CN110283279A - Copolymer, preparation method and the rubber composition of 1,3- butadiene and 1- butylene - Google Patents

Abstract

The invention provides a copolymer of 1,3-butadiene and 1-butene, which is a random copolymer or multi-block copolymer containing butadiene structural units and 1-butene structural units, the The random copolymer or the multi-block copolymer does not have a crystallization temperature; the content of cis-1,4 in the butadiene structural unit in the copolymer is more than 70mol%, and the butadiene structural unit in the copolymer The content of 1,2- in the copolymer is less than 30mol%; the content of the 1-butene part in the copolymer is 5mol%-60mol%. The copolymer of butadiene and 1-butene provided by the application has excellent aging resistance, ozone resistance, wear resistance, heat resistance, crack growth resistance and sealing performance, and it can be used as rubber application.

Description

Copolymer of 1,3-butadiene and 1-butene, its preparation method and rubber composition

technical field

The invention relates to the technical field of novel rubber, in particular to a copolymer of 1,3-butadiene and 1-butene, a preparation method thereof and a rubber composition.

Background technique

The copolymers obtained by copolymerization of two or more monomers can be divided into random copolymers, alternating copolymers, block copolymers, gradient copolymers and graft copolymers according to the different repeating monomer units arranged. Although there have been recent reports on random copolymers of ethylene and butadiene, there have been no reports on random copolymers of α-olefins with more than three carbons and butadiene.

JP11-228743A discloses an unsaturated elastomer composition composed of an unsaturated olefin-based copolymer as a random copolymer and rubber. However, the copolymer includes various structures having not only 1,4 bonds and 1,2 bonds (including 3,4 bonds), but also three-membered rings and five-membered rings, and thus their arrangement is unclear.

The Chinese patent with the publication number CN103140516B discloses a copolymer of a conjugated diene compound and a non-conjugated diene. Regular copolymers, excluding multi-block parts and block parts. In addition, the inventor of this patent emphasizes that in the copolymer of conjugated diene compound and non-conjugated olefin, the content of 1,2 (or 3,4) adduct in the conjugated diene structural unit should be less than 5% .

Publication No. CN103154058B discloses copolymers of conjugated diene compounds and non-conjugated olefins, but there is no description of the arrangement of monomer units in the copolymer of conjugated diene compounds and non-conjugated olefins, nor is there any requirement for crystallinity illustrate.

Chinese Patent Publication No. CN103492439A discloses a copolymer of conjugated diene compound and non-conjugated olefin, wherein the cis 1,4-content of the conjugated diene compound is greater than 92%, and the 1,2-content is less than 5%. The inventors in the patent specifically proposed that if the content of 1,2 units in the conjugated diene is greater than 5%, the resulting conjugated diene compound/non-conjugated olefin copolymer and the conjugated diene polymer to be described later are due to Formation of free radicals may have less extended crystallinity and resistance to crack growth and reduced weatherability. The copolymer disclosed in above-mentioned patent can be used as the composition of rubber, to improve the performance of rubber, but only has improved the partial performance of rubber, and the comprehensive performance of rubber needs to be further improved.

Contents of the invention

The technical problem solved by the present invention is to provide a copolymer of butadiene and 1-butene, which has excellent aging resistance, ozone resistance, wear resistance, heat resistance, crack growth resistance and sealing properties, and can Used as rubber.

In view of this, the application provides a copolymer of butadiene and 1-butene, which is a random copolymer or multi-block copolymer containing butadiene structural units and 1-butene structural units, the The random copolymer or the multi-block copolymer does not have a crystallization temperature;

The cis-1,4 bond content of the butadiene structural unit in the copolymer is more than 70mol%, and the 1,2-content in the butadiene structural unit of the copolymer is less than 30mol%;

The content of the 1-butene part in the copolymer is 5mol%-60mol%.

Preferably, the stereoselectivity of the 1-butene structural unit in the copolymer is isotactic or random.

Preferably, the number average molecular weight of the copolymer is 10,000-1,000,000, and the molecular weight distribution of the copolymer is 1-10.

Preferably, the glass transition temperature of the copolymer is -110 to -60°C.

Preferably, the content of cis-1,4 in the butadiene structural unit of the copolymer is 80-93 mol%.

Preferably, the content of 1,2- in the butadiene structural unit of the copolymer is 7-20 mol%.

Preferably, the content of 1-butene in the copolymer is 10mol%-50mol%.

The application also provides the preparation method of the copolymer of described butadiene and 1-butene, comprising:

Butadiene monomer solution, catalyst composition and 1-butene monomer solution are mixed, initiate polymerization, obtain copolymer;

Alternatively, the 1-butene monomer solution, part of the butadiene solution and the catalyst composition are mixed to initiate polymerization, and the remaining butadiene solution is gradually added to the polymerization system to carry out polymerization reaction to obtain a copolymer;

The catalyst composition is a mixture of a rare earth catalyst, an organoaluminum compound and an organoboron salt compound.

Preferably, during the polymerization reaction, the ratio of the concentration of the 1-butene monomer solution to the butadiene monomer solution>1.0.

The present application also provides a rubber composition, including the copolymer of 1,3-butadiene and 1-butene described in the above scheme or the 1,3-butadiene prepared by the preparation method described in the above scheme Copolymer with 1-butene.

The application provides a copolymer of butadiene and 1-butene, which is a random copolymer or multi-block copolymer containing butadiene structural units and 1-butene structural units, and further defines the copolymerization The content of butadiene structural unit and 1-butene part in the product; the application partially introduces 1-butene monomer on the main chain of butadiene rubber, so that the double bond on the main chain of the copolymer is reduced, so that the obtained copolymer It has excellent aging resistance, ozone resistance and abrasion resistance, and the introduction of butene-1 moiety with side groups in the copolymer can further improve the sealing property of the copolymer.

Description of drawings

Fig. 1 is the ¹ HNMR spectrogram of the copolymer sample prepared in Example 1 of the present invention;

Fig. 2 is the ¹ HNMR spectrogram of the copolymer sample prepared in Example 6 of the present invention;

Fig. 3 is the ¹³ C NMR spectrogram of the copolymer sample prepared in Example 1 of the present invention;

Fig. 4 is the ¹³ C NMR spectrogram of the copolymer sample prepared in Example 6 of the present invention;

Fig. 5 is the DSC figure of the copolymer sample that the embodiment of the present invention 3 prepares;

Fig. 6 is a DSC chart of the copolymer sample prepared in Example 6 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 the examples, but 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.

The embodiment of the present invention discloses a copolymer of butadiene and 1-butene, which is a random copolymer or multi-block copolymer containing butadiene structural units and 1-butene structural units. A regular copolymer or said multi-block copolymer does not have a crystallization temperature;

In the copolymer, the content of the cis-1,4 bond in the butadiene structural unit is more than 70mol%, and the content of the 1,2-butadiene structural unit in the copolymer is less than 30mol%;

The content of the 1-butene part in the copolymer is 5mol%-60mol%.

The application provides a copolymer of butadiene and 1-butene, which does not have block copolymers and gradient copolymers containing long 1-butene structural units, but only includes irregularly arranged 1-butene Random or multi-block copolymers of butene structural units and short 1-butene structural units without crystallization temperature. The copolymer has the characteristics of aging resistance, ozone resistance, wear resistance, heat resistance, crack growth resistance and excellent sealing performance, and can be used as rubber.

Specifically, the application provides a copolymer of butadiene and 1-butene, the content of cis-1,4 in the butadiene structural unit of the copolymer is more than 70mol%. In a specific embodiment, the butadiene structural unit The cis-1,4 content in the copolymer is greater than 80 mol%, and more specifically, the cis-1,4 content of the butadiene structural unit in the copolymer is 80-93 mol%. The 1,2- content of the butadiene structural unit in the copolymer is less than 30 mol%, and in a specific embodiment, the 1,2- content of the butadiene structural unit is 7 mol% to 20 mol%. In the present application, the content of the 1-butene part is 5mol%～60mol%, in a specific embodiment, the content of the 1-butene part is 10～50mol%, more specifically, the 1-butene The content of the olefin moiety is 20 to 50 mol%. In the present application, the stereoselectivity of the 1-butene structural unit is isotactic or random. 1-butene is introduced into the copolymer to reduce the double bonds on the main chain of the copolymer, so that the copolymer has properties such as aging resistance, ozone resistance and wear resistance, and at the same time, the side chain of 1-butene makes the copolymer The sealing performance is enhanced; the introduction of 1-butene structural unit reduces the double bonds on the main chain, and the higher the content, the better the wear resistance.

The number average molecular weight of the copolymer of butadiene and 1-butene provided by the application is 10000～1000000, in a specific embodiment, the number average molecular weight of the copolymer of butadiene and 1-butene is 100000～ 600000. The molecular weight distribution of the copolymer is 1-10, in a specific embodiment, the molecular weight distribution of the copolymer is 1-5, more specifically, the molecular weight distribution of the copolymer is 1-4. If the molecular weight distribution is too large, it is not a copolymer, but a mixture) The glass transition temperature of the copolymer of butadiene and 1-butene is -110～-60°C. In a specific embodiment, the butadiene The glass transition temperature of the copolymer with 1-butene is -105°C to -70°C.

The application also provides the preparation method of the copolymer of butadiene and 1-butene, comprising:

The butadiene monomer solution and the 1-butene monomer solution of the catalyst combination are mixed to initiate polymerization to obtain a copolymer;

Alternatively, the 1-butene monomer solution, part of the butadiene solution and the catalyst composition are mixed to initiate polymerization, and the remaining butadiene solution is gradually added to the polymerization system for polymerization to obtain a copolymer; the catalyst composition The compound is a mixture of rare earth catalyst, organoaluminum compound and organoboron salt compound.

The above-mentioned copolymer of butadiene and 1-butene can be carried out in the following manner more specifically: in the presence of a catalyst composition, (1) the mixed solution containing butadiene and 1-butene is initiated to polymerize; ( 2) obtained by adding butadiene to the polymerization system in the presence of 1-butene; (3) obtained by adding 1-butene to the polymerization system in the presence of butadiene.

The above-mentioned catalyst composition is specifically a rare earth catalyst, an organoaluminum compound and an organoboron salt compound, wherein the rare earth catalyst is selected from one of the following structural formulas: a monocene rare earth complex represented by the following general formula (1), represented by the following general formula ( 2) The monocene rare earth complexes with sidewalls and the monocene rare earth complexes with sidewalls represented by the following general formula (3):

Where M is selected from: scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd) , terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu);

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same or different from each other, and each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetal-containing alkane having 1 to 10 carbon atoms group, an alkyl group of 1 to 10 carbon atoms containing a ketal, an alkyl group of 1 to 20 carbon atoms containing an ether group, an alkenyl group containing 2 to 20 carbon atoms, and an alkyl group of 2 to 20 carbon atoms containing an acetal Atomic alkenyl, alkenyl of 2 to 20 carbon atoms containing ketal, alkenyl of 2 to 20 carbon atoms containing ether group, aralkyl containing 6 to 20 carbons, 6 to 20 carbon atoms containing acetal Aralkyl groups of 20 carbon atoms, aralkyl groups of 6 to 20 carbon atoms containing ketals, aralkyl groups of 6 to 20 carbon atoms containing ether groups, silyl groups of 1 to 14 carbon atoms 1. One of a silyl group of 1 to 14 carbon atoms containing acetal, a silyl group of 1 to 14 carbon atoms containing a ketal, and a silyl group of 1 to 14 carbon atoms containing an ether group; Or two or more groups in R ¹ to R ⁵ can be connected to each other to form an alicyclic or aromatic ring;

E is O, S, or N-R, wherein R is methyl, phenyl, or substituted phenyl;

X ₁ and X ₂ are monoanionic ligands linked by rare earth metals, X ₁ and X ₂ can be the same or different, X ₁ and X ₂ are each independently hydrogen, or a straight chain or branched chain containing 1 to 20 carbon atoms Chain aliphatic group or alicyclic group, phenyl group, or straight chain or branched chain alkyl or cyclic aliphatic group containing 1 to 20 carbon atoms or aromatic group containing 6 to 20 carbon atoms Group-substituted phenyl, straight-chain or branched alkoxy groups containing 1-20 carbon atoms, straight-chain or branched-chain alkylamino groups containing 1-20 carbon atoms, 6-20 carbon atoms Straight chain or branched aryl amino group, straight chain or branched silyl group containing 1 to 20 carbon atoms, borohydrogen group, allyl group, allyl derivatives, halogen, etc.;

L _w is a neutral Lewis base, such as one of tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether or pyridine; w is an integer from 0 to 3.

Cp in the formula is cyclopentadienyl derivative C ₅ A ₄ , indenyl derivative C ₉ A ₆ or fluorenyl derivative C ₁₃ A ₈ ; A is the substituent of cyclopentadienyl, the substitution of indenyl A substituent on the base or fluorenyl, A is the same or different, and A is selected from hydrogen, aliphatic hydrocarbon group, aromatic hydrocarbon group or silyl group; R is a substituent _on the skeleton pyridine ring, selected from hydrogen, methyl, ethyl , isopropyl, tert-butyl or phenyl; _R is a substituent on the skeleton pyridine ring, selected from hydrogen, methyl, ethyl, isopropyl, tert _- butyl or phenyl; R is a skeleton pyridine ring The substituent on is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl; R is the substituent _on the skeleton pyridine ring, selected from hydrogen, methyl, ethyl, isopropyl , tert-butyl, phenyl, 2,6-dimethylphenyl, 4-methylphenyl, mes-trimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-tri Isopropylphenyl or 2,6-di-tert-butylphenyl;

Ln represents a rare earth metal selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;

X is a monoanionic ligand selected from CH ₂ SiMe ₃ , CH(SiMe ₃ ) ₂ , 1,3-C ₃ H ₅ , 1,3-C ₃ H ₄ (Me) or 1,3-C ₃ H ₃ (SiMe ₃ ) ₂ .

Cp is a cyclopentadienyl derivative C ₅ A ₄ , an indenyl derivative C ₉ A ₆ or a fluorenyl derivative C ₁₃ A ₈ ; A is a cyclopentadienyl substituent, an indenyl substituent or fluorene The substituent on the base, A is the same or different, and A is selected from hydrogen, aliphatic hydrocarbon group, aromatic hydrocarbon group or silyl group; R2 is the substituent _on the skeleton pyridine ring, selected from hydrogen, methyl, ethyl, isopropyl base, tert-butyl or phenyl; _R3 is a substituent on the pyridine ring of the skeleton, selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl; R4 is a substituent _on the pyridine ring of the skeleton R is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl; R is a substituent _on the skeleton pyridine ring, selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl Base, phenyl, 2,6-dimethylphenyl, 4-methylphenyl, mes-trimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropyl Phenyl or 2,6-di-tert-butylphenyl;

Ln represents a rare earth metal selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; X is a single anion ligand selected from CH ₂ SiMe ₃ , CH(SiMe ₃ ) ₂ , 1,3-C ₃ H ₅ , 1,3-C ₃ H ₄ (Me) or 1,3-C ₃ H ₃ (SiMe ₃ ) ₂ ;

Lw is a neutral Lewis base, such as one of tetrahydrofuran, ether, ethylene glycol dimethyl ether or pyridine; _w is an integer from 0 to 3;

n is greater than or equal to 1.

The organoaluminum compound in the catalytic system of the present invention contains at least one carbon-aluminum bond and is represented by the following structural formula (4):

Wherein R is selected from alkyl (including cycloalkyl), alkoxy, aryl, _alkaryl , aralkyl and hydrogen _; R is selected from alkyl (including cycloalkyl), aryl, alkaryl , aralkyl, and hydrogen; and R _is selected from alkyl (including cycloalkyl), aryl, alkaryl, and aralkyl.

Typical compounds corresponding to the above structures are: diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, Dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl n-propyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-tolyl n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, benzyl ethyl Benzyl aluminum hydride, benzyl n-propyl aluminum hydride, benzyl isopropyl aluminum hydride and other organoaluminum hydrides. Also includes ethylaluminum dihydride, butylaluminum dihydride, isobutylaluminum dihydride, octylaluminum dihydride, pentylaluminum dihydride and other organoaluminum dihydrides; also includes diethylaluminum ethoxide and dipropylene aluminum ethoxide; also trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tri- Cyclohexyl aluminum, trioctyl aluminum, triphenyl aluminum, tri-p-cresyl aluminum, tribenzyl aluminum, ethyl diphenyl aluminum, ethyl di-p-tolyl aluminum, ethyl dibenzyl aluminum, diethyl Phenylaluminum, diethyl-p-tolylaluminum, diethylbenzylaluminum and other triorganoaluminum compounds.

The organoboron salt compound of the present invention may be an ionic compound composed of an organoboron anion and a cation; the organoboron anion includes 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, [three (pentafluorophenyl) ), phenyl]borate, and undecahydro-7,8-dicadecadecaborate; cations include carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations, and transition metal-containing Ferrocenium cations; wherein the carbenium cations include trisubstituted carbenium cations such as triphenylcarbenium cations ([Ph ₃ C] ⁺ ) and tri(substituted phenyl)carbenium cations, and tri(substituted phenyl More specific examples of carbenium cations include tris(tolyl)carbenium cations; ammonium cations include trialkylammonium cations such as trimethylammonium cations, triethylammonium cations ([NEt ₃ H] ⁺ ), triethylammonium cations ([NEt 3 H] + ), Propylammonium and tributylammonium cations; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation ([PhNMe ₂ H] ⁺ ), N,N-diethylanilinium cations and N,N-2,4,6-pentamethylanilinium cations; and dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations. Phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cations, tris(tolyl)phosphonium cations, and tris(xylyl)phosphonium cations.

Examples of organoboron salt compounds include [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], [PhNMe ₂ H][BPh ₄ ], [NEt ₃ H][BPh ₄ ], [PhNMe ₂ H][B (C ₆ F ₅ ) ₄ ] and so on. Organoboron compounds having the same function as organoboron salt compounds, such as B(C ₆ F ₅ ) ₃ , can also be used.

The ratio of each component in the catalytic system for preparing the copolymer of the present invention is: the molar ratio of the organoaluminum compound to the rare earth metal M is adjustable between 2:1 and 300:1, preferably between 4:1 and 200:1 between, most preferably between 8:1 and 100:1; the molar ratio of organoboron salt compound to rare earth metal M is adjustable between 1:10 and 10:1, preferably between 0.5:1 and 5:1.

The amount of catalyst used to initiate polymerization can vary widely; a low concentration catalyst system is ideal in this application because it minimizes ash generation problems. Polymerization will occur when the amount of rare earth M catalyst used varies between 0.05 and 1.0 millimole metal/100 grams of monomer; the preferred ratio is between 0.1 and 0.3 millimole metal/100 grams of monomer.

The polymerization reaction temperature of this application can be adjusted between extremely low temperature (such as -60°C) and higher temperature (such as 150°C); in specific embodiments, the polymerization temperature is preferably 10°C to 150°C, more preferably 25°C to 100°C, more preferably 25°C to 80°C. The polymerization reaction can be carried out under one atmospheric pressure, or one atmospheric pressure or more than one atmospheric pressure. The pressure of 1-butene is preferably 1 to 10 atmospheres.

The polymerization reaction is carried out in a hydrocarbon solvent, suitable solvents include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides or cycloalkanes, preferably hexane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene , or one or more mixtures of bromobenzene.

During the polymerization reaction, the solution of butadiene monomer is usually added to the polymerization reaction system of butene-1 solution containing rare earth catalyst, organoaluminum compound and organoboron salt compound catalyst component; preferably the butadiene The solution is gradually added to the solution containing butene-1, rare earth catalyst, organoaluminum compound and organoboron salt compound, more preferably, the butadiene solution is added at a constant speed during the entire polymerization reaction; or the butene-1 Add the solution of rare earth catalyst, organic aluminum compound and organic boron salt compound to the mixed solution of butadiene to initiate polymerization.

In addition, according to the preparation method of the copolymer of butadiene and butene-1 of the present invention, the concentration (mol/L) of butadiene and the concentration (mol/L) of 1-butene in the polymerization process preferably satisfy the following relationship : 1-butene/butadiene concentration>1.0; further preferably satisfy the following relationship: 1-butene/butadiene concentration≥2.

The application also provides a rubber composition, which comprises the copolymer of butadiene and 1-butene described in the above scheme.

According to actual needs, other diene-based elastomers such as natural rubber, polybutadiene and styrene-butadiene rubber can also be added to the rubber composition, and various additives can also be added, including fillers such as carbon black and silica, vulcanizing agents such as Sulfur and accelerators, process oils, fatty acids, waxes, resins and antidegradants. The rubber provided in this application can be used in different parts in the tire, such as tread, sidewall and other parts composed of rubber.

The copolymer of the present invention can be generally used for elastomeric articles, particularly tire members and various rubber articles such as vibration-absorbing rubber, belts (conveyor belts), rubber tracks, various types of hoses and seals.

In order to further understand the present invention, below in conjunction with embodiment the copolymer of butadiene and 1-butene provided by the present invention and preparation method thereof are described in detail, protection scope of the present invention is not limited by following examples.

Example 1

Add 250mL of toluene to a 2L stainless steel reaction kettle fully purged with nitrogen, and fill it with 1.0atm 1-butene gas under vigorous stirring, so that it reaches a saturated state in the toluene solution; in the glove box, the formula 5 Complex (74mg, ^146μmol ), Ali Bu ₃ (1.5mL, 1.46mmol, 1.0M toluene solvent) and triphenylcarbonate tetrakis(pentafluorophenyl) borate [Ph ₃ C][B (C ₆ F ₅ ) ₄ ] (135 mg, 146 μmol) was dissolved in 20 mL of toluene to prepare a catalyst solution; after that, the catalyst solution was taken out from the glove box and quickly added to the polymerization reaction system at 40 ° C to initiate polymerization; meanwhile, the toluene of butadiene The solution (130 g solution, 26.7% by weight butadiene) was fed into the polymerization system at a constant speed, and the dropping speed of the butadiene solution was controlled by a flow meter. 1-Butene was also fed throughout the polymerization. After the butadiene solution was added dropwise, immediately add 20mL of methanol hydrochloric acid solution to terminate the reaction; then add a large amount of ethanol to separate the copolymer, and dry the copolymer in vacuum at 40°C until the weight of the polymer does not change. The material is marked as sample A and characterized, and the results are shown in Figure 1, Figure 3 and Table 1.

Example 2

Add 250mL toluene in the 2L stainless steel reaction kettle, then fully purging with nitrogen, simultaneously, the toluene solution of butadiene and 1-butene joins in the polymerization system; In the glove box, the complex (74mg, 150μmol ), Ali Bu ₃ (1.5mL, 1.5mmol, 1.0M toluene solvent) and tetrakis(pentafluorophenyl) borate triphenylcarbonate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] ( ^139mg , 150 μmol) was dissolved in 20 mL of toluene, the catalyst solution was taken out from the glove box and quickly added to the polymerization reaction system at 40 ° C to initiate polymerization; at the same time, the toluene solution of butadiene and 1-butene was added to the polymerization at a constant speed In the system, after the mixed solution of butadiene and 1-butene has been added dropwise, immediately add 20mL of methanolic hydrochloric acid solution to terminate the reaction; then add a large amount of ethanol to separate the copolymer, and dry the copolymer in vacuum at 40°C until the polymer Until there was no change in weight, the obtained polymer was labeled as sample B and characterized, the results are shown in Table 1.

Example 3

250 mL of toluene was added to a 2L stainless steel reaction kettle, and then fully purged with nitrogen, and at the same time, the toluene solution of butadiene and 1-butene was added to the polymerization system. In the glove box, the complex of formula 7 (73 mg, 150 μmol), Ali ^Bu ₃ (1.5 mL, 1.5 mmol, 1.0 M toluene solvent) and triphenylcarbonate tetrakis(pentafluorophenyl) borate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ](139mg, 150μmol) was dissolved in 20mL of toluene, the catalyst solution was taken out from the glove box and quickly added to the polymerization reaction system at 40°C to initiate polymerization, meanwhile, butane Add the toluene mixed solution of ene and 1-butene to the polymerization system at a constant speed; after the butadiene and 1-butene mixed solution is added dropwise, immediately add 20mL of methanol hydrochloric acid solution to terminate the reaction; then add a large amount of ethanol to separate the copolymerization The copolymer was vacuum-dried at 40°C until there was no change in the weight of the polymer. The obtained polymer was marked as sample C and characterized, and the results are shown in Figure 5 and Table 1.

Example 4

Add 250mL of toluene to a 2L stainless steel reactor fully purged with nitrogen, and fill it with 1.0atm1-butene gas under vigorous stirring to make it saturated in the toluene solution; in the glove box, the compound of formula 8 (91 mg, 150 μmol), Ali ^Bu ₃ (1.5 mL, 1.5 mmol, 1.0 M toluene solvent) and tetrakis(pentafluorophenyl) borate triphenylcarbonate [Ph ₃ C][B (C ₆ F ₅ ) ₄ ] (139 mg, 150 μmol) was dissolved in 20 mL of toluene to prepare a catalyst solution; after that, the catalyst solution was taken out from the glove box and quickly added to the polymerization reaction system at 40 ° C to initiate polymerization, while the toluene solution of butadiene Added to the polymerization system, the pressure of 1-butene was increased to 4.0atm, and 1-butene was introduced throughout the polymerization process; after the polymerization reaction was carried out to the specified time, 20mL methanol hydrochloric acid solution was added immediately to terminate the reaction; then A large amount of ethanol was used to isolate the copolymer, and the copolymer was vacuum dried at 40°C until there was no change in the weight of the polymer. The obtained polymer was marked as sample D and characterized, and the results are shown in Table 1.

Example 5

Add 250mL of toluene to a 2L stainless steel reactor fully purged with nitrogen, and fill it with 1.0atm1-butene gas under vigorous stirring to make it saturated in the toluene solution; in the glove box, the compound of formula 9 (81 mg, 150 μmol), Ali ^Bu ₃ (1.5 mL, 1.5 mmol, 1.0 M toluene solvent) and tetrakis(pentafluorophenyl) borate triphenylcarbonate [Ph ₃ C][B (C ₆ F ₅ ) ₄ ] (139 mg, 150 μmol) was dissolved in 20 mL of toluene to prepare a catalyst solution; after that, the catalyst solution was taken out from the glove box and quickly added to the polymerization reaction system at 40 ° C to initiate polymerization, while the toluene solution of butadiene Added to the polymerization system, the pressure of 1-butene was increased to 4.0atm, and 1-butene was introduced throughout the polymerization process; after the polymerization reaction was carried out to the specified time, 20mL methanol hydrochloric acid solution was added immediately to terminate the reaction; then A large amount of ethanol was used to isolate the copolymer, and the copolymer was vacuum dried at 40°C until there was no change in the weight of the polymer. The obtained polymer was labeled as sample E and characterized, and the results are shown in Table 1.

Example 6

Add 250mL toluene in 2L stainless steel reaction kettle, then fully purged with nitrogen, simultaneously, the toluene solution of butadiene and 1-butene joins in the polymerization system; ), Ali Bu ₃ (1.5mL, 1.5mmol, 1.0M toluene solvent) and tetrakis(pentafluorophenyl) borate triphenylcarbonate [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] ( ^139mg , 150 μmol) was dissolved in 20mL of toluene, the catalyst solution was taken out from the glove box and quickly added to the polymerization reaction system at 25°C to initiate polymerization, meanwhile, the toluene solution of butadiene and 1-butene was added to the polymerization at a constant speed system; after the dropwise addition of the mixed solution of butadiene and 1-butene, immediately add 20mL of methanolic hydrochloric acid solution to terminate the reaction; then add a large amount of ethanol to separate the copolymer, and vacuum dry the copolymer at 40°C until the polymer The weight does not change so far. The polymer obtained was labeled as sample F and characterized, the results are shown in Figure 2, Figure 4, Figure 6 and Table 1.

Comparative example 1

The copolymers A to F of Examples 1 to 6 and the butadiene rubber of Comparative Example 1 were characterized in the following manner to study the microstructure, 1-butene content, number average molecular weight (M _n ), and molecular weight distribution (M _w /M _n ) and DSC curves.

1) Determination of cis 1,4 structural unit and 1,2-structural unit content in butadiene structural unit in copolymer:

The content of cis 1,4-structural unit and 1,2-structural unit in the butadiene structural unit in the copolymer is determined according to the ¹³ C NMR spectrum and ¹ HNMR of the polymer;

The regioselectivity (1,2- and 1,4) of the butadiene moiety in the copolymer was determined by the ^1,2 -vinyl bond component (4.8ppm _- 5.05 ppm) and 1,4-butadiene bond component (5.25ppm-5.6ppm to determine the integral ratio, butadiene moiety cis 1,4- and trans 1,4-selectivity in the copolymer is based on ¹³ C- The integral ratio of the cis-1,4 bond component (27ppm-28.2ppm) and the anti-1,4 bond component (31.5ppm-33ppm) of the NMR spectrum (25°C, CDCl ₃ ) was determined.

2) Determination of 1-butene content in the copolymer:

The content of the 1-butene structural unit in the copolymer is calculated according to the ¹ H NMR spectrogram of the copolymer measured in _CDCl3 , _fbutylene =2*I _(0.97-0.72) /[6*(I _{(5.05-4.87 )} )+3*(I _(5.48-5.27) -1)+2*I _(0.97-0.72) ].

3) Determination of copolymer glass transition temperature (Tg):

The glass transition temperature of the copolymer is determined by differential scanning calorimetry (DSC) according to GB/T 29611-2013.

4) Determination of copolymer number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ):

The number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) of the copolymer were determined by gel permeation chromatography (GPC) using polystyrene as a standard at 150°C with 1,2,4-C ₆ Cl ₃ H ₃ was determined as the mobile phase.

Table 1 Butadiene and 1-butene copolymerization result data sheet

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

The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those 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 invention. Therefore, the present invention will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A copolymer of butadiene and 1-butene is a random copolymer or multi-block copolymer containing butadiene structural unit and 1-butene structural unit, and the random copolymer or the The multi-block copolymer does not have a crystallization temperature; The cis-1,4 bond content of the butadiene structural unit in the copolymer is more than 70mol%, and the 1,2-link content in the butadiene structural unit of the copolymer is less than 30mol%; The content of the 1-butene part in the copolymer is 5mol%-60mol%. 2. The copolymer according to claim 1, characterized in that, the stereoselectivity of the 1-butene structural unit in the copolymer is isotactic or random. 3. The copolymer according to claim 1, characterized in that, the number average molecular weight of the copolymer is 10,000-1,000,000, and the molecular weight distribution of the copolymer is 1-10. 4. The copolymer according to claim 1, characterized in that the glass transition temperature of the copolymer is -110 to -60°C. 5. The copolymer according to claim 1, characterized in that the content of cis-1,4 in the butadiene structural unit of the copolymer is 80-93 mol%. 6. The copolymer according to claim 1, characterized in that the content of 1,2- in the butadiene structural unit of the copolymer is 7-20 mol%. 7. The copolymer according to claim 1, characterized in that the content of 1-butene in the copolymer is 10mol%-50mol%. 8. the preparation method of the copolymer of butadiene and 1-butene described in claim 1, comprises: mixing the butadiene monomer solution, the catalyst composition and the 1-butene monomer solution to initiate polymerization to obtain a copolymer; Alternatively, the 1-butene monomer solution, part of the butadiene solution and the catalyst composition are mixed to initiate polymerization, and the remaining butadiene solution is gradually added to the polymerization system for polymerization reaction to obtain a copolymer; The catalyst composition is a mixture of a rare earth catalyst, an organoaluminum compound and an organoboron salt compound. 9. The preparation method according to claim 8, characterized in that, during the polymerization reaction, the concentration ratio of the 1-butene monomer solution to the butadiene monomer solution is >1.0. 10. A rubber composition, comprising the copolymer of 1,3-butadiene and 1-butene described in any one of claims 1 to 7 or prepared by the preparation method described in any one of claims 8 to 9 Copolymer of 1,3-butadiene and 1-butene prepared.