CN118373937A - A terpolymer of isoprene, alpha-olefin and cycloolefin compound and preparation method thereof - Google Patents

Abstract

The present invention provides a terpolymer, which is prepared from isoprene, an alpha-olefin compound and a cycloolefin compound, wherein the main chain of the terpolymer comprises a cycloolefin unit, an isoprene unit and an alpha-olefin unit; based on the main chain of the terpolymer, the content of the cycloolefin unit is greater than 3 mol% and less than 20 mol%, the content of the isoprene unit is greater than 10 mol% and less than 85 mol%, and the content of the alpha-olefin unit is greater than 10 mol% and less than 85 mol%. The terpolymer provided by the present invention has excellent strength and elongation at break compared with polyisoprene, while maintaining high weather resistance, aging resistance, ozone resistance and crack growth resistance.

Description

A terpolymer of isoprene, α-olefin and cycloolefin compounds and its preparation method

Technical Field

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

Background technique

Elastomer materials are used in various fields due to their excellent mechanical properties. In recent years, the performance requirements for elastomer materials have become increasingly diverse, and there is a desire for elastomer materials with excellent properties, such as high tensile strength, high elongation at break, low temperature resistance, and crack growth resistance.

Ethylene homopolymer is plastic, polyisoprene is rubber, and cyclic olefin polymer is transparent resin; polyethylene molecular chain is highly flexible, has strong crystallization ability, high modulus and strength, good toughness, and tear resistance, while isoprene rubber molecular chain is pliable and has excellent elasticity, but low tensile and tear strength. If ethylene, isoprene, and cyclic olefin monomers are copolymerized to prepare a new type of "plastic-rubber" that has both the elasticity of rubber and the toughness and tear resistance of plastic, while improving wear resistance, fatigue resistance, and thermal oxidation aging properties, it is expected to become a new type of rubber-plastic material with excellent performance.

In the patent documents disclosed so far, the conjugated diene monomer in the copolymer of conjugated diene and non-conjugated olefin is mostly butadiene, and the non-conjugated diene monomer is ethylene. In the multipolymer of conjugated diene and non-conjugated diene, the conjugated diene 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 differences in polymerization activity, making it difficult to achieve copolymerization, and ethylene, cyclic olefin and isoprene terpolymers have not been reported so far.

Summary of the invention

The technical problem solved by the present invention is to provide a terpolymer of isoprene, α-olefin and cyclic olefin compounds, which can realize the copolymerization of isoprene, α-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 ternary copolymer prepared from isoprene, an α-olefin compound and a cycloolefin compound, wherein the main chain of the ternary copolymer comprises a cycloolefin unit, an isoprene unit and an α-olefin unit; based on the main chain of the ternary copolymer, the content of the cycloolefin unit is greater than 3 mol% and less than 20 mol%, the content of the isoprene unit is greater than 10 mol% and less than 85 mol%, and the content of the α-olefin unit is greater than 10 mol% and less than 85 mol%.

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

Preferably, the cycloolefin compound is selected from a compound of formula I, a compound of formula II, a compound of formula III or a compound of formula IV:

Formula I; Formula II; Formula III; Formula IV;

R in 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 α-olefin compound includes 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 terpolymer has a glass transition temperature of -50°C to 20°C, and a melting point of 130°C or less or has no melting point.

Preferably, the number average molecular weight of the terpolymer is greater than 20,000, and the molecular weight distribution of the terpolymer is 1-10.

The present application also provides a method for preparing the terpolymer, comprising:

The α-olefin compound, isoprene and cycloolefin compound are polymerized in a reaction medium under the action of a catalyst system to obtain a multi-component copolymer;

The catalytic system includes an organic boron salt compound, an organic aluminum compound and a rare earth metal complex;

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

Formula V;

In Formula V, M is selected from one of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, gadolinium, ytterbium and lutetium;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently selected from hydrogen atom, alkyl group containing 1 to 10 carbon atoms, alkenyl group containing 2 to 20 carbon atoms, aralkyl group containing 6 to 20 carbon atoms, silyl group containing 1 to 14 carbon atoms; or two or more groups of R ¹ to R ⁵ may be connected to each other to form an alicyclic or aromatic ring;

E is selected from O, S or N, R ₂ is selected from methyl, ethyl, isopropyl, phenyl or substituted phenyl;

_X1 and _X2 are monoanionic ligands, and _X1 and _X2 are independently selected from hydrogen, a straight-chain aliphatic group, a branched aliphatic group or an alicyclic group containing 1 to 20 carbon atoms, a phenyl group, a straight-chain alkyl group, a branched alkyl group, a cyclic aliphatic group or a phenyl group substituted with an aromatic group containing 1 to 20 carbon atoms, a straight-chain alkoxy group or a branched alkoxy group containing 1 to 20 carbon atoms, a straight-chain alkylamino group or a branched alkylamino group containing 1 to 20 carbon atoms, a straight-chain arylamino group or a branched arylamino group containing 1 to 20 carbon atoms, a straight-chain or branched silane group containing 1 to 20 carbon atoms, a borohydride group, an allyl group, an allyl derivative or a halogen;

L is a neutral Lewis base;

w is an integer from 0 to 3.

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

Preferably, the organic boron salt compound is an ionic compound formed by an organic boron anion and a cation; the organic boron anion is selected from tetraphenylborate ([BPh ₄ ] ^- ), tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ^- ), tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl), phenyl]borate or undecyl-7,8-dicarbonundecaborate; the cation is selected from carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation or ferrocenium cation containing a transition metal;

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-tolyl)aluminum.

The present application provides a terpolymer of isoprene, α-olefin and cycloolefin compound, which is prepared from isoprene, α-olefin compound and cycloolefin compound, the main chain of the terpolymer includes cycloolefin unit, isoprene unit and α-olefin unit; based on the main chain of the terpolymer, the content of the cycloolefin unit is greater than 3 mol% and less than 20 mol%, the content of the isoprene unit is greater than 10 mol% and less than 85 mol%, and the content of the α-olefin unit is greater than 10 mol% and less than 85 mol%; the copolymer provided by the present application has three monomer sequence distributions that can be adjusted. According to the different contents of each monomer, a copolymer with an elongation of 1000% and a tensile strength of 15 MPa can be obtained.

The present application also provides a method for preparing a terpolymer, which adopts a specific catalyst and changes the polymerization reaction process so that the α-olefin, cycloolefin and isoprene monomers have high catalytic activity, realizes the copolymerization of α-olefin, cycloolefin and isoprene with very different polymerization reaction mechanisms and polymerization activities, and obtains copolymers with different copolymer unit contents.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a ¹ H NMR spectrum of a copolymer sample prepared in Example 7 of the present invention;

FIG2 is a ¹ H NMR spectrum of the copolymer sample prepared in Example 8 of the present invention;

FIG3 is a ¹ H NMR spectrum of the copolymer sample prepared in Example 9 of the present invention;

FIG4 is a graph showing the mechanical properties of the copolymer sample prepared in Example 5 of the present invention;

FIG5 is a graph showing the mechanical properties of the copolymer sample prepared in Example 8 of the present invention.

Detailed ways

In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

In view of the problem that the polymerization mechanism and polymerization activity of cycloolefin compounds, isoprene and α-olefin compounds in the prior art are very different and difficult to copolymerize, the present application provides a terpolymer and a preparation method thereof, which introduces a specific polymerization system and polymerization process conditions to make cycloolefin compounds, isoprene and α-olefin compounds have high catalytic activity, thereby obtaining copolymers of three different contents of cycloolefin units, isoprene units and α-olefin units, improving the elongation at break and tensile strength of the terpolymer, so that it can completely become a new elastic material. Specifically, the present invention provides a terpolymer, which is prepared from isoprene, α-olefin compounds and cycloolefin compounds, and the main chain of the terpolymer includes cycloolefin units, isoprene units and α-olefin units; based on the main chain of the terpolymer, the content of the cycloolefin units is greater than 3 mol% and less than 20 mol%, the content of the isoprene units is greater than 10 mol% and less than 85 mol%, and the content of the α-olefin units is greater than 10 mol% and less than 85 mol%.

In the present application, the terpolymer is a random copolymer or a multi-block copolymer.

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

In the present invention, the cycloolefin compound is selected from a compound of formula I, a compound of formula II, a compound of formula III or a compound of formula IV:

Formula I; Formula II; Formula III; Formula IV;

R in 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 containing more than 3 carbon atoms, preferably selected from at least one of norbornene, dicyclopentadiene, tricyclopentadiene, tetracyclododecene, vinyl norbornene, cyclohexene and ethylidene norbornene, more preferably selected from norbornene, dicyclopentadiene, ethylidene norbornene, vinyl norbornene or tetracyclododecene.

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

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

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

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

In the present invention, the melting point of the multi-polymer is preferably below 130°C or has no melting point, more preferably 70 ^° C to 110°C, more preferably 80°C to 100°C, most preferably 90°C or has no melting point.

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

The present invention provides a method for preparing the terpolymer described in the above technical solution, comprising:

The α-olefin compound, the conjugated diene compound and the cycloolefin compound are polymerized in a reaction medium under the action of a catalyst system to obtain a multi-component copolymer;

The catalytic system includes an organic boron salt compound, an organic aluminum compound and a rare earth metal complex;

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

Formula V;

In Formula V, M is selected from one of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, gadolinium, ytterbium and lutetium;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently selected from hydrogen atom, alkyl group containing 1 to 10 carbon atoms, alkenyl group containing 2 to 20 carbon atoms, aralkyl group containing 6 to 20 carbon atoms, silyl group containing 1 to 14 carbon atoms; or two or more groups of R ¹ to R ⁵ may be connected to each other to form an alicyclic or aromatic ring;

E is selected from O, S or N, R ₂ is selected from methyl, ethyl, isopropyl, phenyl or substituted phenyl;

_X1 and _X2 are monoanionic ligands, and _X1 and _X2 are independently selected from hydrogen, a straight-chain aliphatic group, a branched aliphatic group or an alicyclic group containing 1 to 20 carbon atoms, a phenyl group, a straight-chain alkyl group, a branched alkyl group, a cyclic aliphatic group or a phenyl group substituted with an aromatic group containing 1 to 20 carbon atoms, a straight-chain alkoxy group or a branched alkoxy group containing 1 to 20 carbon atoms, a straight-chain alkylamino group or a branched alkylamino group containing 1 to 20 carbon atoms, a straight-chain arylamino group or a branched arylamino group containing 1 to 20 carbon atoms, a straight-chain or branched silane group containing 1 to 20 carbon atoms, a borohydride group, an allyl group, an allyl derivative or a halogen;

L is a neutral Lewis base;

w is an integer from 0 to 3.

In the present invention, the types of the α-olefin compounds, isoprene and cycloolefin compounds are consistent with those described in the above technical solution and will not be repeated here.

In the present invention, the organic boron compound is preferably an ionic compound formed by an organic boron anion and a cation; the organic boron anion is preferably selected from tetraphenylborate ([BPh ₄ ] ^- ), tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ^- ), tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tri(pentafluorophenyl), phenyl]borate or undecyl-7,8-dicarbonundecaborate; the cation is preferably selected from carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations or ferrocenium cations containing transition metals; the carbonium cation preferably comprises a trisubstituted carbonium cation or a tri(substituted phenyl)carbonium cation, the trisubstituted carbonium cation specifically being selected from triphenylcarbonium cation ([Ph ₃ C] ⁺ ), the tri(substituted phenyl)carbonium cation specifically being selected from tri(tolyl)carbonium cation; the ammonium cation preferably comprises a trialkylammonium cation, an N,N-dialkylanilinium cation or a dialkylammonium cation, the trialkylammonium cation specifically being selected from trimethylammonium cation, triethylammonium cation ([NEt ₃ H] ⁺ ), tripropylammonium cation or tributylammonium cation, the N,N-dialkylanilinium cation is specifically selected from N,N-dimethylanilinium cation ([PhNMe ₂ H] ⁺ ), N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation, the dialkylammonium cation is specifically selected from diisopropylammonium cation and dicyclohexylammonium cation; the phosphonium cation preferably includes a triarylphosphonium cation, and the triarylphosphonium cation is specifically selected from triphenylphosphonium cation, tri(tolyl)phosphonium cation or tri(xylyl)phosphonium cation.

In the present invention, the organic boron salt compound can be preferably selected from [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], [PhNMe ₂ H][BPh ₄ ], [NEt ₃ H][BPh ₄ ] or [PhNMe ₂ H][B(C ₆ F ₅ ) ₄ ]; an organic boron compound having the same function as the organic boron salt compound, such as B(C ₆ F ₅ ) ₃ , can also be used.

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

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

.

The present invention has no particular limitation on the source of the rare earth metal complex, and the rare earth metal complex can be prepared according to methods well known to those skilled in the art, such as 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 WO2015/051569.

The present invention has no particular limitation on the usage ratio of the isoprene, α-olefin compound and cycloolefin compound. Those skilled in the art can adjust the usage ratio of each raw material according to the desired content of each structural unit in the terpolymer.

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

The present invention has no particular limitation on the amount of the catalyst system. Those skilled in the art can select a suitable amount of the catalyst system according to the amount of catalyst for monomer polymerization known in the art and actual conditions to ensure the polymerization reaction proceeds.

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

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

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

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

In addition, the polymerization reaction time of the present invention is not particularly limited and is selected according to the amount of catalyst used and the size of the reaction system. If the polymerization reaction is carried out in an intermittent reactor, the reaction time is 1 minute to 10 hours; if the polymerization reaction is carried out in a continuous reactor, the reaction time is 1 day to 10 days.

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

The present invention has no particular limitation on the amount of the reaction medium. Those skilled in the art can select a suitable amount of the reaction medium according to actual conditions to ensure that the polymerization reaction can proceed.

In the present invention, the polymerization method preferably comprises:

The mixed solution of the conjugated diene compound and the cycloolefin compound is added to the polymerization reaction system of the saturated solution of the α-olefin compound (ethylene) containing the rare earth metal complex, the organoaluminum compound and the organoboron compound. In the present invention, it is preferred to gradually add the mixed solution of the conjugated diene compound and the cycloolefin compound to the solution containing the α-olefin compound (ethylene), the rare earth metal complex, the organoaluminum compound and the organoboron compound. In the present invention, the isoprene compound and the α-olefin compound can be added in a pulsed manner or at a constant speed during the entire polymerization reaction.

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

The rare earth metal complex, the organoaluminum compound and the organoboron salt compound are mixed with the α-olefin compound, isoprene and the cycloolefin monomer to initiate a polymerization reaction. In the present invention, the α-olefin compound is preferably continuously introduced at a constant pressure during the polymerization reaction, and the isoprene and the cycloolefin compound are preferably added in the form of monomer pulses.

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

During the polymerization reaction, a solution of isoprene monomer is added to a mixed solution of α-olefin compounds and cycloolefin compounds containing a catalyst system to initiate polymerization; the mixed solution of isoprene monomer and cycloolefin compound monomer can be added in a pulsed manner or at a constant speed.

In the present invention, after the polymerization reaction is completed, a methanol-hydrochloric acid solution is preferably added to terminate the reaction.

In the present invention, after the polymerization reaction is terminated, ethanol is preferably added to separate the prepared copolymer and then dried; the drying method is preferably vacuum drying; the drying temperature is preferably 30-50°C, more preferably 35-45°C, and most preferably 40°C.

The present invention adopts three monomers, α-olefin, isoprene and cyclic olefin, which have very different polymerization reaction mechanisms and polymerization activities, improves the polymerization activity of the polymerization monomers by adjusting the catalyst structure, changes the polymerization reaction process to achieve copolymerization of α-olefin, cyclic olefin compound and isoprene, and obtains a terpolymer. According to the different contents of each component in the copolymer, the elongation at break of the copolymer can reach 1000% and the tensile strength can reach 15MPa. The copolymer is a new type of elastomeric material that has not been reported in patents and literature 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 provided by the present invention are described in detail below in conjunction with examples. The protection 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 commodities.

Example 1

40 mmol of isoprene, 1.2 g (10 mmol) of ethylidene norbornene (ENB) and 40 ml of toluene were added to a 150 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, the complex of formula 2 (4.7 mg, 10 μmol), Al ⁱ Bu ₃ (0.1 mL, 50 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (9.2 mg, 10 μmol) were dissolved in 2 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40°C to initiate polymerization; during the entire polymerization process, three monomers were added according to the reaction progress, and after 5 minutes of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction. Then, a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40°C until the polymer weight did not change.

Example 2

40 mmol of isoprene, 1.2 g (10 mmol) of ethylidene norbornene (ENB) and 40 ml of toluene were added to a 150 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, the complex of formula 3 (5.1 mg, 10 μmol), Al ⁱ Bu ₃ (0.1 mL, 50 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (9.2 mg, 10 μmol) were dissolved in 2 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40°C to initiate polymerization. During the entire polymerization process, three monomers were added according to the progress of the reaction; after 5 minutes of reaction, 20 mL of methanolic hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40°C until the polymer weight did not change.

Example 3

40 mmol of isoprene, 1.2 g (10 mmol) of ethylidene norbornene (ENB) and 40 ml of toluene were added to a 150 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, a complex of formula 5 (5.9 mg, 10 μmol), Al ⁱ Bu ₃ (0.1 mL, 50 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (9.2 mg, 10 μmol) were dissolved in 2 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40°C to initiate polymerization; during the entire polymerization process, three monomers were added according to the progress of the reaction; after 5 minutes of reaction, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40°C until the polymer weight did not change.

Example 4

40 mmol of isoprene, 1.2 g (10 mmol) of ethylidene norbornene (ENB) and 40 ml of toluene were added to a 150 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system;

In a glove box, a complex of formula 6 (5.3 mg, 10 μmol), Al ⁱ Bu ₃ (0.1 mL, 50 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (9.2 mg, 10 μmol) were dissolved in 2 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40° C. to initiate polymerization; after reacting for 5 minutes, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40° C. until the polymer weight did not change.

Example 5

20 mmol (0.25 mol/L) of isoprene, 2.4 g (20 mmol) of ethylidene norbornene (ENB) and 80 ml of toluene were added to a 350 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, a complex of formula 6 (10.6 mg, 20 μmol), Al ⁱ Bu ₃ (0.2 mL, 100 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (18.4 mg, 20 μmol) were dissolved in 4 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40°C to initiate polymerization; after reacting for 5 minutes, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40°C until the polymer weight did not change.

The mechanical properties of the copolymer prepared in Example 5 of the present invention were tested, and the test results are shown in FIG4 .

Example 6

40 mmol (0.5 mol/L) of isoprene, 2.4 g (20 mmol) of ethylidene norbornene (ENB) and 80 ml of toluene were added to a 350 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, a complex of formula 6 (10.6 mg, 20 μmol), Al ⁱ Bu ₃ (0.2 mL, 100 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (18.4 mg, 20 μmol) were dissolved in 4 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40°C to initiate polymerization; after reacting for 5 minutes, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40°C until the polymer weight did not change.

Example 7

40 mmol (0.5 mol/L) of isoprene, 1.92 g (16 mmol) of ethylidene norbornene (ENB) and 80 ml of toluene were added to a 350 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, a complex of formula 6 (10.6 mg, 20 μmol), Al ⁱ Bu ₃ (0.2 mL, 100 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] 18.4 mg, 20 μmol) were dissolved in 4 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40°C to initiate polymerization; after reacting for 5 minutes, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40°C until the polymer weight did not change.

The copolymer prepared in Example 7 of the present invention was subjected to hydrogen nuclear magnetic resonance spectrum detection, and the detection result is shown in FIG1 .

Example 8

40 mmol (0.5 mol/L) of isoprene, 2.4 g (20 mmol) of ethylidene norbornene (ENB) and 80 ml of toluene were added to a 350 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, a complex of formula 6 (10.6 mg, 20 μmol), Al ⁱ Bu ₃ (0.2 mL, 100 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (18.4 mg, 20 μmol) were dissolved in 4 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40° C. and the ethylene pressure was adjusted to 4 atm to initiate polymerization; after reacting for 5 minutes, 20 mL of methanolic hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40° C. until the polymer weight did not change.

The copolymer prepared in Example 8 of the present invention was subjected to hydrogen nuclear magnetic resonance spectrum detection, and the detection result is shown in FIG2 .

The mechanical properties of the copolymer prepared in Example 8 of the present invention were tested, and the test results are shown in FIG5 .

Example 9

30 mmol (0.75 mol/L) of isoprene, 1.88 g (10 mmol) of tricyclopentadiene (TCPD) and 40 ml of toluene were added to a 150 ml stainless steel reactor fully purged with nitrogen, and 1.0 atm of ethylene was introduced into the reactor under vigorous stirring to saturate the toluene solution, thereby forming a polymerization reaction system.

In a glove box, a complex of formula 6 (5.3 mg, 10 μmol), Al ⁱ Bu ₃ (0.1 mL, 50 μmol, 0.5 mol/L toluene solvent) and triphenylcarbonium tetrakis(pentafluorophenyl)borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (9.2 mg, 10 μmol) were dissolved in 2 mL of toluene to prepare a catalyst solution; then, the catalyst solution was taken out of the glove box and quickly added to the above polymerization reaction system at 40° C. to initiate polymerization; after reacting for 5 minutes, 20 mL of methanol-hydrochloric acid solution was immediately added to terminate the reaction, and then a large amount of ethanol was added to separate the copolymer, and the copolymer was vacuum dried at 40° C. until the polymer weight did not change.

The copolymer prepared in Example 9 of the present invention was subjected to hydrogen nuclear magnetic resonance spectrum detection, and the detection result is shown in FIG3 .

Performance Testing

The performance of the terpolymer prepared in the embodiment of the present invention was tested according to the following method:

The contents of ethylene (E), isoprene (IP) and ethylidene norbornene (ENB) in the copolymer were calculated based on the ¹ H NMR spectrum of the copolymer measured in C ₆ D ₄ Cl ₂ at 110°C, respectively, using the following formulas:

The integral of I _5.07-4.87 is set to 2, I _5.58-5.29 is the integral of one H of the double bond of isoprene 1,4 structure and one H of the double bond of trans-ethylene in ENB, I _5.07-4.87 is the integral of two H of the double bond of isoprene 3,4 structure, I _3.04-2.92 and I _2.73-2.58 are the integral of one H of the tertiary carbon No. 4 of cis-ethylene ENB and trans-ethylene ENB, respectively, and I _2.55-0.90 is the integral of all H of methyl, methylene and methine in the main chain and side chains of the polymer.

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 contents of ethylene (E), isoprene (IP) and tricyclopentadiene (TCPD) in the copolymer were calculated based on the ¹ H NMR spectrum of the copolymer measured in C ₆ D ₄ Cl ₂ at 110°C, respectively, using the following formulas:

The integral of I _4.96-4.50 is set to 2, I _5.70-5.56 and I _5.56-5.40 are the integrals of the two H's of the double bond of the side chain of TCPD in the polymer, I _5.26-5.09 is the integral of one H's of the double bond of the 1,4 structure of isoprene, I _4.96-4.50 is the integral of the two H's of the double bond of the 3,4 structure of isoprene, I _3.10-2.92 is the integral of one H's of the ortho-tertiary carbon of the double bond of TCPD, and I _2.55-0.60 is the integral sum of the H's of all methyl, methylene and methine groups in the main chain and side chains 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 glass transition temperature (T _g ) of copolymers: The glass transition temperature of the copolymers was determined by differential scanning calorimetry (DSC) using a Mettler TOPEM TM.

Determination of number average molecular weight ( _Mn ) and molecular weight distribution (PDI) of copolymers: The number average molecular weight ( _Mn ) and molecular weight distribution (PDI) of copolymers were determined by gel permeation chromatography (GPC) at 150°C with _polystyrene as standard _{and C6H3Cl3} as mobile phase.

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

The test results of the copolymers prepared in Examples 1 to 4 are shown in Table 1:

Table 1 Performance test results of copolymers prepared in Examples 1 to 4 of the present invention

Table 2 Performance test results of copolymers prepared in Examples 5 to 8 of the present invention

The above embodiments are only used to help understand the method and core idea of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to 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).