CN110283279A - Copolymer, preparation method and the rubber composition of 1,3- butadiene and 1- butylene - Google Patents
Copolymer, preparation method and the rubber composition of 1,3- butadiene and 1- butylene Download PDFInfo
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- CN110283279A CN110283279A CN201910418478.9A CN201910418478A CN110283279A CN 110283279 A CN110283279 A CN 110283279A CN 201910418478 A CN201910418478 A CN 201910418478A CN 110283279 A CN110283279 A CN 110283279A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Abstract
The present invention provides the copolymers of a kind of 1,3-butadiene and 1- butylene, and for random copolymer or segmented copolymer containing butadiene structural units and 1- butylene structural unit, the random copolymer or the segmented copolymer do not have crystallization temperature；The content of content 1,2- in butadiene structural units in 70mol% or more, the copolymer of cis- Isosorbide-5-Nitrae is less than 30mol% in butadiene structural units in the copolymer；The content of 1- butylene part is 5mol%~60mol% in the copolymer.The copolymer of butadiene provided by the present application and 1- butylene has excellent ageing-resistant, resistance to ozone, wear-resisting, heat resistance, resistance to crack growth resistance and leakproofness, it can be used as rubber applications.
Description
Technical field
The present invention relates to the copolymers of new type rubber technical field more particularly to 1,3-butadiene and 1- butylene, its preparation
Method and rubber composition.
Background technique
According to the different repeated monomer units of arrangement in the copolymer that two kinds or the above monomer copolymerizable obtain, can divide
At random copolymer, alternate copolymer, block copolymer, gradient copolymer and graft copolymer.Although have recently ethylene and
The report of butadiene random copolymer, but for it is more than three carbon alpha-olefin and butadiene random copolymer have not been reported.
JP11-228743A is disclosed to be made of not the ethylenic unsaturation hydrocarbon type copolymer and rubber as random copolymer
It is saturated elastic composition.However, the copolymer includes various structures, not only there is Isosorbide-5-Nitrae key and 1,2 keys (including 3,4
Key), but also there is three-membered ring and five-membered ring, thus its arrangement is unclear.
The Chinese patent of Publication No. CN103140516B is disclosed with conjugated diene compound and non-conjugated diene
Copolymer, the copolymer are the random copolymerization of the monomeric unit irregular alignment of conjugated diene compound and non-conjugated diene
Object does not include more block sections and block section.In addition, the patent inventor emphasize conjugated diene compound with it is non-conjugated
In the copolymer of alkene, 1,2 (or 3,4) adduct contents will be lower than 5% in the conjugated diene structural unit.
Publication number CN103154058B discloses the copolymer of conjugated diene compound Yu non-conjugated alkene, but for altogether
The arrangement of conjugate diene compound and monomeric unit in the polymerized copolymers of non-conjugated alkene does not illustrate, also not to crystallinity
Explanation.
The Chinese patent of publication number CN103492439A discloses the copolymerization of conjugated diene compound Yu non-conjugated alkene
Object, wherein the conjugated diene compound part is greater than 92% along Isosorbide-5-Nitrae-content, 1,2- content is less than 5%.Inventor in patent
It specially proposes, the content of Unit 1,2 is greater than 5% in conjugated diene, then gained conjugated diene compound/non-conjugated olefin-copolymerization
Object and later by the conjugated diene polymer of description due to formed free radical and may have lesser extension crystallization and
Resistance to crack growth resistance and reduced weatherability.The copolymer of above-mentioned patent disclosure all can be used as the ingredient of rubber, to improve rubber
The performance of glue, but the partial properties of rubber are only improved, the comprehensive performance of rubber needs to be further increased.
Summary of the invention
Present invention solves the technical problem that being to provide the copolymer of a kind of butadiene and 1- butylene, which has
Excellent ageing-resistant, resistance to ozone, wear-resisting, heat resistance, resistance to crack growth resistance and leakproofness, can be used as rubber applications.
In view of this, this application provides the copolymer of a kind of butadiene and 1- butylene, to contain butadiene structural units
With the random copolymer or segmented copolymer of 1- butylene structural unit, the random copolymer or the segmented copolymer
Without crystallization temperature；
The content of the cis- Isosorbide-5-Nitrae key of butadiene structural units is in 70mol% or more, the fourth of the copolymer in the copolymer
1,2- content is less than 30mol% in diene structure unit；
The content of 1- butylene part is 5mol%~60mol% in the copolymer.
Preferably, the stereoselective of 1- butylene structural unit is complete same or random in the copolymer.
Preferably, the number-average molecular weight of the copolymer is 10000~1000000, the molecular weight distribution of the copolymer
It is 1~10.
Preferably, the copolymer glass transition temperature is -110~-60 DEG C.
Preferably, the content of cis- Isosorbide-5-Nitrae is 80~93mol% in the butadiene structural units of the copolymer.
Preferably, the content of 1,2- is 7~20mol% in the butadiene structural units of the copolymer.
Preferably, in the copolymer 1- butylene part content 10mol%~50mol%.
Present invention also provides the preparation methods of the butadiene and the copolymer of 1- butylene, comprising:
Divinylic monomer solution, carbon monoxide-olefin polymeric and 1- butene monomers solution are mixed, causes polymerization, is copolymerized
Object；
It polymerize alternatively, causing after 1- butene monomers solution, some butadiene solution and carbon monoxide-olefin polymeric are mixed, remains
Under butadiene solution be gradually added in polymerization system and carry out polymerization reaction, obtain copolymer；
The carbon monoxide-olefin polymeric is the mixture of rare earth catalyst, organo-aluminum compound and organoboron salt compound.
Preferably, in polymerization process, the concentration of the 1- butene monomers solution and the divinylic monomer solution
Ratio > 1.0.
Present invention also provides a kind of rubber compositions, including 1,3-butadiene described in above scheme and 1- butylene
The copolymer of 1,3- butadiene and 1- butylene prepared by preparation method described in copolymer or above scheme.
This application provides the copolymers of a kind of butadiene and 1- butylene, to contain butadiene structural units and 1- fourth
The random copolymer or segmented copolymer of alkene structural unit, and further define in copolymer butadiene structural units with
The content of 1- butylene part；The application separates on cis-butadiene cement main chain top into 1- butene monomers, so that double in copolymer chain
Key is reduced, and the copolymer made has excellent ageing-resistant, ozone resistance and wearability, is introduced in copolymer and is had side group
Butene-1 part, can further improve the leakproofness of copolymer.
Detailed description of the invention
Fig. 1 is copolymer sample prepared by the embodiment of the present invention 11HNMR spectrogram；
Fig. 2 is copolymer sample prepared by the embodiment of the present invention 61HNMR spectrogram；
Fig. 3 is copolymer sample prepared by the embodiment of the present invention 113C NMR spectra；
Fig. 4 is copolymer sample prepared by the embodiment of the present invention 613C NMR spectra；
Fig. 5 is the DSC figure of copolymer sample prepared by the embodiment of the present invention 3；
Fig. 6 is the DSC figure of copolymer sample prepared by the embodiment of the present invention 6.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses the copolymers of a kind of butadiene and 1- butylene, to contain butadiene structural units
With the random copolymer or segmented copolymer of 1- butylene structural unit, the random copolymer or the segmented copolymer
Without crystallization temperature；
The copolymer, the content of cis- Isosorbide-5-Nitrae key is in 70mol% or more, the copolymer in butadiene structural units
The content of butadiene structural units 1,2- is less than 30mol%；
The content of 1- butylene part is 5mol%~60mol% in the copolymer.
This application provides the copolymer of a kind of butadiene and 1- butylene, which, which does not have, includes long 1- butylene knot
The block copolymer and gradient copolymer of structure unit, comprise only irregular alignment 1- butylene structural unit and short 1- fourth
The random or segmented copolymer of alkene structural unit, and do not have crystallization temperature.The copolymer has ageing-resistant, resistance to ozone, resistance to
Mill, heat resistance, resistance to crack growth resistance and the excellent feature of leakproofness, can be used as rubber to apply.
Specifically, this application provides the copolymer of butadiene and 1- butylene, in the copolymer butadiene structural units
Cis- Isosorbide-5-Nitrae content is in 70mol% or more, and in a particular embodiment, cis- Isosorbide-5-Nitrae content is greater than in butadiene structural units
80mol%, more specifically, the cis- Isosorbide-5-Nitrae content of butadiene structural units is 80~93mol% in the copolymer.The copolymer
Middle butadiene structural units 1,2- content is less than 30mol%, in a particular embodiment, 1,2- in the butadiene structural units
Content be 7mol%~20mol%.In the application, the content of 1- butylene part is 5mol%~60mol%, is being had
In body embodiment, the content of 1- butylene part is 10~50mol%, and more specifically, the content of 1- butylene part is
20~50mol%.In this application, the stereoselective of the 1- butylene structural unit is complete same or random.In copolymer
Middle introducing 1- butylene, reduces the double bond in copolymer chain, so that copolymer has ageing-resistant, resistance to ozone and wear-resisting etc.
Performance, while side chain existing for 1- butylene, so that the leakproofness of copolymer enhances；The introducing of 1- butylene structural unit reduces
Double bond on main chain, content is higher, and wearability is good.
The number-average molecular weight of the copolymer of butadiene provided by the present application and 1- butylene is 10000~1000000, is being had
In body embodiment, the number-average molecular weight of the copolymer of the butadiene and 1- butylene is 100000~600000.The copolymer
Molecular weight distribution be 1~10, in a particular embodiment, the molecular weight distribution of the copolymer is 1~5, more specifically, institute
The molecular weight distribution for stating copolymer is 1~4.It is not copolymer if molecular weight distribution is too big, is mixture) butadiene
Glass transition temperature with the copolymer of 1- butylene is -110~-60 DEG C, in a particular embodiment, the butadiene and 1-
The glass transition temperature of the copolymer of butylene is -105 DEG C~-70 DEG C.
Present invention also provides the preparation methods of the butadiene and the copolymer of 1- butylene, comprising:
The 1- butene monomers solution of divinylic monomer solution, catalyst combination is mixed, causes polymerization, obtains copolymer；
It polymerize alternatively, causing after 1- butene monomers solution, some butadiene solution and carbon monoxide-olefin polymeric are mixed, remains
Under butadiene solution be gradually added in polymerization system and carry out polymerization reaction, obtain copolymer；The carbon monoxide-olefin polymeric is
The mixture of rare earth catalyst, organo-aluminum compound and organoboron salt compound.
The copolymer of above-mentioned butadiene and 1- butylene can be more specifically carried out as follows: in carbon monoxide-olefin polymeric
In the presence of, (1) will polymerize acquisition with the initiation of the mixed solution of 1- butylene containing butadiene；(2) pass through the presence in 1- butylene
Lower butadiene is added in polymerization system obtains；(3) by the way that 1- butylene is added in polymerization system in the presence of butadiene
It obtains.
Above-mentioned carbon monoxide-olefin polymeric is specially rare earth catalyst, organo-aluminum compound and organoboron salt compound, wherein dilute
Native catalyst is selected from one of following structural formula: by single cyclopentadienyl rare-earth complex of general formula (1) expression, by general formula
(2) the single cyclopentadienyl rare-earth complex with side wall indicated and the single cyclopentadienyl rare-earth complex with side wall indicated by general formula (3):
Wherein M is to be selected from: scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu),
One of gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu)；
R1、R2、R3、R4And R5It is same or different to each other, and is each independently hydrogen atom, contains 1~10 carbon atom
Alkyl, the alkyl of 1~10 carbon atom containing acetal, 1~10 carbon atom containing ketal alkyl, contain ether
The alkyl of 1~20 carbon atom, the alkenyl containing 2~20 carbon atoms, 2~20 carbon atoms containing acetal alkenyl,
The alkenyl of 2~20 carbon atoms containing ketal, the alkenyls of 2~20 carbon atoms containing ether, containing 6~20 carbon
Aralkyl, the aralkyl of 6~20 carbon atoms containing acetal, 6~20 carbon atoms containing ketal aralkyl, contain
Aralkyl, the silicyl containing 1~14 carbon atom, 1~14 carbon containing acetal of 6~20 carbon atoms of ether
The silicyl of atom, the silicyl of 1~14 carbon atom containing ketal, 1~14 carbon atom containing ether
One of silicyl；Or R1~R5In more than two groups can be connected to each other to form alicyclic or aromatic ring；
E is O, S or N-R, and wherein R is methyl, phenyl or substituted phenyl；
X1With X2It is the connected single anion ligand of rare earth metal, X1And X2It can be the same or different, X1And X2Respectively
It is independently hydrogen or linear chain or branched chain aliphatic group or alicyclic group, phenyl containing 1~20 carbon atom or by containing 1
The linear or branched alkyl group or cyclic aliphatic group of~20 carbon atoms or the aromatic group containing 6~20 carbon atoms take
Alkoxy, the linear chain or branched chain alkane containing 1~20 carbon atom of the phenyl in generation, linear chain or branched chain containing 1~20 carbon atom
Amido, the linear chain or branched chain aryl amine containing 6~20 carbon atoms, linear chain or branched chain silylation, boron containing 1~20 carbon atom
Hydrogen-based, allyl, allyl deriv, halogen etc.；
LwFor neutral Lewis base, such as one of tetrahydrofuran, ether, glycol dimethyl ether or pyridine；W is 0 to 3
Integer.
Cp in formula is cyclopentadienyl derivative C5A4, indenyl derivative C9A6Or fluorenyl derivative C13A8；A is ring penta
Substituent group on the substituent group of dialkylene, the substituent group of indenyl or fluorenyl, A is identical or different, and A is selected from hydrogen, aliphatic hydrocarbyl, virtue
Fragrant race's alkyl or silylation； R2For the substituent group on skeleton pyridine ring, selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or
Phenyl；R3For the substituent group on skeleton pyridine ring, it is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl；R4For skeleton pyrrole
Substituent group in phenazine ring is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl；R5For the substitution on skeleton pyridine ring
Base is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, 2,6- 3,5-dimethylphenyl, 4- aminomethyl phenyl, mesitylene
Base, 2,6- diisopropyl phenyl, 2,4,6- triisopropyl phenyl or 2,6- di-tert-butyl-phenyl；
Ln represents 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 single anion ligand, is selected from CH2SiMe3、CH(SiMe3)2, 1,3-C3H5, 1,3-C3H4(Me) or 1,3-C3H3
(SiMe3)2。
Cp is cyclopentadienyl derivative C5A4, indenyl derivative C9A6Or fluorenyl derivative C13A8；A is cyclopentadienyl group
Substituent group, indenyl substituent group or the substituent group on fluorenyl, A is identical or different, A be selected from hydrogen, aliphatic hydrocarbyl, aromatic hydrocarbon
Base or silylation；R2For the substituent group on skeleton pyridine ring, it is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl；R3
For the substituent group on skeleton pyridine ring, it is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl；R4For on skeleton pyridine ring
Substituent group, be selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl；R5For the substituent group on skeleton pyridine ring, it is selected from
Hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, 2,6- 3,5-dimethylphenyl, 4- aminomethyl phenyl, mesitylene base, 2,6-
Diisopropyl phenyl, 2,4,6- triisopropyl phenyl or 2,6- di-tert-butyl-phenyl；
Ln represents 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 single anion ligand, is selected from CH2SiMe3、CH(SiMe3)2、1,3-C3H5、1,3-C3H4(Me) or 1,3-C3H3
(SiMe3)2；
LwFor neutral Lewis base, such as one of tetrahydrofuran, ether, glycol dimethyl ether or pyridine；W is 0 to 3
Integer；
N is more than or equal to 1.
The organo-aluminum compound in catalyst system in the present invention contains at least one carbon-aluminium key and by tying as follows
Structure formula (4) indicates:
Wherein R6Selected from alkyl (including naphthenic base), alkoxy, aryl, alkaryl, aralkyl and hydrogen；R7Selected from alkyl
(including naphthenic base), aryl, alkaryl, aralkyl and hydrogen；And R8Selected from alkyl (including naphthenic base), aryl, alkaryl and
Aralkyl.
Typical compound corresponding with above structure are as follows: diethylaluminum hydride, diη-propyl aluminum hydride, di-n-butyl
Aluminum hydride, diisobutyl aluminium hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl hydrogen
Change aluminium, phenyl n-propyl aluminum hydride, p-methylphenyl ethyl aluminum hydride, p-methylphenyl n-propyl aluminum hydride, p-methylphenyl isopropyl
Aluminum hydride, benzyl ethyl aluminum hydride, benzyl n-propyl aluminum hydride, benzyl isopropyl aluminum hydride and other organic alanates.
Further include ethyl dihydroaluminium, butyl aluminum dihydride, isobutyl group aluminum dihydride, octyl aluminum dihydride, pentyl aluminum dihydride and its
His organo-aluminium dihydride；It further include diethylaluminum ethoxide and dipropyl aluminium ethylate；It further include trimethyl aluminium, triethyl aluminum, three
It is n-propyl aluminium, triisopropylaluminiuand, three n-butylaluminums, triisobutyl aluminium, three amyl aluminium, three hexyl aluminium, thricyclohexyl aluminium, three pungent
Base aluminium, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl diphenyl aluminium, ethyl di-p-tolyl aluminium, ethyl dibenzyl
Aluminium, diethyl phenyl aluminium, diethyl p-methylphenyl aluminium, diethylbenzyl aluminium and other three organo-aluminum compounds.
Organoboron salt compound of the invention can be for by the ionic chemical combination of organoboron anion and cation composition
Object；Organoboron anion includes tetraphenylborate ([BPh4]-), four (single fluorophenyl) borates, four (difluorophenyl) boric acid
Root, four (trifluorophenyl) borates, four (tetrafluoro phenyl) borates, four (pentafluorophenyl group) borate ([B (C6F5)4]-), four
(trifluoromethyl phenyl) borate, four (tolyl) borates, four (xylyl) borates, (triphenyl, pentafluorophenyl group)
Borate, [three (pentafluorophenyl groups), phenyl] borate and 11 hydrogenation -7, bis- carbon 11-borate root of 8-；Cation includes carbon
Cation, oxygen cation, ammonium cation, phosphonium cation, cycloheptatriene base cation and the ferrocene containing transition metal
Cation；Wherein carbocation includes trisubstituted carbocation such as triphenylcarbenium cation ([Ph3C]+) and three (take
The phenyl in generation) carbocation, and the more specific example of three (substituted phenyl) carbocations includes three (tolyls)
Carbocation；Ammonium cation includes trialkylammonium cation such as trimethyl ammonium cation, triethyl ammonium cation ([NEt3H]+)、
Tripropyl ammonium cation and tributyl ammonium cation；N, N- dialkylanilinium such as N, N- dimethylanilinium cation
([PhNMe2H]+), N, N- diethylbenzene ammonium cation and N, N-2,4,6- pentamethylbenzene ammonium cation；With dialkyl ammonium sun from
Son such as diisopropyl ammonium cation and dicyclohexyl ammonium cation.Phosphonium cation includes San Fang Ji phosphonium cation such as triphenyl phosphonium
Cation, three (tolyl) phosphonium cation and three (xylyl) phosphonium cations.
The example of organoboron salt compound includes [Ph3C][B(C6F5)4]、[PhNMe2H][BPh4]、 [NEt3H][BPh4]、
[PhNMe2H][B(C6F5)4] etc..Also the organoboron compound with organoboron salt compound said function, such as B can be used
(C6F5)3。
The ratio of each component in the catalyst system for preparing present copolymer are as follows: organo-aluminum compound and rare earth metal M
Molar ratio be 2:1 to adjustable between 300:1, preferably 4:1 is between 200:1, and most preferably 8:1 is between 100:1；Have
The molar ratio of organic boron salts compound and rare earth metal M are 1:10 to adjustable between 10:1, and preferably 0.5:1 is between 5:1.
Range for causing the usage amount of the catalyst of polymerization is very wide；The catalyst system of low concentration in this application
It is more satisfactory, because it can make to lead to the problem of ash content minimum.When the catalyst usage amount of rare earth metal M exists
When changing between 0.05 to 1.0 mM of metal/100 gram monomer, polymerization will occur；Preferred ratio is 0.1 to 0.3 milli
Between the monomer of mole metal/100 gram.
The polymeric reaction temperature of the application can extremely low temperature (such as -60 DEG C)~higher temperature (such as 150 DEG C) it
Between it is adjustable；In a particular embodiment, preferably 10 DEG C~150 DEG C of polymerization temperature, more preferable 25 DEG C~100 DEG C, more preferable 25 DEG C~
80℃.Polymerization reaction can carry out at one atm, can also under an atmospheric pressure or more than one atmospheric pressure into
Row.The pressure of 1- butylene preferably 1~10 atmospheric pressure.
Polymerization reaction carries out in hydrocarbon solvent, and suitable solvent includes sturated aliphatic hydrocarbon, aromatic hydrocarbon, aryl halogenation
One or more of object or cycloalkane, preferably hexane, hexamethylene, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes or bromobenzene
Mixture.
In polymerization process, usually the solution of divinylic monomer is added to containing rare earth catalyst, organic calorize
In the polymerization reaction system for closing the butene-1 solution of object and organoboron salt compound catalytic component；It is preferred that by the molten of butadiene
Liquid is added step-wise in the solution containing butene-1, rare earth catalyst, organo-aluminum compound and organoboron salt compound, more excellent
It is selected in entire polymerization process, butadiene solution is added with constant speed；Or by the mixed of butene-1 and butadiene
It closes in solution, the solution of rare earth catalyst, organo-aluminum compound and organoboron salt compound is added, cause polymerization.
In addition, the preparation method of the copolymer of butadiene according to the present invention and butene-1, butadiene in polymerization process
Concentration (mol/L) and the concentration (mol/L) of 1- butylene preferably satisfy following relationship: 1- butylene/butadiene concentration > 1.0；Into
One step preferably satisfies following relationship: 1- butylene/butadiene concentration >=2.
Present invention also provides a kind of rubber compositions comprising butadiene described in above scheme and 1- butylene are total to
Polymers.
According to actual needs, other diene based elastomers such as natural rubber, polybutadiene can also be added in rubber composition
Alkene and butadiene-styrene rubber, equally can also various additives, including filler such as carbon black and white carbon black, vulcanizing agent such as sulphur and promotor,
Processing oil, fatty acid, wax, resin and antidegradant.Rubber provided by the present application can be used for the different parts in tire, such as tire
Face, sidewall and other positions being made of rubber.
Copolymer of the invention can commonly used in elastomeric article, especially structural tire part and various rubber products such as every
Shake rubber, banding (conveyer belt), rubber belt track, various types of hoses and sealing ring.
For a further understanding of the present invention, butadiene provided by the invention and 1- butylene are total to below with reference to embodiment
Polymers and preparation method thereof is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
250mL toluene is added into the 2L stainless steel cauldron sufficiently purged with nitrogen, is vigorously stirred down and is filled with thereto
1.0atm 1- butene gas, makes it reach saturation state in toluene solution；In glove box, by the complex of formula 5
(74mg, 146 μm of ol), AliBu3(1.5mL, 1.46mmol, 1.0M toluene solvant) and four (pentafluorophenyl group) borates
Salt [Ph3C][B (C6F5)4] (135mg, 146 μm of ol) be dissolved in the toluene of 20mL, prepare catalyst solution；Later, it will urge
Agent solution in glove box from taking out and be added rapidly to cause polymerization in 40 DEG C of polymerization reaction system；Meanwhile butadiene
Toluene solution (130g solution, 26.7 weight % butadiene) constant speed be added in polymerization system, the drop of butadiene solution
Acceleration is controlled by flowmeter.Also it is passed through 1- butylene always in entire polymerization process.Butadiene solution is added dropwise
Afterwards, 20mL methanolic HCl solution is added immediately and terminates reaction；Then plus largely ethyl alcohol is to separate copolymer, vacuum at 40 DEG C
The polymeric marker of acquisition is sample A and characterized, tied by the dry copolymer until polymer weight does not change
Fruit is as shown in Fig. 1, Fig. 3 and table 1.
Embodiment 2
250mL toluene is added in 2L stainless steel cauldron, is then sufficiently purged with nitrogen, meanwhile, butadiene and 1- butylene
Toluene solution be added in polymerization system；In glove box, by complex (74mg, 150 μm of ol), the Al of formula 6iBu3
(1.5mL, 1.5mmol, 1.0M toluene solvant) and four (pentafluorophenyl group) borate salt [Ph3C][B(C6F5)4]
(139mg, 150 μm of ol) are dissolved in the toluene of 20mL, and catalyst solution is taken out and is added rapidly to from glove box
Cause polymerization in 40 DEG C of polymerization reaction system；Meanwhile the toluene solution constant speed of butadiene and 1- butylene is added to polymerization
In system, after butadiene and 1- butylene mixed solution are added dropwise, 20mL methanolic HCl solution is added immediately and terminates reaction；So
Ethyl alcohol is dried in vacuo the copolymer to separate copolymer afterwards plus largely at 40 DEG C, until polymer weight does not change and is
Only, it is sample B by the polymeric marker of acquisition and characterizes, is as a result shown in Table 1.
Embodiment 3
250mL toluene is added in 2L stainless steel cauldron, is then sufficiently purged with nitrogen, meanwhile, by butadiene and 1- fourth
The toluene solution of alkene is added in polymerization system.In glove box, by complex (73mg, 150 μm of ol), the Al of formula 7iBu3
(1.5mL, 1.5mmol, 1.0M toluene solvant) and four (pentafluorophenyl group) borate salt [Ph3C][B(C6F5) 4]
(139mg, 150 μm of ol) are dissolved in the toluene of 20mL, and catalyst solution is taken out from glove box and is added rapidly to 40
DEG C polymerization reaction system in cause polymerization, meanwhile, the toluene mixed solution constant speed of butadiene and 1- butylene is added to poly-
In zoarium system；After butadiene and 1- butylene mixed solution are added dropwise, 20mL methanolic HCl solution is added immediately and terminates reaction；
Then plus largely ethyl alcohol is dried in vacuo the copolymer to separate copolymer at 40 DEG C, until polymer weight does not change
Until.It is sample C by the polymeric marker of acquisition and characterizes, as a result as shown in Fig. 5 and table 1.
Embodiment 4
250mL toluene is added into the 2L stainless steel cauldron sufficiently purged with nitrogen, is vigorously stirred down and is filled with thereto
1.0atm1- butene gas, makes it reach saturation state in toluene solution；In glove box, by the complex of formula 8 (91mg,
150μmol)、AliBu3(1.5mL, 1.5mmol, 1.0M toluene solvant) and four (pentafluorophenyl group) borate salt [Ph3C]
[B (C6F5)4] (139mg, 150 μm of ol) be dissolved in the toluene of 20mL, prepare catalyst solution；Later, by catalyst solution
From taking out and be added rapidly to cause in 40 DEG C of polymerization reaction system polymerization in glove box, meanwhile, the toluene of butadiene is molten
Liquid is added in polymerization system, and the pressure of 1- butylene is increased to 4.0atm, is passed through 1- butylene always in entire polymerization process；
After polymerization reaction proceeds to specified time, 20mL methanolic HCl solution is added immediately and terminates reaction；Then plus largely ethyl alcohol
To separate copolymer, the copolymer is dried in vacuo at 40 DEG C, until polymer weight does not change.By the poly- of acquisition
It closes substance markers and is sample D and characterizes that the results are shown in Table 1.
Embodiment 5
250mL toluene is added into the 2L stainless steel cauldron sufficiently purged with nitrogen, is vigorously stirred down and is filled with thereto
1.0atm1- butene gas, makes it reach saturation state in toluene solution；In glove box, by the complex of formula 9 (81mg,
150μmol)、AliBu3(1.5mL, 1.5mmol, 1.0M toluene solvant) and four (pentafluorophenyl group) borate salt [Ph3C]
[B (C6F5)4] (139mg, 150 μm of ol) be dissolved in the toluene of 20mL, prepare catalyst solution；Later, by catalyst solution
From taking out and be added rapidly to cause in 40 DEG C of polymerization reaction system polymerization in glove box, meanwhile, the toluene of butadiene is molten
Liquid is added in polymerization system, and the pressure of 1- butylene is increased to 4.0atm, is passed through 1- butylene always in entire polymerization process；
After polymerization reaction proceeds to specified time, 20mL methanolic HCl solution is added immediately and terminates reaction；Then plus largely ethyl alcohol
To separate copolymer, the copolymer is dried in vacuo at 40 DEG C, until polymer weight does not change.By the poly- of acquisition
It closes substance markers and is sample E and characterizes that the results are shown in Table 1.
Embodiment 6
250mL toluene is added in 2L stainless steel cauldron, is then sufficiently purged with nitrogen, meanwhile, butadiene and 1- butylene
Toluene solution be added in polymerization system；In glove box, by complex (81mg, 150 μm of ol), the Al of formula 9iBu3
(1.5mL, 1.5mmol, 1.0M toluene solvant) and four (pentafluorophenyl group) borate salt [Ph3C][B(C6F5)4]
(139mg, 150 μm of ol) are dissolved in the toluene of 20mL, and catalyst solution is taken out and is added rapidly to from glove box
Cause polymerization in 25 DEG C of polymerization reaction system, meanwhile, the toluene solution constant speed of butadiene and 1- butylene is added to polymerization
In system；After butadiene and 1- butylene mixed solution are added dropwise, 20mL methanolic HCl solution is added immediately and terminates reaction；So
Ethyl alcohol is dried in vacuo the copolymer to separate copolymer afterwards plus largely at 40 DEG C, until polymer weight does not change and is
Only.It is sample F by the polymeric marker of acquisition and characterizes, is as a result shown in Fig. 2, Fig. 4, Fig. 6 and table 1.
Comparative example 1
The butadiene rubber of copolymer A~F of Examples 1 to 6, comparative example 1 is characterized respectively in the following manner,
To study microstructure, 1- butene content, the equal average molecular weight (M of numbern), molecular weight distribution (Mw/Mn) and DSC curve.
1) measurement in copolymer in butadiene structural units along 1,4 structural units and 1,2- structural unit content:
In copolymer in butadiene structural units along 1,4- structural unit and 1,2- structural unit content according to polymer
's13C NMR spectra and1HNMR measurement；
The regioselectivity (1,2- and 1,4) of butadiene fraction is by being based in copolymer1H-NMR spectrum (25 DEG C, CDCl3)
1,2- vinyl bonds component (4.8ppm-5.05ppm) and 1,4- butadiene key component (the integral ratio of 5.25ppm-5.6ppm
It determines, butadiene fraction is along Isosorbide-5-Nitrae-and anti-Isosorbide-5-Nitrae-selectivity by being based in copolymer13C-NMR spectrum (25 DEG C, CDCl3) it is suitable
The integral ratio of -1,4 key component (27ppm-28.2ppm) of formula and anti-1,4 key component (31.5ppm-33ppm) determines.
2) in copolymer 1- butene content measurement:
The content of 1- butylene structural unit is according in CDCl in copolymer3The copolymer of middle measurement1H NMR spectra calculates
It obtains, 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) measurement of copolymer glass transition temperature (Tg):
The glass transition temperature of copolymer is measured by differential scanning calorimetry (DSC) according to GB/T 29611-2013.
4) copolymer number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) measurement:
Number-average molecular weight (the M of copolymern) and molecular weight distribution (Mw/Mn) by using polystyrene as the gel of reference substance
Permeation chromatography (GPC) is at 150 DEG C, with 1,2,4-C6Cl3H3For mobile phase measurement.
1 butadiene of table and 1- butene result data table
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, defined herein
General Principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to special with principles disclosed herein and novelty
The consistent widest scope of point.
Claims (10)
1. the copolymer of a kind of butadiene and 1- butylene, to be total to containing butadiene structural units and the random of 1- butylene structural unit
Polymers or segmented copolymer, the random copolymer or the segmented copolymer do not have crystallization temperature；
The content of the cis- Isosorbide-5-Nitrae key of butadiene structural units is in 70mol% or more, the butadiene of the copolymer in the copolymer
1,2- content is less than 30mol% in structural unit；
The content of 1- butylene part is 5mol%~60mol% in the copolymer.
2. copolymer according to claim 1, which is characterized in that the vertical structure choosing of 1- butylene structural unit in the copolymer
Selecting property is complete same or random.
3. copolymer according to claim 1, which is characterized in that the number-average molecular weight of the copolymer be 10000~
1000000, the molecular weight distribution of the copolymer is 1~10.
4. copolymer according to claim 1, which is characterized in that the copolymer glass transition temperature be -110~-
60℃。
5. copolymer according to claim 1, which is characterized in that cis- Isosorbide-5-Nitrae in the butadiene structural units of the copolymer
Content be 80~93mol%.
6. copolymer according to claim 1, which is characterized in that 1,2- in the butadiene structural units of the copolymer
Content is 7~20mol%.
7. copolymer according to claim 1, which is characterized in that the content of 1- butylene part in the copolymer
10mol%~50mol%.
8. the preparation method of the copolymer of butadiene described in claim 1 and 1- butylene, comprising:
Divinylic monomer solution, carbon monoxide-olefin polymeric and 1- butene monomers solution are mixed, causes polymerization, obtains copolymer；
It polymerize alternatively, causing after 1- butene monomers solution, some butadiene solution and carbon monoxide-olefin polymeric are mixed, remaining fourth
Diene solution, which is gradually added in polymerization system, carries out polymerization reaction, obtain copolymer；
The carbon monoxide-olefin polymeric is the mixture of rare earth catalyst, organo-aluminum compound and organoboron salt compound.
9. preparation method according to claim 8, which is characterized in that in polymerization process, the 1- butene monomers
Ratio > 1.0 of the concentration of solution and the divinylic monomer solution.
10. a kind of rubber composition, the copolymer including claim 1~7 described in any item 1,3-butadienes and 1- butylene
Or the copolymer of 1,3- butadiene and 1- butylene prepared by the described in any item preparation methods of claim 8~9.
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| CN112851841A (en) * | 2021-03-17 | 2021-05-28 | 中国科学院长春应用化学研究所 | Preparation method of polyalkyl vinyl ether |
| CN113174001A (en) * | 2021-06-09 | 2021-07-27 | 中国科学院长春应用化学研究所 | Ethylene-butadiene random copolymer and preparation method and application thereof |
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