CN102372822A - Method for preparing isomonoolefine-polyene copolymer - Google Patents
Method for preparing isomonoolefine-polyene copolymer Download PDFInfo
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Abstract
The invention relates to a method for preparing an isomonoolefine-polyene copolymer. According to the method, at a temperature of -120 DEG C to -20 DEG C, in presence of an inert organic solvent, at least one C4-C8 isomonoolefine monomer and at least one C4-C14 polyene monomer contact with an initiator system which is composed of monoalkyl aluminum dihalide as presented by formula (I) in the specification and halogen-multifunctionalized organic halide as presented by formula (II) in the specification, wherein, variables in compounds of formula (I) and formula (II) are as defined in the specification. The prepared isomonoolefine-polyene copolymer has broad molecular weight distribution and even has bimodal molecular weight distribution, and the copolymer has a high molecular weight.
Description
Technical field
The present invention relates to a kind of method for preparing isomonoolefin-multi-olefin copolymer, this method can prepare the isomonoolefin-multi-olefin copolymer with wide molecular weight distribution.More specifically, the present invention relates to a kind of method that in the presence of the initiator system of forming by monoalkyl dihalide aluminium and the multiple functionalized Organohalogen compounds of halogen, isomonoolefin and polyene hydrocarbon copolymerization can be obtained having the isomonoolefin-multi-olefin copolymer of wide molecular weight distribution.
Background technology
The history that butyl rubber (IIR) comes out and apart from modern arranged six more than ten years as commodity becomes one of most important viton kind owing to it has excellent characteristics such as resistance to air loss, damping and amortization, heat-resistant aging, anti-ozone and weathering resistance.
At present; Except adopting solution polymerization process, Russian Togliatti company produces the butyl rubber; It is that the slurry polymerization process of solvent is produced butyl rubber that other companies all adopt with the monochloro methane, like ExxonMobile company, Lanxess company, Russian NKNK company and Chinese Yanshan Petrochemical company.
Adopt slurry polymerization process to produce butyl rubber, in the industrial production generally with H
2O/AlCl
3As initiator system, because the shipwreck in the solvent is to eliminate the very difficult control of actual water content; And solid AlCl
3Also as easy as rolling off a log suction need adopt a large amount of refining solvents to wash before use; Again because AlCl
3Solubleness in the solvent monochloro methane is very low, makes H
2O/AlCl
3The compounding system of initiator system is huge, relates to the refining and useless AlCl of recovery of solvent
3Handle, and water-content is difficult to stable control, increased difficulty for the production control of butyl rubber.
Adopt slurry polymerization process to produce butyl rubber, another major issue that relates to is exactly the processability issues of butyl rubber.Find that through years of researches in fact the processing characteristics of butyl rubber has very important relation with MWD; When producing butyl rubber; Except will guaranteeing enough weight-average molecular weight; The balance that also need keep suitable high low molecular weight part, HMW part are in order to obtaining enough green strengths, and low molecular weight part is in order to guarantee certain stress relaxation rate.Contrast is found; The butyl rubber of narrow molecular weight distributions is cracked easily on mixing roll; Add wide molecular weight distribution and can eliminate such problem; And also no longer need extreme mixing step just can reach dispersion in the mixing process with the carbon black uniform and delicate, make goods have better physical and mechanical properties; Butyl rubber with wide molecular weight distribution also has more stable size and dimension in the course of processing.Yet; The MWD of polymkeric substance before processing greatly depends on polymerization reaction mechanism; The polyreaction of confirming has just determined the weight distributing characteristic of this polymkeric substance, will realize that therefore the purpose of widening molecular weight distribution often need take some special method or means.At present, adopt slurry polymerization process to produce butyl rubber, ExxonMobile company and Lanxess company can produce molecular weight polydispersity coefficient M
w/ M
nCan reach the butyl rubber more than 3.5, and its molecular weight polydispersity coefficient of butyl rubber M of Russia and China's production
w/ M
nAll be lower than 3.0, processing characteristics is relatively poor.
About widening the butyl rubber MWD or improving the method for butyl rubber processing characteristics; Patent US2781334 and US2729626 are proposed in and add coupling agent Vinylstyrene (DVB) in the polymerization system; Make part molecular chain generation coupling generate a small amount of high-molecular weight branching macromole, will bring tangible gel problem but the DVB consumption is many slightly to improve the initial strength of polymkeric substance.Patent WO0216452 improves this method, under the prerequisite that adds polyene hydrocarbon linking agent such as DVB, introduces an amount of chain-transfer agent such as diisobutylene again and also improves the processing characteristics of polymkeric substance simultaneously to alleviate the gel problem.The tetrahalide composition composite initiator of IV family metal in the metal halide that patent US3780002 propose to adopt II family in the periodic table of elements or III-th family and the periodic table of elements is as with AlCl
3With TiCl
4Compound use, or with AlCl
3With SnCl
4Compound use makes wherein that each initiator can cause cationoid polymerisation independently, the synthetic MWD coefficient M that obtains under the butyl rubber polymerizing condition of routine
w/ M
nAt the butyl rubber more than 5.0.Patent US5071913 has invented and in monomer mixture solution, has added a spot of SBS or SIS segmented copolymer; Unsaturated double-bond wherein just can directly generate part through chain transfer or participation copolymerization mode and have the very highly branched star-shaped molecule of high-molecular weight in polymerization process; Obtain having the butyl rubber of bimodal molecular weight distribution, i.e. the star butyl rubber product developed of ExxonMobile company.Patent US5194538 discloses and has adopted the different initiator of functional group's number to carry out compound use, promptly at traditional butyl rubber H
2O/AlCl
3Add a kind of compound that contains 2-4 hydroxyl in the initiator system more in addition, the result obtains appearing the butyl polymer of bimodal molecular weight distribution.US20030166809 proposes in the mixed system of dialkylaluminum chloride and monoalkyl al dichloride, to add a small amount of acvator aikyiaiurnirsoxan beta initiator system is carried out activation modification, is used for solution polymerization and synthesizes the butyl rubber with wide molecular weight distribution.CN1966537A discloses with H
2O/AlCl
3For adding some additives in the slurry polymerization system of initiator system, like compounds such as alcohols, phenols, amine or pyridines, amides, carboxylic acid esters or ketones, with AlCl
3Carry out ageing reaction back and form composite initiator system, through regulating this additive and AlCl
3Usage ratio, molecular weight and the MWD that can regulate butyl rubber within the specific limits.
Visible by above art methods, widen the butyl rubber MWD, all need adopt the mode of adding additional component, and all can bring otherwise problem in varying degrees.Therefore, seeking a kind of simple and practical method produces the butyl rubber that has than wide molecular weight distribution or excellent machinability and is necessary.
Organic cpds with a plurality of halogen atoms is commonly used to functional polymers such as synthetic multi-arm star polymkeric substance, segmented copolymer or telechelic polymer, and for example patent US4740572 has proposed with the Organohalogen compounds (formula as follows) and the BCl that contain a plurality of halogen atoms
3Forming initiator system makes isobutene polymerisation obtain the telechelic polymer that molecule chain end has active halo atom end group.
Patent US4946899 and US4276394 also adopt such compound and TiCl
4Or BCl
3And electron donor forms initiator system and carries out living cationic polymerization, synthesized telechelic polymer or had thermoplastic segmented copolymer.
Patent US4942210 has proposed to adopt the diamantane and the aikyl aluminum halide that contain 2-4 halogen atom to form synthetic multi-arm of initiator system or star-branched isoolefin homopolymer or multipolymer.
The initiator system that the present invention is intended to adopt the Organohalogen compounds that contain many halogens functional group and monoalkyl dihalide aluminium to form is used for synthetic butyl polymer with wide molecular weight distribution.
The object of the present invention is to provide a kind of simple and economic and practical initiator system to prepare butyl polymer; Wherein the solvability of each component in polymer solvent of this initiator system is good; Blending process is simple, and concentration adjustment is convenient, and not only the efficiency of initiation of initiator system is high, polymerization activity is stable; And the also more stable control more easily of polymerisation slurry system, the butyl polymer that adopts conventional butyl rubber polymerization method just can prepare high-molecular weight, have wide molecular weight distribution.
Summary of the invention
The inventor unexpectedly finds; Isomonoolefin-multi-olefin copolymer is synthesized in copolymerization through being used to cause isomonoolefin and polyene hydrocarbon by the initiator system that functionalized Organohalogen compounds of many halogens and monoalkyl dihalide aluminium are formed; Gained isomonoolefin-multi-olefin copolymer not only molecular weight is high, and can have wide molecular weight distribution.
Therefore the present invention provides a kind of method for preparing isomonoolefin-multi-olefin copolymer, this method to comprise and makes at least a C
4-C
8Isomonoolefin monomer and at least a C
4-C
14Multi-olefin monomer under-120 ℃ to-20 ℃ temperature, in the presence of inert organic solvents, contacts with the initiator system of being made up of the multiple functionalized Organohalogen compounds of halogen of the monoalkyl dihalide aluminium of following formula (I) and following formula (II),
AlRY
2 (I)
In the formula (I), R is straight or branched C
1-C
8Alkyl and 2 Y are halogen independently of one another,
In the formula (II),
N is 2,3 or 4;
R
1For being selected from down the abutment of group:
The C of-straight or branched
1-C
10The alkyl abutment,
-phenyl abutment, this phenyl abutment can be unsubstituted, also can be by 1-4 straight or branched C
1-C
6Alkyl replaces;
R
2And R
3Be hydrogen, straight or branched C independently of one another
1-C
8Alkyl, phenyl, the inferior C of phenyl straight or branched
1-C
4Alkyl, straight or branched C
1-C
4Alkyl phenylene or C
3-C
8Naphthenic base, wherein R
2And R
3Can be the same or different; And
X is a halogen.
For the purpose of the present invention, " halogen " is meant fluorine, chlorine, bromine or iodine, preferred chlorine or bromine, especially chlorine.
For the purpose of the present invention, term " straight or branched C
1-C
4Alkyl " refer to the straight chain that contains 1-4 carbon atom or the alkyl of branching.The example of these alkyl includes but not limited to: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-and the tertiary butyl.
For the purpose of the present invention, term " the inferior C of straight or branched
1-C
4Alkyl " refer to the straight chain that contains 1-4 carbon atom or the divalent alkyl of branching.The example of these alkyl includes but not limited to: methylene radical, ethylidene, propylidene, isopropylidene, inferior normal-butyl, inferior sec.-butyl, isobutylidene and the inferior tertiary butyl.
For the purpose of the present invention, term " straight or branched C
1-C
6Alkyl " refer to the straight chain that contains 1-6 carbon atom or the alkyl of branching.The example of these alkyl except preceding text for " straight or branched C
1-C
4Alkyl " mentioned each be beyond the instance, also include but not limited to: n-pentyl, 2-amyl group, 2-methylbutyl, 3-methylbutyl, 1,1-dimethyl propyl, 1; 2-dimethyl propyl, 2,2-dimethyl propyl, 1-ethyl propyl, n-hexyl, 2-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,2-dimethylbutyl, 1; 3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2; 2-dimethylbutyl, 3,3-dimethylbutyl, 1,1; 2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, 1-ethyl-butyl, 2-ethyl-butyl and 1-ethyl-2-methyl-propyl.
For the purpose of the present invention, term " straight or branched C
1-C
8Alkyl " refer to the straight chain that contains 1-8 carbon atom or the alkyl of branching.The example of these alkyl except preceding text for " straight or branched C
1-C
6Alkyl " mentioned each be beyond the instance, also include but not limited to: n-heptyl, 1-methyl hexyl, 2-methyl hexyl, 3-methyl hexyl, 1,1-dimethyl-amyl group, 1; 2-dimethyl-amyl group, 1,3-dimethyl-amyl group, 1,4-dimethyl-amyl group, 2; 2-dimethyl-amyl group, 2,3-dimethyl-amyl group, 2,4-dimethyl-amyl group, 3; 3-dimethyl-amyl group, 3,4-dimethyl-amyl group, 4,4-dimethyl-amyl group, 1-ethyl pentyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, 1-n-propyl butyl, 1-sec.-propyl butyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1; 1-dimethyl-hexyl, 1,2-dimethyl-hexyl, 1,3-dimethyl-hexyl, 1; 4-dimethyl-hexyl, 1,5-dimethyl-hexyl, 2,2-dimethyl-hexyl, 2; 3-dimethyl-hexyl, 2,4-dimethyl-hexyl, 2,5-dimethyl-hexyl, 3; 3-dimethyl-hexyl, 3,4-dimethyl-hexyl, 3,5-dimethyl-hexyl, 4; 4-dimethyl-hexyl, 4,5-dimethyl-hexyl, 5,5-dimethyl-hexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-n-propyl amyl group, 2-n-propyl amyl group, 1-sec.-propyl amyl group and 2-sec.-propyl amyl group.
For the purpose of the present invention, term " straight or branched C
1-C
10Alkyl " refer to the straight chain that contains 1-10 carbon atom or the alkyl of branching.The example of these alkyl except preceding text for " straight or branched C
1-C
8Alkyl " mentioned each be beyond the instance, also include but not limited to: n-nonyl, 1-Methyl Octyl, 2-Methyl Octyl, 3-Methyl Octyl, 4-Methyl Octyl, 5-Methyl Octyl, 6-Methyl Octyl, 7-Methyl Octyl, 1,1-dimethyl-heptyl, 1; 2-dimethyl-heptyl, 1,3-dimethyl-heptyl, 1,4-dimethyl-heptyl, 1; 5-dimethyl-heptyl, 1,6-dimethyl-heptyl, 2,2-dimethyl-heptyl, 2; 3-dimethyl-heptyl, 2,4-dimethyl-heptyl, 2,5-dimethyl-heptyl, 2; 6-dimethyl-heptyl, 3,3-dimethyl-heptyl, 3,4-dimethyl-heptyl, 3; 5-dimethyl-heptyl, 3,6-dimethyl-heptyl, 4,4-dimethyl-heptyl, 4; 5-dimethyl-heptyl, 4,6-dimethyl-heptyl, 5,5-dimethyl-heptyl, 5; 6-dimethyl-heptyl, 6,6-dimethyl-heptyl, 1-ethyl heptyl, 2-ethyl heptyl, 3-ethyl heptyl, 4-ethyl heptyl, 5-ethyl heptyl, 1-n-propyl hexyl, 2-n-propyl hexyl, 3-n-propyl hexyl, 1-sec.-propyl hexyl, 2-sec.-propyl hexyl, 3-sec.-propyl hexyl, 1-normal-butyl amyl group, 1-isobutyl-amyl group, 1-sec.-butyl amyl group, 1-tertiary butyl amyl group, positive decyl, 1-methyl nonyl, 2-methyl nonyl, 3-methyl nonyl, 4-methyl nonyl, 5-methyl nonyl, 6-methyl nonyl, 7-methyl nonyl, 8-methyl nonyl, 1,1-dimethyl-octyl group, 1; 2-dimethyl-octyl group, 1,3-dimethyl-octyl group, 1,4-dimethyl-octyl group, 1; 5-dimethyl-octyl group, 1,6-dimethyl-octyl group, 1,7-dimethyl-octyl group, 2; 2-dimethyl-octyl group, 2,3-dimethyl-octyl group, 2,4-dimethyl-octyl group, 2; 5-dimethyl-octyl group, 2,6-dimethyl-octyl group, 2,7-dimethyl-octyl group, 3; 3-dimethyl-octyl group, 3,4-dimethyl-octyl group, 3,5-dimethyl-octyl group, 3; 6-dimethyl-octyl group, 3,7-dimethyl-octyl group, 4,4-dimethyl-octyl group, 4; 5-dimethyl-octyl group, 4,6-dimethyl-octyl group, 4,7-dimethyl-octyl group, 5; 5-dimethyl-octyl group, 5,6-dimethyl-octyl group, 5,7-dimethyl-octyl group, 6; 6-dimethyl-octyl group, 6,7-dimethyl-octyl group, 7,7-dimethyl-octyl group, 1-ethyl octyl group, 2-ethyl octyl group, 3-ethyl octyl group, 4-ethyl octyl group, 5-ethyl octyl group, 6-ethyl octyl group, 1-n-propyl heptyl, 2-n-propyl heptyl, 3-n-propyl heptyl, 4-n-propyl heptyl, 1-sec.-propyl heptyl, 2-sec.-propyl heptyl, 3-sec.-propyl heptyl, 4-sec.-propyl heptyl, 1-normal-butyl hexyl, 2-normal-butyl hexyl, 1-sec.-butyl hexyl, 2-sec.-butyl hexyl, 1-isobutyl-hexyl, 2-isobutyl-hexyl, 1-tertiary butyl hexyl and 2-tertiary butyl hexyl.
For the purpose of the present invention, term " C
3-C
8Naphthenic base " refer to the cyclic alkyl that contains 3-8 ring carbon atom, it includes but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.
In the methods of the invention, initiator system comprises the monoalkyl dihalide aluminium of formula (I).For the monoalkyl R that this compound comprised, it can be to contain 1-8, preferred 1-6, the straight or branched alkyl of 1-4 carbon atom more preferably, is preferably ethyl especially.For two halogen atoms that the monoalkyl dihalide aluminum compound of formula (I) is comprised, preferred said two halogen atoms are identical, for example are chlorine or bromine, especially are chlorine.
As the monoalkyl dihalide aluminium of formula (I), it includes but not limited to: dichloromethyl aluminium, ethyl aluminum dichloride, two chloropropyl aluminium, two chlorobutyl aluminium, dichloro aluminium isobutyl, dichloro amyl group aluminium, dichloro hexyl aluminium, dichloro heptyl aluminium, dichloro octyl group aluminium, dichloro 2-ethylhexyl aluminium, dibromo aluminium trimethide, dibromo aluminium triethyl, dibromopropyl aluminium, two brombutyl aluminium, dibromo-isobutyl base aluminium, dibromo amyl group aluminium, dibromo hexyl aluminium, dibromo heptyl aluminium, dibromo octyl group aluminium, dibromo 2-ethylhexyl aluminium, a chlorine monobromo aluminium trimethide, a chlorine monobromo aluminium triethyl, a chlorine one bromopropyl aluminium, a chlorine one brombutyl aluminium, a chlorine monobromo aluminium isobutyl, a chlorine monobromo amyl group aluminium, a chlorine monobromo hexyl aluminium, a chlorine monobromo heptyl aluminium, a chlorine monobromo octyl group aluminium and a chlorine monobromo 2-ethylhexyl aluminium.
In a preferred embodiment of the inventive method, the formula of use (I) compound is the monoalkyl dihalide aluminium that contains the straight or branched alkyl of 1-4 carbon atom for monoalkyl wherein.In another preferred embodiment, the formula of use (I) compound is the monoalkyl dihalide aluminium of chlorine atom or bromine atoms for two halogen atoms wherein.In a special preferred embodiment of the inventive method, as formula (I) compound, using monoalkyl wherein is to contain the straight or branched alkyl of 1-4 carbon atom and the monoalkyl dihalide aluminium that two halogen atoms are the chlorine atom.The monoalkyl dihalide aluminium of formula (I) especially is selected from down group: dichloromethyl aluminium, ethyl aluminum dichloride, two chloropropyl aluminium, two chlorobutyl aluminium and dichloro aluminium isobutyl, particularly ethyl aluminum dichloride.
In the methods of the invention, initiator system comprises the multiple functionalized Organohalogen compounds of halogen of formula (II).In this compound, as the R of abutment
1Group depends on n, and it can be divalence, trivalent or quaternary, and promptly abutment can be divalent abutment, trivalent abutment or tetravalence abutment.
In formula (II) compound, as the R of multivalence abutment
1Group, it can be the C of straight or branched
1-C
10The alkyl abutment, the C of preferred straight or branched
1-C
4The alkyl abutment, it includes but not limited to: methylene radical, 1,1-ethylidene, ethylene, trimethylene, 2,2-propylidene, 1; 2,3-trivalent propyl group, tetramethylene, 1,2-dimethyl--ethylene, pentamethylene, 2; 2-dimethyl--trimethylene, season penta tetramethylene, hexamethylene, 1, the inferior heptyl of 7-, octamethylene, 2,2; 3,3-tetramethyl--tetramethylene, nonamethylene, 1, the inferior decyl and 1,1 of 10-; 4,4-tetravalence butyl, preferred especially methylene radical, ethylene, trimethylene and tetramethylene.
As the multivalence abutment R in formula (II) compound
1, it can also be the phenyl abutment, this phenyl abutment can be unsubstituted, also can be by 1-4 straight or branched C
1-C
6Alkyl replaces.This does not replace or substituted phenyl abutment can be connected with C atom shown in the general formula (I) with any position, and for example when this phenyl was divalent abutment, it can be with 1,2-position, 1, and 3-position or 1, the 4-position connects; When this phenyl was the trivalent abutment, it can be with 1,2,3-position, 1,2, and 4-position or 1,3, the 5-position connects; When this phenyl was the tetravalence abutment, it can be with 1,2,3,4-position, 1,2,3, and 5-position or 1,2,4, the 5-position connects.In a preferred embodiment, abutment R
1For unsubstituted phenyl or have a substituent phenyl, for example be 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 5-substituting group (are straight or branched C
1-C
6Alkyl)-1,3-phenylene, 1,3,5-phenenyl abutment or 1,2,4,5-tetravalence phenyl abutment, especially 1,4-phenylene or 1,3,5-phenenyl abutment.
In formula (II) compound, R
2And R
3Be hydrogen, straight or branched C independently of one another
1-C
8Alkyl, phenyl, the inferior C of phenyl straight or branched
1-C
4Alkyl, straight or branched C
1-C
4Alkyl phenylene or C
3-C
8Naphthenic base, wherein R
2And R
3Can be the same or different.
In formula (II) compound, X is a halogen atom, and preferred chlorine or bromine is preferably the chlorine atom especially.
As formula (II) examples for compounds, can mention following: 1,4-two chloro-1,1,4,4-tetraphenyl butane, 1,4-two chloro-1,1; 4,4-4-methyl-butane, 1,4-two bromo-1,1,4,4-tetraphenyl butane, 1,4-two bromo-1,1; 4,4-4-methyl-butane, 2,5-two chloro-2,5-dimethylhexane, 2,5-two chloro-2,5-phenylbenzene hexane, 2,5-two bromo-2,5-dimethylhexane, 2; 5-two bromo-2,5-phenylbenzene hexane, 2,6-two chloro-2,4,4,6-tetramethyl-heptane, 2,6-two chloro-2,4; 4,6-tetraphenyl heptane, 2,6-two bromo-2,4,4,6-tetramethyl-heptane, 2,6-two bromo-2,4; 4,6-tetraphenyl heptane, right-xylylene dichlorides, right-xylylene bromide, right-two (1-chloroethyl) benzene, right-two (1-bromotrifluoromethane) benzene, right-two (2-chloro-2-propyl group) benzene, right-two (2-bromo-2-propyl group) benzene, 1,3-two (2-chloro-2-propyl group)-5-tert.-butylbenzene, 1,3-two (2-bromo-2-propyl group)-5-tert.-butylbenzene, 1,3-two (2-chloro-2-propyl group)-5-isopropyl benzene, 1,3-two (2-bromo-2-propyl group)-5-isopropyl benzene, 2,4-two chloro-2,4-dimethylpentane, 2; 4-two bromo-2,4-dimethylpentane, 5,7-two chloro-5,7-dimethyl-undecane, 5,7-two bromo-5,7-dimethyl-undecane, 5,8-two chloro-5; 8-dimethyl-dodecyl, 5,8-two bromo-5,8-dimethyl-dodecyl, 2,5-two chloro-2,5-two (p-methylphenyl) hexane, 2,5-two bromo-2,5-two (p-methylphenyl) hexane, 2; 5-two chloro-2,5-dibenzyl hexane, 2,5-two bromo-2,5-dibenzyl hexane, 2,7-two chloro-2,7-two cyclopropyl octanes, 2,7-two bromo-2; 7-two cyclopropyl octanes, 1,3,5-three (chloromethyl) benzene, 1,3,5-three (brooethyl) benzene, 1,3,5-three (1-chloroethyl) benzene, 1; 3,5-three (1-bromotrifluoromethane) benzene, 1,3,5-three (2-chloro-2-propyl group) benzene, 1,3,5-three (2-bromo-2-propyl group) benzene, 1,3; 5-three (2-chloro-2-butyl) benzene, 1,3,5-three (2-bromo-2-butyl) benzene, 1,2,4,5-four (chloromethyl) benzene, 1,2; 4,5-four (brooethyl) benzene, 1,2,4,5-four (1-chloroethyl) benzene, 1,2,4; 5-four (1-bromotrifluoromethane) benzene, 1,2,4,5-four (2-chloro-2-propyl group) benzene and 1,2,4,5-four (2-bromo-2-propyl group) benzene.
In the present invention, formula (I) compound is a coinitiator, and formula (II) compound is an initiator.Usually use with homogeneous phase solution according to initiator system of the present invention, disclosed butyl rubber polymerization solvent for use all can be used for initiator system of the present invention in prior art, for example monochloro methane, methylene dichloride, hexane or its mixture.Generally speaking, in initiator system, initiator concentration is controlled at 10
-5～10
-2In the mol/L scope, the concentration of coinitiator is controlled at 10
-3～10
-1In the mol/L scope.Perhaps, the mol ratio of formula (I) compound and formula (II) compound is 0.1 to 1000, preferred 0.5-500, more preferably 1～100.
Isomonoolefin-multi-olefin copolymer through the inventive method preparation has wide molecular weight distribution.In order to obtain the mentioned isomonoolefin-multi-olefin copolymer with wide molecular weight distribution of the inventive method, the comonomer of use comprises C
4-C
8Isomonoolefin monomer and C
4-C
14Multi-olefin monomer.
For the present invention, term " C
4-C
8Isomonoolefin " refer to and contain the isoolefine that 4-8 carbon atom and the first carbon atom have olefinic double bond.
As C
4-C
8The isomonoolefin monomer can be mentioned 2-methyl isophthalic acid-propylene (iso-butylene), 2-methyl-1-butene alkene, 3-methyl-1-butene, 2,3-dimethyl--1-butylene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2; 3-dimethyl--1-amylene, 2,4-dimethyl--1-amylene, 2-methyl isophthalic acid-hexene, 2,3-dimethyl--1-hexene, 2; 4-dimethyl--1-hexene, 2,5-dimethyl--1-hexene, 2,4; 4-trimethylammonium-1-amylene, preferred iso-butylene.
For the present invention, term " C
4-C
14Multi-olefin monomer " refer to the alkene that contains 4-14 carbon atom and two or more olefinic double bonds.This C
4-C
14Polyene hydrocarbon is preferably the C of straight or branched
4-C
14Diolefine, the more preferably C of straight or branched
4-C
8Conjugated diene also is preferably C
4-C
14The cyclic diene hydrocarbon.
As C
4-C
14Multi-olefin monomer can be mentioned divinyl, isoprene, 2,3-dimethyl--1,3-butadiene, 1,3-pentadiene, cyclopentadiene, methyl cyclopentadiene, cyclohexadiene etc., preferred isoprene.
In the methods of the invention, make the C that occupies the majority usually
4-C
8Isomonoolefin monomer, for example 80-99.5 weight %, preferably 90-99.5 weight %, the more preferably C of 95-99.5 weight %
4-C
8Isomonoolefin monomer (for example iso-butylene) and the C that occupies the minority
4-C
14Multi-olefin monomer, for example 20-0.5 weight %, preferably 10-0.5 weight %, the more preferably C of 5-0.5 weight %
4-C
14Multi-olefin monomer (for example divinyl or isoprene) reacts and prepares, and aforementioned percentage composition is based on the summation of all comonomers.
In a preferred embodiment of the invention, use iso-butylene as C
4-C
8The isomonoolefin monomer, and use isoprene as C
4-C
14Multi-olefin monomer.In a particularly preferred embodiment of the present invention, the iso-butylene of 95-99.5 weight % and the isoprene of 5-0.5 weight % are used as comonomer, aforementioned percentage composition is based on the weight summation of all comonomers.
The organic solvent that can be used in the polymerization method of the present invention is the organic solvent of under the polymeric reaction condition that the inventive method relates to, not participating in polyreaction, is inert organic solvents.As this solvent, disclosed butyl rubber polymerization solvent for use all can be used for the present invention in prior art.This solvent can be the alkyl halide solvent, preferred C
1-C
4Alkyl halide, for example monochloro methane, methylene dichloride, monochlorethane and ethylene dichloride.Also can use aliphatic solvents, preferred C
5-C
8Aliphatic hydrocarbon, for example Skellysolve A, iso-pentane, hexane, heptane, octane-iso etc.Can also use the cycloaliphates solvent, preferred C
5-C
10Cycloaliphates, for example pentamethylene, hexanaphthene, methylcyclohexane etc.As selection, can also use aforementioned one or more alkyl halides, preferred C
1-C
4Alkylogen, aforementioned one or more aliphatic solventss, preferred C
5-C
8Aliphatic hydrocarbon, and one or more aforementioned cycloaliphates solvents, preferred C
5-C
10Alicyclic mixture.As solvent, especially preferably use monochloro methane, methylene dichloride, pentane, hexane or its mixture.The solvent usage quantity is conventional, as long as can make copolyreaction smoothly, it can account for the 40-99% of mixture (comonomer and solvent) gross weight, and preferable range is 60-99%.
The inventive method can be carried out with slurry polymerization, also can carry out with solution polymerization.For example; The inventive method can adopt alkylogen as solvent and with the slurry system polymerization; Also can adopt aliphatic hydrocarbon or cycloaliphates to carry out with solution polymerization as solvent; Can also adopt the mixed system polymerization of aforementioned solvents, for example monochloro methane and pentane mixed solvent or monochloro methane and hexane mixed solvent preferably are the slurry system polymerization of solvent with the alkylogen.
The polyreaction that the inventive method relates to is carried out in-120 ℃ to-20 ℃ TR, and preferred polymeric is carried out in-110 ℃ to-50 ℃ TR.Polymerization pressure is conventional, is preferably normal pressure.Because polyreaction according to the present invention is exceedingly fast, polyreaction is promptly basic the completion after the initiator system interpolation finishes, thereby polymerization reaction time corresponds essentially to the interpolation time of initiator system.
Usually, through the isomonoolefin-multi-olefin copolymer of the inventive method preparation, it has HMW, and its weight-average molecular weight is at least greater than 200,000; Be preferably greater than 400,000 ten thousand, most preferably 400,000-1,000; 000, especially be 500,000-1,000,000.In the present invention, the molecular weight of polymkeric substance and PL-220 type liquid phase gel permeation chromatography (GPC) appearance that adopts Britain PL company to produce that distributes thereof are measured, and wherein adopt polystyrene standard to carry out calibration curve and measure.
In the methods of the invention; Through adopting the two-pack initiator system of forming by the multiple functionalized Organohalogen compounds of halogen of the monoalkyl dihalide aluminium of formula (I) and formula (II) to cause isomonoolefin and polyene hydrocarbon carries out copolymerization; Can obtain having wide molecular weight distribution, even have the multipolymer of bimodal distribution.Through the isomonoolefin-multi-olefin copolymer of the inventive method preparation, its molecular weight polydispersity coefficient M
w/ M
nBe at least 3.0, preferably be at least 3.5, most preferably be 4.0-7.0.
For the wide molecular weight distribution more clearly the present invention being described and being mentioned even the isomonoolefin-multi-olefin copolymer of bimodal distribution, do not receive the restriction of any theory here, carry out briefly bright.The copolymerization that the initiator system that hereinafter is formed with Bifunctionalized Organohalogen compounds of the halogen of formula (II) and ethyl aluminum dichloride causes iso-butylene and isoprene describes.Utilize traditional cationic polymerization to have the characteristics of initiated polymerization and transfer polymerization; The Bifunctionalized Organohalogen compounds activation under the effect of ethyl aluminum dichloride of halogen forms the trigger monomer polymerization of both-end active site and generates the linear molecule with duplex structure; And the chainpropagation active site is through generate the simple function active site once more to monomeric chain transfer reaction; Continue the trigger monomer polymerization and obtain linear strand macromole, therefore final polymer body is differed two kinds of mixtures that linear molecule is formed of one times by molecular weight.
Can regulate the halid efficiency of initiation of bifunctional through the proportionlity of regulating ethyl aluminum dichloride and difunctionality Organohalogen compounds; Further form both-end initiated polymerization and single-ended initiated polymerization; Form thereby adjust in the polymkeric substance two kinds of macromolecular ratios at an easy rate, further adjust molecular weight and the MWD of polymkeric substance even obtain the polymkeric substance of bimodal distribution.
The present invention utilizes traditional cationoid polymerisation to have the characteristics of chain transfer; Adopt the initiated polymerization of bifunctional Organohalogen compounds to form double-stranded linear macromolecule; And utilization forms the strand macromole of one times of molecular weight and molecular weight to monomeric transfer polymerization; This two common butyl polymer of forming with wide molecular weight distribution; Need not to add again other regulators; Only need just can regulate efficiency of initiation at an easy rate, reach the molecular weight of telomerized polymer and the purpose of MWD thereby further regulate two kinds of macromolecular ratio content, even can produce butyl polymer with bimodal molecular weight distribution through the proportionlity of regulating monoalkyl dihalide aluminium and bifunctional Organohalogen compounds.If the above Organohalogen compounds of employing three-functionality-degree are initiator; Then form the multichain star-like macromolecules through initiation reaction; And utilize the strand macromole that forms molecular weight and molecular weight to monomeric transfer polymerization, this two common butyl polymer of forming with wide molecular weight distribution.Through regulating the proportionlity of the multiple functionalized Organohalogen compounds of monoalkyl dihalide aluminium and halogen; Form more complicated initiated polymerization situation; Can regulate the ratio content of high low molecular weight fraction; Thereby reach the molecular weight of telomerized polymer and the purpose of MWD, even can produce butyl polymer with bimodal molecular weight distribution.
Description of drawings
Fig. 1 is the weight differential distribution plan of the molecular weight of the prepared isobutylene-isoprene copolymer of embodiment 1;
Fig. 2 is the weight differential distribution plan of the molecular weight of the prepared isobutylene-isoprene copolymer of embodiment 3;
Fig. 3 is the weight differential distribution plan of the molecular weight of the prepared isobutylene-isoprene copolymer of embodiment 4;
Fig. 4 is the weight differential distribution plan of the molecular weight of the prepared isobutylene-isoprene copolymer of embodiment 10; And
Fig. 5 is the weight differential distribution plan of the molecular weight of the prepared isobutylene-isoprene copolymer of embodiment 12.
In above each figure; Ordinate zou dWf/dLog [M] among the figure is the differential of weight fraction to the molecular weight logarithmic value; Wf wherein is that weight fraction and Log [M] are the logarithmic value of molecular weight, is obtained the weight differential distribution plan of molecular weight by the different differential values of dWf/dLog [M].
Following examples only are used to explain the present invention, but the present invention does not receive the restriction of these embodiment.
Embodiment
Testing method
In present specification and following examples, adopted following testing method:
1. adopt weighting method to measure polymer yield.
2. PL-220 type liquid phase gel permeation chromatography (GPC) appearance that adopts Britain PL company to produce, the single aperture chromatographic column is PL10
6 
, 10
5 
, 10
4 , 10
3 
, the molecular weight and the MWD of mensuration polymkeric substance, moving phase is THF, and flow velocity is 0.7ml/min, and strength of solution is 0.6mg/ml, sample size 200 μ l, probe temperature is 35 ℃.Adopting polystyrene standard to carry out calibration curve measures.
3. adopt Switzerland Bruker AVANCE400 NMR (400Hz), magneticstrength 9.40 teslas are with CDCl
3Make solvent, TMS is interior mark, room temperature test initiator structure and multipolymer degree of unsaturation.
Reference implementation example 1:1,4-two (2-chloro-2-propyl group) benzene (dicumyl chlorine, DCC) synthetic
The three mouthfuls of round-bottomed flasks of 500ml that to be furnished with inlet pipe of the slotting end and escape pipe and magnetic agitation place ice-water bath, to wherein adding 8g α, α '-dihydroxyl-1,4-diisopropyl benzene, the anhydrous CaCl of 10g
2With 100ml CH
2Cl
2Produce HCl gas through the vitriol oil being added drop-wise among the solid NaCl, the bubbler of this gas through the 10ml vitriol oil is housed is again through being equipped with anhydrous CaCl
2Drying tower carry out drying back and feed in the aforementioned there-necked flask, control HCl flow is advisable stirring reaction 10 hours to observe in the bubbler slowly continuous bubbling.Reaction is filtered after finishing, and obtains settled solution, vacuum removal HCl and CH
2Cl
2, obtaining colourless acicular crystal, thick product yield 96% carries out recrystallization with the thick product of gained and obtains refined prod in normal hexane.
1H-NMR characterizes: the 12H:2.00ppm of cumyl methyl; 4H:7.56 on the phenyl ring.
Reference implementation example 2:1,3,5-three (2-chloro-2-propyl group) benzene (three cumyl chlorine, TCC) synthetic
The synthetic of three cumyl chlorine is raw material with the trimesic acid; Obtain the trimesic acid ester through carrying out esterification with methyl alcohol; React with Grignard reagent (diethyl ether solution of methyl-magnesium-bromide) again and generate three cumyl alcohols; Obtain three cumyl chlorine through hydrochlorination at last, concrete chemical reaction process is following:
1) by 1,3, the 5-benzene tricarboxylic acid carries out esterification and generates 1,3,5-benzene tricarboxylic acid methyl esters
In two mouthfuls of round-bottomed flasks of the 1000ml that is furnished with magnetic agitation, prolong and constant pressure funnel, add 1,3; 5-benzene tricarboxylic acid 18g (0.086mol) and 500ml anhydrous methanol slowly drip vitriol oil 20ml through constant pressure funnel under reflux state, begin to keep stirring and refluxing reaction 30 hours from dripping acid; Product is cooled to room temperature, and under-5 ℃, deposits 12 hours, leach solid product and with distilled water wash till anacidity; Obtain highly purified colourless 1; 3,5-benzene tricarboxylic acid methyl esters crystal, product yield 92%.
1H-NMR characterizes: methyl 9H:3.98ppm on the ester group; Phenyl ring 3H:8.86ppm.
2) 1,3,5-benzene tricarboxylic acid methyl esters carries out Grignard reaction and generates three cumyl alcohols
In two mouthfuls of round-bottomed flasks of the 500ml that is furnished with magnetic agitation, under the drying nitrogen protection, benzene tricarboxylic acid methyl esters 16g is dissolved among the anhydrous THF of 280ml, and is cooled to 0 ℃.Start stirring, slowly drip the diethyl ether solution 120ml that volumetric molar concentration is the methyl-magnesium-bromide of 3M through constant pressure funnel then, keep 0 ℃ of reaction 18 hours.Then mixture is joined trash ice and the 18g ammonium chloride (NH of 280g under the state that stirs
4Cl) in the mixture, adopt ether to extract, extraction liquid is used anhydrous MgSO
4Drying is filtered the back evaporation except that desolvating with solution, obtains crude product three cumyl alcohols, product yield 87%.Three cumyl alcohols are carried out recrystallization in vinyl acetic monomer, obtain refined products.
1H-NMR characterizes (CCl
4/ CD
3OD): isopropyl methyl 18H:1.61ppm; Phenyl ring 3H:7.52ppm.
3) three cumyl alcohols carry out hydrochlorination and generate three cumyl chlorine
This method and reference implementation example 1 are basic identical, and difference is: that in three mouthfuls of round-bottomed flasks, at first add is three cumyl alcohol 6g, anhydrous CaCl
212g and CH
2Cl
2120ml.Thick product yield 84%.
1H-NMR characterizes: isopropyl methyl 18H:2.01-2.03ppm; Phenyl ring 3H:7.72ppm.
Above compound method can be referring to document Polymer Bulletin, and 1987,17,307-314 or J.Macro.Sci.-Pure Appl.Chem.1992, A29 (11), 1017-1030.
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 7.86ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.89ml, and DCC (dichloromethane solution of 0.04M) 1.25ml, [EtAlCl
2]/[DCC] mol ratio=16.0, form initiator solution, and with this initiator solution ageing 4min under this temperature, for use.
Polyreaction is carried out in the nitrogen operation box, in-100 ℃ low temperature cryostat, in the glass reactor that the powerful constant speed of being furnished with of 500ml stirs, injects-80 ℃ monochloro methane 128g, iso-butylene 32g and isoprene 0.82g, forms monomer solution.This monomer solution is cooled to-97 ℃, goes through the initiator solution 5ml after dripping ageing in 8 minutes, adopt the liquid nitrogen temperature control during this, polymerization temperature is remained-94.6 ℃ to-101.7 ℃, this polymerization time is corresponding to the time that drips initiator.Slurry system good dispersion during this period.Add extremely-60 ℃ methyl alcohol 5ml termination reaction of precooling afterwards, unreacted monomer of vacuum removal and solvent, polymkeric substance is through being dried to constant weight behind the distilled water wash under 40 ℃ in vacuum drying oven, and the result gets polymkeric substance 15.3g, transformation efficiency 46.6%, M
n=136800, M
w=614600, M
w/ M
n=4.49, degree of unsaturation 1.41%.The weight differential distribution plan of the molecular weight of this polymkeric substance is seen Fig. 1, can be found out by this figure, and polymer body differs two kinds of macromole of one times by molecular weight and forms.
Embodiment 2
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 8.02ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.78ml, and DCC (dichloromethane solution of 0.05M) 1.20ml, [EtAlCl
2]/[DCC] mol ratio=11.7, form initiator solution, and with this initiator solution ageing 110min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution after the Dropwise 5 ml ageing in 15 fens clockwise monomer solutions, polymerization temperature remains-95 ℃ to-101 ℃ during this.
The result obtains polymkeric substance, heavy 20.8g, weight yield 63.4%, M
n=189300, M
w=698500, M
w/ M
n=3.69, degree of unsaturation 1.72%.
Embodiment 3
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 13.02ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.38ml, and DCC (dichloromethane solution of 0.05M) 1.60ml, [EtAlCl
2]/[DCC] mol ratio=4.3, form initiator solution, and with initiator solution ageing 5min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution after dripping the 11ml ageing in the clockwise monomer solution in 12 minutes, polymerization temperature remains-95 ℃ to-102 ℃ during this.
The result obtains polymkeric substance, heavy 15.2g, weight yield 46.3%, M
n=119100, M
w=557000, M
w/ M
n=4.68, degree of unsaturation 1.45%.The weight differential distribution plan of the molecular weight of this polymkeric substance is seen Fig. 2, can be found out that by this figure MWD presents the bimodal distribution characteristic, and promptly polymer body differs two kinds of macromole of one times by molecular weight and forms.
Embodiment 4
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 13.03ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.17ml, and DCC (dichloromethane solution of 0.05M) 1.80ml, [EtAlCl
2]/[DCC] mol ratio=1.7, form initiator solution, and with this initiator solution ageing 6min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution after dripping the 13ml ageing in the clockwise monomer solution in 10 minutes, polymerization temperature remains-95.6 ℃ to-101.2 ℃ during this.
The result obtains polymkeric substance, heavy 13.6g, weight yield 41.5%, M
n=110600, M
w=493400, M
w/ M
n=4.46, degree of unsaturation 1.36%.The weight differential distribution plan of the molecular weight of this polymkeric substance is seen Fig. 3, can be found out that by this figure MWD presents the bimodal distribution characteristic, and promptly polymer body differs two kinds of macromole of one times by molecular weight and forms.
Embodiment 5
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 7.61ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.89ml, and DCC (dichloromethane solution of 0.04M) 1.5ml, [EtAlCl
2]/[DCC] mol ratio=13.4, form initiator solution, and with this initiator solution ageing 6min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: contain monochloro methane 128g, iso-butylene 32g and isoprene 1g in the monomer solution; Go through dripping initiator solution 4ml in the clockwise monomer solution in 7 minutes, polymerization temperature remains-96 ℃ to-102 ℃ during this.
The result obtains polymkeric substance, heavy 9.6g, weight yield 29.1%, M
n=179100, M
w=684600, M
w/ M
n=3.82, degree of unsaturation 1.57%.
Embodiment 6
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 7.94ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.56ml, and DCC (dichloromethane solution of 0.04M) 1.5ml form initiator solution, [EtAlCl
2]/[DCC] mol ratio=8.4, and with this initiator solution ageing 8min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: contain monochloro methane 136g, iso-butylene 24g and isoprene 1g in the monomer solution; Go through dripping initiator solution 2ml in the clockwise monomer solution in 4 minutes, polymerization temperature remains-97 ℃ to 100 ℃ during this.
The result obtains polymkeric substance, heavy 3.4g, weight yield 13.6%, M
n=116800, M
w=443700, M
w/ M
n=3.80, degree of unsaturation 2.11%.
Embodiment 7
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 9.18ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.67ml, and DCC (dichloromethane solution of 0.05M) 0.15ml form initiator solution, [EtAlCl
2]/[DCC] mol ratio=80.0, and with this initiator solution ageing 4min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution after dripping the 4ml ageing in the clockwise monomer solution in 6 minutes, polymerization temperature remains-93.6 ℃ to-102 ℃ during this.
The result obtains polymkeric substance, heavy 9.5g, weight yield 29.0%, M
n=254100, M
w=822200, M
w/ M
n=3.24, degree of unsaturation 1.28%.
Embodiment 8
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 9.03ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.67ml, and DCC (dichloromethane solution of 0.05M) 0.30ml form initiator solution, [EtAlCl
2]/[DCC] mol ratio=40.0, and with this initiator solution ageing 6min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution after dripping the 9.5ml ageing in the clockwise monomer solution in 15 minutes, polymerization temperature remains-93 ℃ to-103 ℃ during this.
The result obtains polymkeric substance, heavy 21.2g, weight yield 64.6%, M
n=164200, M
w=634000, M
w/ M
n=3.86, degree of unsaturation 1.46%.
Embodiment 9
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 4.60ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.80ml, and TCC (dichloromethane solution of 0.04M) 0.60ml, [EtAlCl
2]/[TCC] mol ratio=30.0, and with this initiator solution ageing 7min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution after dripping the 4ml ageing in the clockwise monomer solution in 10 minutes, polymerization temperature remains-92 ℃ to-101 ℃ during this.
The result obtains polymkeric substance, heavy 19.7g, weight yield 60.0%, M
n=211100, M
w=737300, M
w/ M
n=3.49, degree of unsaturation 1.55%.
Embodiment 10
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 5.00ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.40ml, and TCC (dichloromethane solution of 0.04M) 0.60ml, [EtAlCl
2]/[TCC] mol ratio=15.0, form initiator solution, and with this initiator solution ageing 8min under this temperature, for use.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution after dripping the 6ml ageing in the clockwise monomer solution in 7 minutes, polymerization temperature remains-97 ℃ to-102 ℃ during this.
The result obtains polymkeric substance, heavy 16.7g, weight yield 50.9%, M
n=184700, M
w=679300, M
w/ M
n=3.68, degree of unsaturation 1.40%.The weight differential distribution plan of the molecular weight of this polymkeric substance is seen shown in Figure 4.
Embodiment 11
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 8.42ml, EtAlCl under-85 ℃
2(hexane solution of 0.9M) 0.78ml, and TCC (dichloromethane solution of 0.05M) 0.8ml, [EtAlCl
2]/[TCC] mol ratio=17.5, form initiator solution, with this initiator solution ageing, in ageing process, make this solution be warming up to-30 ℃ naturally, total digestion time 126min.Repeat the method for embodiment 1 subsequently, different is: go through the initiator solution 4.5ml after dripping ageing in the clockwise monomer solution in 9 minutes, polymerization temperature remains-94 ℃ to-101 ℃ during this.
The result obtains polymkeric substance, heavy 15.2g, weight yield 46.3%, M
n=187400, M
w=751400, M
w/ M
n=4.01, degree of unsaturation is 1.42%.
Embodiment 12
In the goat's horn bottle of 60ml, injecting refined methylene dichloride 5.27ml, EtAlCl under-70 ℃
2(hexane solution of 0.9M) 0.13ml, and TCC (dichloromethane solution of 0.04M) 0.60ml, [EtAlCl
2]/[TCC] mol ratio=5.0, and with this initiator solution ageing 8min under this temperature, for use.Repeat the method for embodiment 1, different is: go through the initiator solution after the Dropwise 5 .5ml ageing in 5 fens clockwise monomer solutions, polymerization temperature remains-96 ℃ to-102 ℃ during this.
The result obtains polymkeric substance, heavy 6.7g, weight yield 20.4%, M
n=96600, M
w=620600, M
w/ M
n=6.43, degree of unsaturation 1.28%.The weight differential distribution plan of the molecular weight of this polymkeric substance is seen Fig. 5, can be found out that by this figure MWD has the bimodal distribution characteristic.
Claims (12)
1. method for preparing isomonoolefin-multi-olefin copolymer, this method comprises makes at least a C
4-C
8Isomonoolefin monomer and at least a C
4-C
14Multi-olefin monomer under-120 ℃ to-20 ℃ temperature, in the presence of inert organic solvents, contacts with the initiator system of being made up of the multiple functionalized Organohalogen compounds of halogen of the monoalkyl dihalide aluminium of following formula (I) and following formula (II),
AlRY
2 (I)
In the formula (I), R is straight or branched C
1-C
8Alkyl and 2 Y are halogen independently of one another,
In the formula (II),
N is 2,3 or 4;
R
1For being selected from down the abutment of group:
The C of-straight or branched
1-C
10The alkyl abutment and
-phenyl abutment, this phenyl abutment can be unsubstituted, also can be by 1-4 straight or branched C
1-C
6Alkyl replaces;
R
2And R
3Be hydrogen, straight or branched C independently of one another
1-C
8Alkyl, phenyl, the inferior C of phenyl straight or branched
1-C
4Alkyl, straight or branched C
1-C
4Alkyl phenylene or C
3-C
8Naphthenic base, wherein R
2And R
3Can be the same or different; And
X is a halogen.
2. the method for claim 1, in its Chinese style (I), R is straight or branched C
1-C
4Alkyl, preferred ethyl and 2 Y are bromine or chlorine independently of one another, especially are chlorine.
3. according to claim 1 or claim 2 method, in its Chinese style (II),
R
1For being selected from down the abutment of group:
The C of-straight or branched
1-C
10The alkyl abutment,
-phenyl abutment, this phenyl abutment can be unsubstituted, also can be by 1-4 straight or branched C
1-C
6Alkyl replaces;
R
2And R
3Be hydrogen, straight or branched C independently of one another
1-C
4Alkyl, phenyl, the inferior C of phenyl straight or branched
1-C
4Alkyl, straight or branched C
1-C
4Alkyl phenylene or C
3-C
8Naphthenic base, wherein R
2And R
3Can be the same or different; And
X is a chlorine or bromine;
4. the method for claim 1, its Chinese style (I) compound is an ethyl aluminum dichloride, and formula (II) compound is 1,4-two (2-chloro-2-propyl group) benzene or 1,3,5-three (2-chloro-2-propyl group) benzene.
5. like each described method among the claim 1-4, the mol ratio of its Chinese style (I) compound and formula (II) compound is 0.1-1000, preferred 0.5-500, more preferably 1～100.
6. like each described method, wherein C among the claim 1-5
4-C
8The isomonoolefin monomer is selected from down one or more in the group: iso-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2,3-dimethyl--1-butylene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2,3-dimethyl--1-amylene, 2; 4-dimethyl--1-amylene, 2-methyl isophthalic acid-hexene, 2,3-dimethyl--1-hexene, 2,4-dimethyl--1-hexene, 2; 5-dimethyl--1-hexene, 2; 4,4-trimethylammonium-1-amylene especially is an iso-butylene; And C
4-C
14Multi-olefin monomer is selected from down one or more in the group: divinyl, isoprene, 2,3-dimethyl--1,3-butadiene, 1,3-pentadiene, cyclopentadiene, methyl cyclopentadiene and cyclohexadiene especially are isoprene.
7. like each described method, wherein C among the claim 1-6
4-C
8The monomeric consumption of isomonoolefin is 80-99.5 weight %, and C
4-C
14The consumption of multi-olefin monomer is 20-0.5 weight %; Preferred C
4-C
8The monomeric consumption of isomonoolefin is 90-99.5 weight %, and C
4-C
14The consumption of multi-olefin monomer is 10-0.5 weight %; More preferably C
4-C
Through 8The monomeric consumption of isomonoolefin is 95-99.5 weight %, and C
4-C
14The consumption of multi-olefin monomer is 5-0.5 weight %, and aforementioned percentage composition is based on the weight summation of all comonomers.
8. like each described method among the claim 1-7, wherein the iso-butylene of 95-99.5 weight % and the isoprene of 5-0.5 weight % are used as comonomer, aforementioned percentage composition is based on the weight summation of all comonomers.
9. like each described method among the claim 1-8, the molecular weight polydispersity coefficient M of multipolymer wherein
w/ M
nBe at least 3.0, preferably be at least 3.5, most preferably be 4.0-7.0.
10. like each described method among the claim 1-9, wherein the weight-average molecular weight of isomonoolefin-multi-olefin copolymer is 400,000-1,000,000.
11. like each described method among the claim 1-10, wherein inert organic solvents is C
1-C
4Alkylogen, C
5-C
8Aliphatic hydrocarbon, C
5-C
10Cycloaliphates or its mixture.
12. like each described method among the claim 1-11, when wherein initiator system used with solution, formula (I) compound concentrations was 10
-3～10
-1Mol/L, and formula (II) compound concentrations is 10
-5～10
-2Mol/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536618A (en) * | 2014-04-30 | 2017-03-22 | 阿朗新科新加坡私人有限公司 | Highly unsaturated multi-modal polyisoolefin composition and process for preparation thereof |
| CN106536619A (en) * | 2014-06-30 | 2017-03-22 | 阿朗新科新加坡私人有限公司 | Novel anti-agglomerants for the rubber industry |
| WO2018058245A1 (en) * | 2016-09-29 | 2018-04-05 | ARLANXEO Canada Inc. | Multi-modal polyisoolefin compositions and processes therefor |
| CN116217773A (en) * | 2023-03-29 | 2023-06-06 | 山东京博中聚新材料有限公司 | Butyl rubber with wide molecular weight distribution and synthetic method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1729204A (en) * | 2002-12-20 | 2006-02-01 | 埃克森美孚化学专利公司 | Polymerization processes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729204A (en) * | 2002-12-20 | 2006-02-01 | 埃克森美孚化学专利公司 | Polymerization processes |
| CN1738843A (en) * | 2002-12-20 | 2006-02-22 | 埃克森美孚化学专利公司 | Polymers with new sequence distributions |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536618A (en) * | 2014-04-30 | 2017-03-22 | 阿朗新科新加坡私人有限公司 | Highly unsaturated multi-modal polyisoolefin composition and process for preparation thereof |
| CN106536618B (en) * | 2014-04-30 | 2019-04-16 | 阿朗新科新加坡私人有限公司 | High unsaturation multimodal polyisoolefines composition and preparation method thereof |
| CN106536619A (en) * | 2014-06-30 | 2017-03-22 | 阿朗新科新加坡私人有限公司 | Novel anti-agglomerants for the rubber industry |
| WO2018058245A1 (en) * | 2016-09-29 | 2018-04-05 | ARLANXEO Canada Inc. | Multi-modal polyisoolefin compositions and processes therefor |
| CN109844013A (en) * | 2016-09-29 | 2019-06-04 | 阿朗新科加拿大公司 | Multimodal polyisoolefines composition and its method |
| US10865299B2 (en) | 2016-09-29 | 2020-12-15 | ARLANXEO Canada Inc. | Multi-modal polyisoolefin compositions and processes therefor |
| RU2760441C2 (en) * | 2016-09-29 | 2021-11-25 | Арланксео Сингапур Пте. Лтд. | Multimodal polyisoolefin compositions and methods for them |
| CN109844013B (en) * | 2016-09-29 | 2022-02-08 | 阿朗新科加拿大公司 | Multimodal polyisoolefin compositions and methods |
| CN116217773A (en) * | 2023-03-29 | 2023-06-06 | 山东京博中聚新材料有限公司 | Butyl rubber with wide molecular weight distribution and synthetic method thereof |
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