5.29-I_5.07-4.87-6I_3.04-2.92)*100%;

f_ENB=(4I_3.04-2.92+4I_2.73-2.58)/(I_2.55-0.90-3I_2.73-2.58-3I_5.58-5.29-I_5.07-4.87-6I_3.04-2.92)*100%;

f_IP=(2I_5.07-4.87+4I_5.58-5.29-4I_2.73-2.58)/(I_2.55-0.90-3I_2.73-2.58-3I_5.58-5.29-I_5.07-4.87-6I_3.04-2.92)*100%;

f_1,4=(4I_5.58-5.29-4I_2.73-2.58)/(I_2.55-0.90-3I_2.73-2.58-3I_5.58-5.29-I_5.07-4.87-6I_3.04-2.92)*100%;

f_3,4=2I_5.07-4.87/(I_2.55-0.90-3I_2.73-2.58-3I_5.58-5.29-I_5.07-4.87-6I_3.04-2.92)*100%；

The ethylene (E), isoprene (IP) and Tricyclopentadiene (TCPD) contents of the copolymer were calculated from the ¹ H NMR spectrum of the copolymer measured at 110℃in C ₆D₄Cl₂, respectively, using the following formulae:

The integral of I _4.96-4.50 is defined as 2, I _5.70-5.56 and I _5.56-5.40 are respectively the integral of two H of the side chain double bond of TCPD in the polymer, I _5.26-5.09 is the integral of one H of the isoprene 1,4 structure double bond, I _4.96-4.50 is the integral of two H of the isoprene 3,4 structure double bond, I _3.10-2.92 is the integral of one H of the ortho-position tertiary carbon of the TCPD double bond, and I _2.55-0.60 is the integral sum of H of all methyl, methylene and methine groups of the main chain and the side chain of the polymer.

f_E=(I_2.55-0.60-3I_4.96-4.50-7I_5.26-5.09-15I_5.70-5.56)/( I_2.55-0.60-I_4.96-4.50-3I_5.26-5.09-11I_5.70-5.56)*100%;

f_TCPD=4I_5.70-5.56/( I_2.55-0.60-I_4.96-4.50-3I_5.26-5.09-11I_5.70-5.56)*100%；

f_IP=(4I_5.26-5.09+2I_4.96-4.50)/(I_2.55-0.60-I_4.96-4.50-3I_5.26-5.09-11I_5.70-5.56)*100%；

f_1,4=4I_5.26-5.09/( I_2.55-0.60-I_4.96-4.50-3I_5.26-5.09-11I_5.70-5.56)*100%；

f_3,4=2I_4.96-4.50/(I_2.55-0.60-I_4.96-4.50-3I_5.26-5.09-11I_5.70-5.56)*100%；

Determination of the copolymer glass transition temperature (T _g): the glass transition temperature of the copolymer was determined by Differential Scanning Calorimetry (DSC) using a Metler TOPEM TM.

Determination of copolymer number average molecular weight (M _n) and molecular weight distribution (PDI): the number average molecular weight (M _n) and molecular weight distribution (PDI) of the copolymer were determined by Gel Permeation Chromatography (GPC) with polystyrene as standard, at 150℃using C ₆H₃Cl₃ as mobile phase.

Determination of copolymer tensile Strength and elongation at break: the tensile strength and elongation at break of the copolymers were determined by means of a universal mechanical tester according to GB/T528-1998. The test results show that the tensile strength of the polymers prepared in examples 5 and 8 is 13.3-3.6 MPa, and the elongation at break is 750-920%, as shown in FIGS. 4 and 5.

The results of the detection of the copolymers prepared in examples 1 to 4 are shown in Table 1:

TABLE 1 results of Performance test of the copolymers prepared in examples 1 to 4 of the present invention

TABLE 2 detection results of Properties of the copolymers prepared in examples 5 to 8 of the present invention

The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A terpolymer prepared from isoprene, an alpha-olefin compound and a cycloolefin compound, the terpolymer backbone comprising cycloolefin units, isoprene units and alpha-olefin units; the content of the cycloolefin unit is more than 3mol% and less than 20mol%, the content of the isoprene unit is more than 10mol% and less than 85mol%, and the content of the alpha-olefin unit is more than 10mol% and less than 85mol% based on the terpolymer main chain.

2. The terpolymer according to claim 1, wherein the terpolymer is a random copolymer.

3. Terpolymer according to claim 1 wherein the isoprene units consist of 1, 4-structural units and 3, 4-structural units and the content of 3, 4-structural units is less than 70mol%, based on the total amount of isoprene units.

4. The terpolymer according to claim 1 wherein the cyclic olefin compound is selected from the group consisting of a compound of formula I, a compound of formula II, a compound of formula III or a compound of formula IV:

A formula I; A formula II; formula III; A formula IV;

R in the formula I is selected from a hydrogen atom, a C1-6 hydrocarbon group, a phenyl group, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group or a silicon-containing group;

n in formula III is 0,1 or 2;

r in formula IV is selected from a hydrogen atom, a C1-6 hydrocarbon group, a phenyl group, a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a silicon-containing group.

5. The terpolymer according to claim 1 wherein the alpha olefin compound comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene or 1-octene; the cycloolefin compound includes at least one of norbornene, dicyclopentadiene, tricyclopentadiene, tetracyclododecene, vinyl norbornene, cyclohexene and ethylidene norbornene.

6. The terpolymer according to claim 1, wherein the terpolymer has a glass transition temperature of-50 ℃ to 20 ℃, a melting point of 130 ℃ or less or no melting point.

7. The terpolymer according to claim 1, wherein the number average molecular weight of the terpolymer is 20000 or more and the molecular weight distribution of the terpolymer is 1 to 10.

8. A process for preparing the terpolymer of claim 1 comprising:

polymerizing alpha-olefin compounds, isoprene and cycloolefin compounds in a reaction medium under the action of a catalytic system to obtain a multipolymer;

the catalyst system comprises an organoboron salt compound, an organoaluminum compound and a rare earth metal complex;

The rare earth metal complex has the structure of formula V:

A formula V;

in the formula V, M is selected from one of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, gadolinium, ytterbium and lutetium;

R ¹、R²、R³、R⁴ and R ⁵ are independently selected from the group consisting of a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 20 carbon atoms, an aralkyl group containing 6 to 20 carbon atoms, a silyl group containing 1 to 14 carbon atoms; or two or more of R ¹ to R ⁵ may be linked to each other to form an alicyclic or aromatic ring;

e is O, S or N, R ₂ is methyl, ethyl, isopropyl, phenyl or substituted phenyl;

X ₁ and X ₂ are monoanionic ligands, X ₁ and X ₂ are independently selected from hydrogen, a linear aliphatic group, a branched aliphatic group or an alicyclic group having 1 to 20 carbon atoms, phenyl, a linear alkyl group, a branched alkyl group, a cyclic aliphatic group or an aromatic group-substituted phenyl group having 1 to 20 carbon atoms, a linear alkoxy group or a branched alkoxy group having 1 to 20 carbon atoms, a linear alkylamino group or a branched alkylamino group having 1 to 20 carbon atoms, a linear arylamino group or a branched arylamino group having 1 to 20 carbon atoms, a linear or branched silyl group having 1 to 20 carbon atoms, a borono group, an allyl derivative or halogen;

L is a neutral Lewis base;

w is an integer of 0 to 3.

9. The method of claim 8, wherein the reaction medium is selected from one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes.

10. The method according to claim 8, wherein the organoboron salt compound is an ionic compound formed of an organoboron anion and a cation; the organoboron anion is selected from tetraphenylborate ([ BPh ₄]^-), tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C ₆F₅)₄]^-), tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl), phenyl ] borate or undecahydride-7, 8-dicarbaundecaborate, the cation being selected from carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations or ferrocenium cations containing transition metals;

The organoaluminum compound is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum or ethyldi (p-tolylaluminum).