CN103764695A - Process for preparing high-reactivity isobutene homo- or copolymers - Google Patents

Process for preparing high-reactivity isobutene homo- or copolymers Download PDF

Info

Publication number
CN103764695A
CN103764695A CN201280039216.8A CN201280039216A CN103764695A CN 103764695 A CN103764695 A CN 103764695A CN 201280039216 A CN201280039216 A CN 201280039216A CN 103764695 A CN103764695 A CN 103764695A
Authority
CN
China
Prior art keywords
alkyl
phenyl
butylene
butyl
iso
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201280039216.8A
Other languages
Chinese (zh)
Inventor
H·M·柯尼希
K·米尔巴赫
T·韦特林
U·艾歇瑙尔
H·迈尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN103764695A publication Critical patent/CN103764695A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Preparation of high-reactivity isobutene homo- or copolymers with a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol% by polymerization of isobutene or isobutene-comprising monomer mixtures in the presence of Lewis acids suitable as polymerization catalysts or of complexes which are effective as polymerization catalysts and are formed from Lewis acids and donors, and in the presence of initiators, wherein the initiators used are organic sulfonic acids Z-SO3H in which the variable Z denotes an alkyl radical, haloalkyl radical, cycloalkyl radical, aryl radical or arylalkyl radical.

Description

Produce the method for highly reactive isobutylene homo or multipolymer
The present invention relates to a kind ofly prepare end vinylidene double bond content that each polyisobutene end of the chain has at least highly reactive isobutylene homo of 50mol% or the novel method of multipolymer.The invention further relates to new isobutene polymer.
Contrary with so-called low reactivity polymkeric substance, highly reactive isobutylene homo or multipolymer are interpreted as referring to comprise high-content based on macromolecular each end of the chain of polyisobutene, are especially in fact generally at least those polyisobutene of the end second olefinic double bond of 80mol% (α-bis-keys).In the application's context, vinylidene is interpreted as those pair of key that refers to that its position in polyisobutene macromole is described by following general formula:
Two keys are present in the α position in polymer chain." polymkeric substance " represents to be abbreviated as the polyisobutenyl of an iso-butylene unit.Vinylidene has highest response, for example steric hindrance reactant as the hot addition on maleic anhydride in, and further the two keys towards macromole inside in most of the cases have more low reactivity in functionalization, if yes.The purposes of highly reactive polyisobutenes for example comprises, as preparing lubricant and the fuel purposes with the intermediate of additive, as described in DE-Α 2702604.
Such highly reactive polyisobutenes for example can be obtained by iso-butylene cationoid polymerisation under boron trifluoride exists as catalyzer in liquid phase by the method for DE-Α 2702604.Shortcoming is now that the polyisobutene obtaining has more much higher dispersiveness.Polymolecularity be resulting polymers chain molecular weight distribution tolerance and corresponding to weight-average molecular weight M wwith number-average molecular weight M nbusiness (PDI=M w/ M n).
There are the two keys in similar end at high proportion but have compared with the polyisobutene of narrow molecular weight distributions and for example can obtain by the method for EP-Α 145235, US5408018 and WO99/64482, wherein be aggregated in catalyst deactivation, for example the title complex of boron trifluoride and alcohol and/or ether carries out under existing.
Highly reactive polyisobutenes also can also make gained polymerisate dehydrohalogenation obtain by the living cationic polymerization of iso-butylene subsequently, for example, by the method for US5340881.Yet the method is complicated, because must eliminate in independent step with the halide end group that living cationic polymerization is introduced, to produce two keys.
Additionally be known that Lewis acid aluminum chloride also can be as the polymerizing catalyst of iso-butylene, for example, by High Polymers, XXIV rolls up (part 2), 713-733 page (editor: Edw α rd C.Leon α rd), J.Wiley & Sons publishers, New York, 1971 is known.
At paper document, " use the cationoid polymerisation of heteropolyacid salt catalyst ", Topics in Catalysis, the 23rd volume, in 175-181 page (2003), James D.Burrington etc. points out to use aluminum chloride as the polymerizing catalyst of iso-butylene, only can obtain having the low reactivity polyisobutene of the two keys (α-bis-keys) of low levels end vinylidene.For example, the table 1 on the 178th page, this paper document shows and uses Α lCl 3the polyisobutene example of preparation, its number-average molecular weight M nfor 1000-2000, polymolecularity M w/ M nfor 2.5-3.5 and vinylidene isomer (α-bis-keys) content are only 5% (except 65% " three ", 5% " β " and 25% " four " outer).
Paper document " for cinnamic accurate living cationic polymerization based on Α lCl 3the novel initiation system of etherate "; Polymer Bulletin, the 52nd volume, in 227-234 page (2004); SergeiV.Kostjuk etc. have described a kind of catalyst system for styrene polymerization, and it consists of 2-phenyl-2-propyl alcohol and aluminum chloride/di-n-butyl ether title complex.The polymolecularity M of the styrene polymer of so preparing w/ M nfor "～2.5 " (seeing general introduction) or "～3 " (seeing the 230th page).
International Patent Application PCT/EP2011/051929 has described and has a kind ofly prepared end vinylidene double bond content that each polyisobutene end of the chain has at least highly reactive isobutylene homo of 50mol% or the method for multipolymer, polymerization iso-butylene or containing the monomer mixture of iso-butylene under the existence of effective aluminum trihalide-donor title complex or aikyl aluminum halide-donor title complex as polymerizing catalyst wherein, wherein said title complex comprise there is at least one ether functional group or carboxylicesters functional group organic compound as donor.
CN101955558A discloses in the Polymerization of Ib that iron(ic) chloride (III) is adapted at preparing highly reactive polyisobutenes and multipolymer thereof as coinitiator.The initiator of recommending is that water, phenol, protonic acid are as sulfuric acid, the tertiary alcohol, tertiary muriate, t-carboxylic acid esters and carboxylic acid itself.For the mentioned Synergist S-421 95 of the system of initiated polymerization, it is especially alkyl oxide.
WO2006/011868 has described use hydrofluoric ether as solvent polymeric alkene.With regard to describing isobutyl-polymkeric substance-more particularly, wherein emphasized isobutylene-isoprene copolymer (" isoprene-isobutylene rubber ")-do not mentioned any possible high end vinylidene double bond content.Polymerization can comprise sulfonic acid and other materials with initiator system.
The object of this invention is to provide and a kind ofly take acceptable yield and prepare end vinylidene double bond content that each polyisobutene end of the chain has as 80mol% at least and there is the highly reactive isobutylene homo of narrow molecular weight distributions (i.e. low polymolecularity) or the method for multipolymer simultaneously.This catalyst system should have enough activity and work-ing life simultaneously, and its processing should not be a problem and it should not be easy to lose efficacy.
This object is prepared end vinylidene double bond content that each polyisobutene end of the chain has at least the highly reactive isobutylene homo of 50mol% or the method for multipolymer realize by a kind of, by be suitable as at least one Lewis acid of polymerizing catalyst or as polymerizing catalyst polymerization iso-butylene or carry out containing the monomer mixture of iso-butylene under the existence effectively and under the existence of the title complex being formed by least one Lewis acid and at least one donor and at least one initiator, described method comprises use general formula Z-SO 3the organic sulfonic acid of H is as at least one initiator, and wherein variable Z represents C 1-C 20alkyl, C 1-C 20haloalkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20arylalkyl.
Isobutylene homo is interpreted as referring to based on this polymkeric substance 98mol% at least, those polymkeric substance that preferably at least 99mol% is formed by iso-butylene in the context of the invention.Therefore, isobutylene copolymers is interpreted as referring to comprise over the monomer beyond the iso-butylene of 2mol% copolymerization as those polymkeric substance of linear butylene.
In the context of the invention, following definition is applicable to the group of General Definition:
C 1-C 8alkyl is linearity or the branched-alkyl with 1-8 carbon atom.The example is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl, amyl group, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, 1-ethyl propyl, n-hexyl, 1, 1-dimethyl propyl, 1, 2-dimethyl propyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butyl, 1, 1, 2-trimethylammonium propyl group, 1, 2, 2-trimethylammonium propyl group, 1-ethyl-1-methyl-propyl, 1-Ethyl-2-Methyl propyl group, n-heptyl, n-octyl and constitutional isomer thereof are as 2-ethylhexyl.Such C 1-C 8alkyl also can comprise heteroatoms on a small quantity as oxygen, nitrogen or halogen atom, and for example chlorine or fluorine, and/or non-proton functional group, as carboxylic acid ester groups, cyano group or nitro.
C 1-C 20alkyl is linearity or the branched-alkyl with 1-20 carbon atom.The example is above-mentioned C 1-C 8alkyl and additionally also have n-nonyl, different nonyl, positive decyl, 2-propylheptyl, n-undecane base, dodecyl, n-tridecane base, isotridecyl, n-tetradecane base, n-hexadecyl, Octadecane base and NSC 62789 base.Such C 1-C 20alkyl also can comprise heteroatoms on a small quantity as oxygen, nitrogen or halogen atom, and for example chlorine or fluorine, and/or non-proton functional group, as carboxylic acid ester groups, cyano group or nitro.
C 1-C 20haloalkyl or C 1-C 8haloalkyl is above-mentioned with regard to C for having 1-C 20alkyl or C 1-C 8the group of the basic skeleton of alkyl defined, but wherein hydrogen atom with higher degree by halogen atom, especially by fluorine and/or chlorine atom, substituted.Preferably all or substantially all hydrogen atoms by halogen atom, especially by fluorine and/or chlorine atom, substituted.The representative instance of such group is wherein at least 60%, especially at least 75%, particularly at least 90% number of hydrogen atoms is substituted by fluorine and/or chlorine atom, for example dichloromethyl, trichloromethyl, difluoromethyl, trifluoromethyl, a chlorodifluoramethyl-, a fluorine dichloromethyl, pentachloro-ethyl or pentafluoroethyl group.
C 5-C 8cycloalkyl is for comprising the saturated cyclic group of alkyl group side chain.The example is cyclopentyl, 2-or 3-methylcyclopentyl, 2,3-, 2,4-or 2,5-dimethylcyclopentyl, cyclohexyl, 2-, 3-or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-or 3,6-Dimethylcyclohexyl, suberyl, 2-, 3-or 4-methyl suberyl, ring octyl group, 2-, 3-, 4-or 5-methyl ring octyl group.Such C 5-C 8cycloalkyl also can comprise heteroatoms on a small quantity as oxygen, nitrogen or halogen atom, and for example chlorine or fluorine, and/or non-proton functional group, as carboxylic acid ester groups, cyano group or nitro.
C 6-C 20aryl or C 6-C 12aryl is preferably the phenyl of optional replacement, the optional naphthyl replacing, the optional anthryl replacing or the optional phenanthryl replacing.Such aryl can be 1-5 non-proton substituting group or non-proton functional group, for example C 1-C 8alkyl, C 1-C 8haloalkyl is as C 1-C 8chloro alkyl or C 1-C 8fluoro-alkyl, halogen is as chlorine or fluorine, nitro, cyano group or phenyl.The example of such aryl is phenyl, naphthyl, xenyl, anthryl, phenanthryl, tolyl, nitrophenyl, chloro-phenyl-, dichlorophenyl, pentafluorophenyl group, five chlorophenyl, (trifluoromethyl) phenyl, two (trifluoromethyl) phenyl, (trichloromethyl) phenyl and two (trichloromethyl) phenyl.
C 7-C 20arylalkyl or C 7-C 12arylalkyl is preferably the C of optional replacement 1-C 4alkyl phenyl, as benzyl, o-, m-or p-methyl-benzyl, 1-or 2-phenylethyl, 1-, 2-or 3-phenyl propyl or 1-, 2-, 3-or 4-phenyl butyl, the optional C replacing 1-C 4alkyl naphthyl is as naphthyl methyl, the optional C replacing 1-C 4alkyl anthryl is as anthryl methyl, or the optional C replacing 1-C 4alkyl phenanthryl is as phenanthryl methyl.Such arylalkyl can be with 1-5 non-proton substituting group or non-proton functional group, especially on aryl structure division, and C for example 1-C 8alkyl, C 1-C 8haloalkyl is as C 1-C 8chlorine alkyl or C 1-C 8fluoroalkyl, halogen are as chlorine or fluorine, nitro or phenyl.
The inventive method of preparing highly reactive isobutylene homo or multipolymer conventionally by cationoid reaction mechanism carry out-by use described as polymerizing catalyst effectively and the title complex being formed by least one Lewis acid and optional at least one donor and initiator cause.
Essential feature of the present invention for being used general formula Z-SO in polymerization process of the present invention 3the organic sulfonic acid of H is as at least one initiator.Should understand and also can use different sulfonic acid Z-SO 3the mixture of H.Except these sulfonic acid initiators, also can use other initiator molecules from other chemical substance classifications.
Variable Z preferably represents C 1-C 8alkyl, C 1-C 8haloalkyl, C 5-C 8cycloalkyl, C 6-C 12aryl or C 7-C 12arylalkyl.Z more preferably represents C 1-C 4alkyl, C 1-C 4haloalkyl, the optional phenyl replacing are as tolyl or xylyl or the optional C replacing 1-C 4alkyl phenyl is as benzyl.
In particularly preferred embodiment of the present invention, at least one initiator used is the organic sulfonic acid that is selected from methanesulfonic, trifluoromethayl sulfonic acid, trichloromethane sulfonic acid and toluenesulphonic acids or its mixture.
Being suitable as polymerizing catalyst or being adapted at as the Lewis acid in the effective title complex of polymerizing catalyst is all lewis acidic inorganic molecules that are defined as in principle, but the especially metal of the periodic table of elements and semimetallic halogen compounds, its valence state by halogen atom, met completely or except halogenic substituent also with one or more organic carbon group, especially C 1-C 4alkyl.Here the useful halogenic substituent in these element halides and alkyl element halide comprises iodine, bromine, especially fluorine, particularly chlorine.Certainly also can use those element halides or those alkyl element halides in each case separately and mutual mixture.
If for example the halogenide of aluminium or alkyl halide, as such Lewis acid, can be used following material: aluminum trifluoride, aluminum chloride, alchlor conventionally; As aikyl aluminum halide, single (C 1-C 4alkyl) dihalide aluminium or two (C 1-C 4alkyl) single aluminum halide, for example methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride or diethyl aluminum chloride.
In preferred embodiments, for the Lewis acid of the polymerizing catalyst as the effective title complex of polymerizing catalyst at least one is selected from the binary fluorine cpd that the binary chlorine of element of periodic table of elements 1-8 transition group and 3-5 main group and the compound of fluorine cpd and binary chlorine compound can be better than these elements.
Such typical binary chlorine compound is ScCl 3, YCl 3, YbCl 3, TiCl 3, TiCl 4, ZrCl 4, HfCl 4, VCl 3, VCl 4, NbCl 3, NbCl 5, TaCl 5, CrCl 2, CrCl 3, MoCl 3, MoCl 5, WCl 5, WCl 6, MnCl 2, ReCl 3, ReCl 5, FeCl 2, FeCl 3, RuCl 3, OsCl 3, CoCl 2, CoCl 3, RhCl 3, IrCl 3, NiCl 2, PdCl 2, PtCl 2, CuCl, CuCl 2, AgCl, AuCl, ZnCl 2, CdCl 2, HgCl, HgCl 2, BCl 3, AlCl 3, GaCl 3, InCl 3, TlCl 3, SiCl 4, GeCl 4, SnCl 2, SnCl 3, SnCl 4, PbCl 2, PbCl 4, PCl 3, PCl 5, AsCl 3, SbCl 3, SbCl 5and BiCl 3.BCl particularly preferably wherein 3, AlCl 3, TiCl 4, FeCl 2, FeCl 3and ZnCl 2.
Such typical binary fluorine cpd are ScF 3, YF 3, YbF 3, TiF 3, TiF 4, ZrF 4, HfF 4, VF 3, VF 4, NbF 3, NbF 5, TaF 5, CrF 2, CrF 3, MoF 3, MoF 5, WF 5, WF 6, MnF 2, ReF 3, ReF 5, FeF 2, FeF 3, RuF 3, OsF 3, CoF 2, CoF 3, RhF 3, IrF 3, NiF 2, PdF 2, PtF 2, CuF, CuF 2, AgF, AuF, ZnF 2, CdF 2, HgF, HgF 2, BF 3, AlF 3, GaF 3, InF 3, TlF 3, SiF 4, GeF 4, SnF 2, SnF 3, SnF 4, PbF 2, PbF 4, PF 3, PF 5, AsF 3, SbF 3, SbF 5and BiF 3.BF particularly preferably wherein 3, AlF 3, TiF 4, FeF 2, FeF 3and ZnF 2.Also can use the mixture of binary chlorine and fluorine cpd.
Conventionally also can use binary bromine compounds as such Lewis acid; Such bromine compounds is for example: TiBr 3, TiBr 4, ZrBr 4, VBr 3, VBr 4, CrBr 2, CrBr 3, MoBr 3, MoBr 5, WBr 5, WBr 6, MnBr 2, FeBr 2, FeBr 3, CoBr 2, CoBr 3, NiBr 2, PdBr 2, PtBr 2, CuBr, CuBr 2, AgBr, AuBr, ZnBr 2, CdBr 2, HgBr, HgBr 2, BBr 3, AlBr 3, SiBr 4, SnBr 2, SnBr 3, SnBr 4, PbBr 2, PbBr 4, PBr 3, PBr 5, AsBr 3, SbBr 3, SbBr 5and BiBr 3.
Very particularly preferably use preferred sulfonic acid initiator methanesulfonic, trifluoromethayl sulfonic acid, trichloromethane sulfonic acid and toluenesulphonic acids and preferred Lewis acid or there is BCl 3, AlCl 3, TiCl 4, FeCl 2, FeCl 3, ZnCl 2, BF 3, AlF 3, TiF 4, FeF 2, FeF 3and/or ZnF 2lewis acid complex together, particularly methanesulfonic and AlCl 3, BF 3or FeCl 3together, especially when using, comprise below regulation as the preferred general formula R of donor 1-O-R 2dialkyl ether and/or general formula R 3-COOR 4the Lewis acid complex of hydrocarbyl carboxylic ester time.
In the methods of the invention, be preferably used as polymerizing catalyst effectively and comprise the title complex as the organic compound with at least one ether functional group or carboxylicesters functional group of donor.Can certainly use the mixture of the different organic compound with at least one ether functional group and/or there is the mixture of the different organic compound of at least one carboxylicesters functional group.If have the organic compound with at least one ether functional group as donor as the effective title complex of polymerizing catalyst, the compound with at least one ether functional group is also interpreted as referring to acetal and hemiacetal.
In a preferred embodiment of the invention, be used as polymerizing catalyst effectively and the title complex being formed by least one Lewis acid and at least one donor, wherein the organic compound as donor is general formula R 1-O-R 2dialkyl ether, variable R wherein 1and R 2be C independently of one another 1-C 20alkyl, especially C 1-C 8alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl, especially C 6-C 12aryl, or C 7-C 20arylalkyl, especially C 7-C 20arylalkyl, general formula R 3-COOR 4hydrocarbyl carboxylic ester, variable R wherein 3and R 4be C independently of one another 1-C 20alkyl, especially C 1-C 8alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl, especially C 6-C 12aryl, or C 7-C 20arylalkyl, especially C 7-C 12arylalkyl.
Described dialkyl ether can be open chain or ring-type, wherein two variable R 1and R 2can be in conjunction with forming ring in the situation that of cyclic ether, wherein this ring can also comprise two or three ether oxygen atoms.The example of such open chain and ring-type dialkyl ether is dme, ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-secondary butyl ether, diisobutyl ether, two n-amylethers, two n-hexyl ethers, two positive heptyl ethers, two octyl ethers, two (2-ethylhexyl) ether, methyl n-butyl ether, methyl sec-butyl ether, methyl-isobutyl ether, methyl tertiary butyl ether, ethyl n-butyl ether, ethyl sec-butyl ether, ethyl isobutyl ether, n-propyl n-butyl ether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyl tertbutyl ether, sec.-propyl n-butyl ether, sec.-propyl sec-butyl ether, isopropyl butyl ether, sec.-propyl tertbutyl ether, diola, methyl n-octyl ether, methyl 2-ethylhexyl ether, ethyl n-hexyl ether, ethyl n-octyl ether, ethyl 2-ethylhexyl ether, normal-butyl n-octyl ether, normal-butyl 2-ethylhexyl ether, tetrahydrofuran (THF), tetrahydropyrans, 1, 2-bis-
Figure BDA0000464856840000071
alkane, 1,3-bis-
Figure BDA0000464856840000072
alkane, Isosorbide-5-Nitrae-bis-
Figure BDA0000464856840000073
alkane, dicyclohexyl ether, diphenyl ether, two-4-tolyl ether, two-xylyl ether and dibenzyl ether.In described dialkyl ether, have been found that di-n-butyl ether and diphenyl ether are advantageous particularly as donor here, especially with Lewis acid BCl 3, AlCl 3, TiCl 4, FeCl 2, FeCl 3and ZnCl 2combination.
The example of described hydrocarbyl carboxylic ester is methyl-formiate, ethyl formate, formic acid n-propyl, isopropyl formate, n-buty formate, sec.-butyl formate, tetryl formate, t-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, tert.-butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, sec-butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester, methyl-butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, the positive butyl ester of butyric acid, the secondary butyl ester of butyric acid, isobutyl butyrate, tert-butyl acetate, naphthenic acid methyl esters, naphthenic acid ethyl ester, naphthenic acid n-propyl, naphthenic acid isopropyl ester, the positive butyl ester of naphthenic acid, the secondary butyl ester of naphthenic acid, naphthenic acid isobutyl ester, the naphthenic acid tert-butyl ester, methyl benzoate, ethyl benzoate, Propyl benzoate, isopropyl benzoate, the positive butyl ester of phenylformic acid, the secondary butyl ester of phenylformic acid, isobutyl benzoate, t-butyl perbenzoate, methyl phenylacetate, Phenylacetic acid ethylester, toluylic acid n-propyl, Isopropyl phenylacetate, the positive butyl ester of toluylic acid, the secondary butyl ester of toluylic acid, isobutyl phenylacetate and the toluylic acid tert-butyl ester.In described hydrocarbyl carboxylic ester, have been found that ethyl acetate is advantageous particularly as donor here, especially with Lewis acid BCl 3, AlCl 3, TiCl 4, FeCl 2, FeCl 3and ZnCl 2combination.
In addition have been found that as donor (especially with Lewis acid BCl, 3, AlCl 3, TiCl 4, FeCl 2, FeCl 3and ZnCl 2combination) particularly advantageous dialkyl ether and hydrocarbyl carboxylic ester are that total carbon number that wherein compound donator has is 3-16, those of preferred 4-16, especially 4-12, particularly 4-8.At dialkyl ether in particular cases, especially preferably altogether there is 6-14, especially those of 8-12 carbon atom.At hydrocarbyl carboxylic ester in particular cases, especially preferably altogether there is 3-10, especially those of 4-6 carbon atom.
In the effective title complex as polymerizing catalyst, described compound donator and Lewis acid, especially with described element halide and alkyl element halide, especially with Lewis acid BCl 3, AlCl 3, TiCl 4, FeCl 2, FeCl 3and ZnCl 2mol ratio conventionally at 0.3:1-1.5:1, especially change in the scope of 0.5:1-1.2:1, particularly 0.7:1-1.1:1; Be in most of the cases 1:1.Yet, can also be with larger excessive compound donator operation, usually up to 10 times, 3 times of molar excess especially; Excessive compound donator now additionally plays solvent or thinner.
As the effective title complex of polymerizing catalyst, conventionally before polymerization, by described Lewis acid (conventionally using with anhydrous form) and compound donator, prepared separately, and subsequently-be conventionally dissolved in inert solvent as halohydrocarbon, for example in methylene dichloride-add in polymerisation medium.Yet this title complex can also preparation on the spot before polymerization.
In a preferred embodiment of the invention, this is aggregated under at least one other initiator of extra use and carries out, described other initiators are simple function or polyfunctional, especially single-, two-or trifunctional and be selected from organic hydroxy compounds, organohalogen compound, protonic acid and water.Can also use the mixture of such other initiators, the mixture of two or more organic hydroxy compounds for example, the mixture of two or more organohalogen compounds, the mixture of one or more organic hydroxy compounds and one or more organohalogen compounds, the mixture of one or more organic hydroxy compounds and water, or the mixture of one or more organohalogen compounds and water, or the mixture of one or more protonic acids and water.This initiator can be single-, two-or polyfunctional, 1,2 or the more hydroxyl or the halogen atom that start polyreaction may reside in this initiator molecule.Two-or Multifunctional initiator in the situation that, conventionally obtain having two or more, especially the distant pawl isobutene polymer of two or three polyisobutene end of the chains.
The organic hydroxy compounds that only has a hydroxyl and be suitable as simple function initiator in molecule especially comprises alcohol and phenol, especially general formula R 5those of-OH, wherein R 5represent C 1-C 20alkyl, especially C 1-C 8alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl, especially C 6-C 12aryl, or C 7-C 20arylalkyl, especially C 7-C 12arylalkyl.In addition radicals R, 5can also comprise the mixture of said structure and/or there are already mentioned other functional groups beyond those, for example ketone group functional group, nitroxyl free radical (nitroxide) or carboxyl, and/or heterocycle structure unit.
The representative instance of such organic monohydroxy compound is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, hexalin, phenol, p methoxy phenol, ortho-cresol, meta-cresol, p-cresol, benzylalcohol, p-methoxybenzyl alcohol, 1-and 2-phenylethyl alcohol, 1-and 2-(p-methoxyphenyl) ethanol, 1-, 2-and 3-phenyl-1-propanol, 1-, 2-and 3-(p-methoxyphenyl)-1-propyl alcohol, 1-and 2-phenyl-2-propyl alcohol, 1-and 2-(p-methoxyphenyl)-2-propyl alcohol, 1-, 2-, 3-and 4-phenyl-n-butyl alcohol, 1-, 2-, 3-and 4-(p-methoxyphenyl)-n-butyl alcohol, 1-, 2-, 3-and 4-phenyl-2-butanols, 1-, 2-, 3-and 4-(p-methoxyphenyl)-2-butanols, 9-methyl-9 H-fluorene-9-alcohol, 1, 1-phenylbenzene ethanol, 1, 1-phenylbenzene-2-propine-1-alcohol, 1, 1-phenylbenzene propyl alcohol, 4-(1-hydroxyl-1-phenylethyl) benzonitrile, cyclopropyl diphenyl-carbinol, 1-hydroxyl-1, 1-diphenylprop-2-ketone, benzilic acid, 9-phenyl-9-fluorenol, triphenylcarbinol, phenylbenzene (4-pyridyl) methyl alcohol, α, α-phenylbenzene-2-piconol, the 4-methoxyl group trityl alcohol polymkeric substance of solid phase bonding (especially as), the chloro-4 '-methyldiphenyl methyl alcohol of α-tertiary butyl-4-, cyclohexyl diphenyl-carbinol, α-(p-methylphenyl) benzhydrol, 1, 1, 2-triphenyl ethanol, α, α-phenylbenzene-2-pyridine ethanol, α, α-4-pyridyl benzhydrol N-oxide compound, 2-fluorine triphenylcarbinol, triphenyl propargyl alcohol, 4-[(phenylbenzene) hydroxymethyl] benzonitrile, 1-(2, 6-Dimethoxyphenyl)-2-methyl isophthalic acid-phenyl-1-propanol, 1, 1, 2-triphenyl third-1-alcohol and p-anisaldehyde methyl alcohol (p-anisaldehydcarbinol).
The organic hydroxy compounds that has two hydroxyls and be suitable as bifunctional initiator in molecule especially dibasic alcohol or total carbon number is 2-30, especially 3-24, the glycol of 4-20 particularly, and total carbon number is 6-30, especially 8-24, the bis-phenol of 10-20 particularly, ethylene glycol for example, 1, 2-and 1, ammediol, 1, 4-butyleneglycol, 1, 6-hexylene glycol, 1, 2-, 1, 3-or 1, 4-bis-(1-hydroxyl-1-methylethyl) benzene is (o-, m-or to dicumyl alcohol), bis-phenol Α, 9, 10-dihydro-9, 10-dimethyl-9, 10-oxanthranol, 1, 1-phenylbenzene-1, 4-butyleneglycol, 2-hydroxyl triphenylcarbinol (2-hydroxytriphenylcarbinol) and 9-[2-(hydroxymethyl) phenyl]-9-fluorenol.
The organohalogen compound that has a halogen atom and be suitable as simple function initiator in molecule is general formula R especially 6the compound of-Hal, wherein Hal is the halogen atom that is selected from fluorine, iodine and especially chlorine and bromine, and R 6represent C 1-C 20alkyl, especially C 1-C 8alkyl, C 5-C 8cycloalkyl or C 7-C 20arylalkyl, especially C 7-C 12arylalkyl.In addition radicals R, 6also can comprise the mixture of said structure and/or there are already mentioned other functional groups beyond those, for example ketone group functional group, nitroxyl free radical or carboxyl, and/or heterocycle structure unit.
The representative instance of such single halogen compounds is methyl chloride, monobromomethane, ethyl chloride, monobromoethane, n-propyl chloride, 1-N-PROPYLE BROMIDE, 2 cbloropropane isopropyl chloride, 2-N-PROPYLE BROMIDE, 1-chlorobutane, 1-n-butyl bromide, sec-butyl chloride, sec-butyl bromide, isobutyl chloride, isobutyl bromide, tertiary butyl chloride, tert.-butyl bromide, 1-chloropentane, 1-bromo pentane silane, 1-chlorohexane, hexyl bromide 1 bromohexane, 1-chloroheptane, 1-heptyl bromide, 1-chloro-octane, 1-bromooctane, the chloro-2-ethyl hexane of 1-, the bromo-2-ethyl hexane of 1-, cyclohexyl chloride, cyclohexyl bromide, benzyl chloride, bromotoluene, 1-phenyl-1-monochloroethane, 1-phenyl-1-monobromethane, 1-phenyl-2-monochloroethane, 1-phenyl-2-monobromethane, 1-phenyl-n-propyl chloride, 1-phenyl-1-N-PROPYLE BROMIDE, 1-phenyl-2 cbloropropane isopropyl chloride, 1-phenyl-2-N-PROPYLE BROMIDE, 2-phenyl-2 cbloropropane isopropyl chloride, 2-phenyl-2-N-PROPYLE BROMIDE, 1-phenyl-3-chloropropane, 1-phenyl-3-N-PROPYLE BROMIDE, 1-phenyl-1-chlorobutane, 1-phenyl-1-n-butyl bromide, 1-phenyl-Sec-Butyl Chloride, 1-phenyl-2-n-butyl bromide, 1-phenyl-3-chlorobutane, 1-phenyl-3-n-butyl bromide, 1-phenyl-4-chlorobutane, 1-phenyl-4-n-butyl bromide, 2-phenyl-1-chlorobutane, 2-phenyl-1-n-butyl bromide, 2-phenyl-Sec-Butyl Chloride, 2-phenyl-2-n-butyl bromide, 2-phenyl-3-chlorobutane, 2-phenyl-3-n-butyl bromide, 2-phenyl-4-chlorobutane and 2-phenyl-4-n-butyl bromide.
The organohalogen compound that has two halogen atoms and be suitable as bifunctional initiator in molecule is for example 1,3-bis-(the bromo-1-methylethyl of 1-) benzene, 1,3-bis-(the chloro-2-propyl group of 2-) benzene (1,3-dicumyl chlorine) and 1,4-bis-(the chloro-2-propyl group of 2-) benzene (Isosorbide-5-Nitrae-dicumyl chlorine).
Other initiators be more preferably selected from wherein one or more hydroxyls separately key in sp 3the organic hydroxy compounds of-hydridization carbon atom (" alcohol ") or aromatic ring (" phenol "), wherein one or more halogen atoms separately key in sp 3the organohalogen compound of-hydridization carbon atom, protonic acid and water.Wherein especially be preferably selected from wherein one or more hydroxyls separately key in sp 3the initiator of the organic hydroxy compounds of-hydridization carbon atom.
The in the situation that of organohalogen compound, particularly preferably other initiators be additionally wherein one or more halogen atoms separately key in secondary or especially tertiary sp 3those of-hydridization carbon atom.
Especially preferably except hydroxyl is with external this sp 3on-hydridization carbon atom with radicals R 5, R 6and R 7other initiators, described group is hydrogen, C independently of one another 1-C 20alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl, C 7-C 20alkylaryl or phenyl, wherein any aromatic ring can also be with one or more, preferably one or two C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4hydroxyalkyl or C 1-C 4haloalkyl is as substituting group, wherein variable R 5, R 6and R 7in at the most one be hydrogen and variable R 5, R 6and R 7in at least one for also can be with one or more, preferred one or two C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4hydroxyalkyl or C 1-C 4haloalkyl is as substituent phenyl.
The example of useful protonic acid comprises hydrochloric acid, Hydrogen bromide, hydrofluoric acid, sulfuric acid, prussic acid and composition thereof.Yet protonic acid used also can be protonated ether.
For the purpose of the present invention, very particularly preferably be selected from water, one or more protonic acids, methyl alcohol, ethanol, 1-phenylethyl alcohol, 1-(p-methoxyphenyl) ethanol, n-propyl alcohol, Virahol, 2-phenyl-2-propyl alcohol (cumene), propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, 1-phenyl-1-monochloroethane, 2-phenyl-2 cbloropropane isopropyl chloride (cumyl chlorine), tertiary butyl chloride and 1, other initiators of 3-or Isosorbide-5-Nitrae-bis-(1-hydroxyl-1-methylethyl) benzene and composition thereof.Wherein especially be preferably selected from water, one or more protonic acids, methyl alcohol, ethanol, 1-phenylethyl alcohol, 1-(p-methoxyphenyl) ethanol, n-propyl alcohol, Virahol, 2-phenyl-2-propyl alcohol (cumene), propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, 1-phenyl-1-monochloroethane and 1, other initiators of 3-or Isosorbide-5-Nitrae-bis-(1-hydroxyl-1-methylethyl) benzene and composition thereof.
General formula Z-SO used according to the invention 3the organic sulfonic acid of H and described in those any other initiator to be used total amount and isobutylene monomer used in iso-butylene homopolymerization situation or each the independent sense position (organic sulfonic acid should be considered as simple function) based on initiator is generally 0.001:1-0.5:1 with the mol ratio of the total amount of polymerisable monomer used in iso-butylene copolymerization situation, especially 0.01:1-0.4:1, particularly 01:1-0.3:1.When being used in combination using water as unique other initiators or with organic hydroxy compounds as other initiators and/or organohalogen compound, separately water and isobutylene monomer used in iso-butylene homopolymerization situation or with the mol ratio of the total amount of polymerisable monomer used in iso-butylene copolymerization situation be especially 0.0001:1-0.1:1, particularly 0.0002:1-0.05:1.
As organic sulfonic acid and the part initiator molecule that optionally adds as organic hydroxyl or halogen compounds, can mix in polymer chain.Ratio (the I of the polymer chain that the organic initiators molecule that mixed by this is initial eff) can be up to 100%, be generally 0-90% and can be 5-90%.Residual polymer chain is derived from as the water that derives from traces of moisture of initiator molecule or is derived from chain transfer reaction.
In another preferred embodiment of the present invention, be aggregated in 0.01-10mmol, especially 0.05-5.0mmol, particularly the nitrogenous basic cpd of 0.1-1.0mmol carries out under existing, in each case the 1mol isobutylene monomer based on using in iso-butylene homopolymerization situation or the 1mol polymerisable monomer total amount used in iso-butylene copolymerization situation.
Such nitrogenous basic cpd used can be general formula R 7-NR 8r 9aliphatic series, alicyclic or aromatic amine, or ammonia, wherein variable R 7, R 8and R 9be hydrogen, C independently of one another 1-C 20alkyl, especially C 1-C 8alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl, especially C 6-C 12aryl, or C 7-C 20arylalkyl, especially C 7-C 12arylalkyl.When these variablees are all not hydrogen, this amine is tertiary amine.When one of these variablees are hydrogen, this amine is secondary amine.In these variablees two while being hydrogen, this amine is primary amine.When all these variablees are hydrogen, this amine is ammonia.
Such general formula R 7-NR 8r 9the representative instance of amine be methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, TERTIARY BUTYL AMINE, sec-butylamine, isobutylamine, tertiary amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, 2-DEHA, cyclopentyl amine, cyclo-hexylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, Diisopropylamine, Di-n-Butyl Amine, two TERTIARY BUTYL AMINE, di-sec-butylamine, diisobutylamine, two tertiary amylamines, two normal hexyl Amines, two positive heptyl amices, two n-octyl amine, two-(2-ethylhexyl) amine, two cyclopentyl amine, dicyclohexylamine, diphenylamine, Trimethylamine 99, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, three TERTIARY BUTYL AMINE, tri sec-butylamine, tri-isobutylamine, three tertiary amylamines, three normal hexyl Amines, three positive heptyl amices, tri-n-octyl amine, three-(2-ethylhexyl) amine, three cyclopentyl amine, thricyclohexyl amine, triphenylamine, dimethylethyl amine, methyl n-butylamine, N-methyl-N-phenyl amine, N, N-dimethyl-N-phenyl amine, N-methyl-N, N-diphenylamine or N-methyl-N-ethyl-N-n-butylamine.
In addition, such nitrogenous basic cpd used can also be a plurality of for having, 2 or 3 nitrogen-atoms and there is the compound of 2-20 carbon atom especially, wherein these nitrogen can be independently of one another with hydrogen atom or aliphatic series, alicyclic or aromatic substituent.The example of such polyamines is 1，2-diaminoethane, 1,3-propylene diamine, Putriscine, diethylenetriamine, N-methyl isophthalic acid, 2-quadrol, N, N-dimethyl-1，2-diaminoethane, N, N '-dimethyl-1，2-diaminoethane or N, N-dimethyl-1,3-propylene diamine.
Yet the suitable nitrogenous basic cpd of this class is especially saturated, part is unsaturated or unsaturated 5 or 6 Yuans nitrogen heterocyclic rings, it comprises 1,2 or 3 theheterocyclic nitrogen atom and can have 1 or 2 other ring hetero atoms and/or alkyl, especially C that is selected from oxygen and sulphur 1-C 4alkyl and/or phenyl, and/or functional group or heteroatoms, especially fluorine, chlorine, bromine, nitro and/or cyano group are as substituting group, for example tetramethyleneimine, pyrroles, imidazoles, 1,2,3-or 1, our (pyrazan), pyrazoles of 2,4-triazole, azoles, thiazole, piperidines, pyrrole, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,2,5-triazine, 1,2,5-thiazine, 2H-1,3,5-thiadiazine or morpholine.
Yet, the nitrogenous basic cpd of very specially suitable this class be pyridine or pyridine derivate (especially single-, two-or three-C 1-C 4the pyridine that alkyl replaces) as 2-, 3-or 4-picoline (picoline class), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-or 3,6-lutidine (lutidine class), 2,4,6-trimethylpyridine (collidine), 2-, 3-or 4-tert .-butylpyridine, the 2-tertiary butyl-6-picoline, 2,4-, 2,5-, 2,6-or 3,5-di-tert-butyl pyridine or 2-, 3-or 4-phenylpyridine.
Can use the mixture of single nitrogenous basic cpd or such nitrogenous basic cpd.
For iso-butylene or containing the monomer mixture of iso-butylene as the purposes for the treatment of polymerization single polymerization monomer, suitable iso-butylene source is pure iso-butylene and isobutylene type C 4hydrocarbon flow, for example C 4raffinate, especially " raffinate 1 ", from the C of dehydrogenation of isobutane 4cut, from the C of steam cracker and FCC cracker (fluid catalystic cracking) 4cut, condition is that they have removed the 1,3-butadiene wherein existing substantially.C from FCC oil refining apparatus 4hydrocarbon flow is also known as " b/b " material stream.The isobutylene type C that other are suitable 4hydrocarbon flow is for example the product stream of propylene-Trimethylmethane co-oxidation or from the product stream of metathesis device, they are use after routine is purified and/or be concentrated conventionally.Suitable C 4hydrocarbon flow conventionally comprises and is less than 500ppm, is preferably less than the divinyl of 200ppm.1-butylene and cis-and the existence of trans-2-butene is substantially inessential.Described C 4isobutylene concentration in hydrocarbon flow is generally 40-60 % by weight.For example, raffinate 1 is conventionally substantially by 30-50 % by weight iso-butylene, 10-50 % by weight 1-butylene, 10-40 % by weight cis-and trans-2-butene and 2-35 % by weight butane form; In polymerization process of the present invention, the not branching butylene in raffinate 1 is inertia conventionally substantially, and only has isobutene polymerisation.
In preferred embodiments, polymerization monomer source used is that iso-butylene content is 1-100 % by weight, especially 1-99 % by weight, particularly 1-90 % by weight, the more preferably industrial C of 30-60 % by weight 4hydrocarbon flow, especially raffinate 1 material stream, from the b/b material stream of FCC oil refining apparatus, from the product stream of propylene-Trimethylmethane co-oxidation or from the product stream of metathesis device.
Especially in the situation that raffinate 1 material stream is originated as iso-butylene, have been found that water as unique other initiators or be useful together with being selected from other initiators of organic hydroxy compounds and organohalogen compound, especially ought be aggregated in-30 ℃ to+50 ℃, while especially carrying out at the temperature of 0 ℃ to+30 ℃.
Described isobutylene type monomers mixture can comprise a small amount of pollutent as water, carboxylic acid or mineral acid and lose without any significant yield or selectivity.Suitable is prevents that by remove such objectionable impurities from isobutylene type monomers mixture these impurity are rich long-pending, for example, by adsorbing on as gac, molecular sieve or ion-exchanger at solid adsorbent.
Can also converted isobutylene or isobutylene type hydrocarbon mixture with can with the monomer mixture of the ethylenically unsaturated monomer of iso-butylene copolymerization.When will be by the monomer mixture of iso-butylene and suitable comonomer copolymerization, this monomer mixture preferably comprises at least 5 % by weight, more preferably at least 10 % by weight, especially at least 20 % by weight iso-butylenes, and preferred 95 % by weight at the most, more preferably 90 % by weight, especially at the most 80 % by weight comonomers at the most.
Useful copolymerisable monomer comprises that vinyl-arene is as vinylbenzene and alpha-methyl styrene, C 1-C 4ring-alkylated styrenes is as 2-, 3-and 4-vinyl toluene and 4-t-butyl styrene, halogenated styrenes is as 2-, 3-or 4-chloro-styrene, and the isoolefine with 5-10 carbon atom, as 2-methyl butene-1,2-methylpentene-1,2-methyl hexene-1,2-ethypentene-1,2-ethyl hexene-1 and 2-propyl group heptene-1.Other useful comonomers comprise the alkene with silyl, as 1-trimethoxysilyl ethene, 1-(trimethoxysilyl) propylene, 1-(trimethoxysilyl)-2-methacrylic-2,1-[tri-(methoxy ethoxy) silyl] ethene, 1-[tri-(methoxy ethoxy) silyl] propylene and 1-[tri-(methoxy ethoxy) silyl]-2-methacrylic-2.In addition, depend on polymerizing condition, useful comonomer also comprises isoprene, 1-butylene and cis-and trans-2-butene.
When preparing multipolymer by the inventive method, the method can be designed to preferentially form unregulated polymer or preferentially form segmented copolymer.In order to prepare segmented copolymer, for example, different monomers can be fed in polyreaction successively, just now the second comonomer especially adds during polymerization at least partly at first comonomer.Can obtain in this way diblock, three blocks and Geng Gao segmented copolymer, its block according to monomer charge order with one or another kind of comonomer is as end block.Yet, in some cases, when being fed to polyreaction simultaneously, all comonomers also form segmented copolymer, but a kind of remarkable in other rapid polymerizations more in them.This is especially at iso-butylene and vinyl aromatic compounds, especially really like this during vinylbenzene copolymerization in the methods of the invention.This is preferably formed the segmented copolymer with polystyrene end blocks.This is attributable to vinyl aromatic compounds, and especially vinylbenzene is than remarkable this fact of slower polymerization of iso-butylene.
Polymerization can be carried out continuously or in batches.Continuation method can be similar to iso-butylene under the catalyst based existence of boron trifluoride in liquid phase the known art methods of successive polymerization carry out.
The inventive method is applicable at low temperatures, for example, at-90 ℃ to 0 ℃, or especially under higher temperature, at least 0 ℃, for example, carries out at 0 ℃ to+50 ℃ or 0 ℃ to+30 ℃.Yet polymerization is in the methods of the invention preferably at-30 ℃ to+50 ℃, especially at the temperature at 0 ℃ to+30 ℃, for example, under room temperature (+20 ℃ to+25 ℃), carry out.
When being aggregated in the methods of the invention carried out under the boiling temperature of polymerization single polymerization monomer or monomer mixture or more than it, preferably at pressurizing vessel, for example, in autoclave or pressurized reactor, carry out.
Polymerization in the methods of the invention is preferably carried out under inert diluent exists.Inert diluent used should be applicable to the reaction soln viscosity conventionally occurring in polymerization process to raise and be reduced to the degree that the reaction heat that can guarantee to discharge is removed.Suitable thinner is agents useful for same to be to those solvents or the solvent mixture of inertia.Suitable thinner is for example that aliphatic hydrocrbon is as normal butane, Skellysolve A, normal hexane, normal heptane, octane and octane-iso, clicyclic hydrocarbon is as pentamethylene and hexanaphthene, aromatic hydrocarbon is as benzene, toluene and xylene, and halohydrocarbon, especially halogenated aliphatic hydrocarbon, as methyl chloride, methylene dichloride and trichloromethane (chloroform), 1, 1-ethylene dichloride, 1, 2-ethylene dichloride, trichloroethane and 1-chlorobutane, and also has halogenated aromatic hydrocarbons and the alkylaromatic hydrocarbon of halo in alkyl group side chain, as chlorobenzene, single methyl fluoride benzene, benzal fluoride and trifluoromethylbenzene, and the mixture of above-mentioned thinner.The preferred halohydrocarbon for inert diluent of describing in context is hydrochloric ether, especially pure hydrochloric ether.Hydrofluoric ether is preferably from getting rid of spendable inert diluent here, to get rid of very basically fluorine content residual in polymkeric substance.Composition used in thinner used or described solvent mixture is also isobutylene type C 4the inert component of hydrocarbon flow.
Polymerization of the present invention is preferably in the aliphatic series as inert diluent, alicyclic or aromatic hydrocarbon, halohydrocarbon, especially halogenated aliphatic hydrocarbon, or aliphatic, alicyclic and/or aromatic hydrocarbon, or halohydrocarbon, especially the mixture of halogenated aliphatic hydrocarbon, or the mixture of at least one halohydrocarbon, especially halogenated aliphatic hydrocarbon and at least one aliphatic series, alicyclic or aromatic hydrocarbon, for example, carry out in the mixture of methylene dichloride and normal hexane, volume ratio is generally 10:90-90:10, especially 50:50-85:15.Before using, preferably from thinner, remove impurity as water, carboxylic acid or mineral acid, for example, by adsorbing on as gac, molecular sieve or ion-exchanger at solid adsorbent.
In another preferred embodiment, the present invention is aggregated in Halogen aliphatic hydrocrbon or especially Halogen aromatic hydrocarbon, especially toluene and carries out.For this embodiment, found that water is particularly advantageous as other initiators, optional and described organic hydroxy compounds and/or the combination of described organohalogen compound.
Polymerization in the methods of the invention is preferably carried out under substantially non-proton property reaction conditions, especially under substantially anhydrous reaction conditions, carries out.Substantially non-proton property and substantially anhydrous reaction conditions are interpreted as referring to respectively in reaction mixture that protic foreign matter content and water-content are less than 50ppm, are especially less than 5ppm.Therefore, conventionally pass through physics and/or chemical dried feed before use.More specifically, having been found that usefully will be as aliphatic series or clicyclic hydrocarbon and the organometallic compound of solvent after routine is purified in advance and be predrying, and for example organolithium, organic-magnesium or organo-aluminium compound are to be enough to substantially remove the amount mixing of trace water from this solvent.The solvent of so processing preferably directly condenses in reaction vessel subsequently.Can also process in a similar manner and treat polymerization single polymerization monomer, especially iso-butylene or isobutylene type mixture.With other conventional drying agent as molecular sieve or pre-dried oxide compound as aluminum oxide, silicon-dioxide, calcium oxide or barium oxide are dry, be also suitable.With metal, as sodium or potassium or by metal alkyls, it is dried to the siccative that is applicable to this object for halogenated solvent that is not an option, for example calcium chloride, Vanadium Pentoxide in FLAKES or molecular sieve are except anhydrating or trace water.Can also be dried in a similar manner by metal alkyls it is processed to those raw materials that are not an option, for example vinyl aromatic compounds.Even when water is used as initiator, residual moisture also should preferably be removed by being dried before reaction substantially or completely from solvent and monomer, using in a controlled manner other water initiator with specified amount, result obtains higher technology controlling and process and result reproducibility.
The polymerization of iso-butylene or isobutylene type raw material is spontaneous carrying out when effective title complex contacts under desired reaction temperature with iso-butylene or isobutylene type monomers mixture as polymerizing catalyst conventionally.The program here can be first to add monomer, optionally, in thinner, makes it reach temperature of reaction and adds subsequently title complex.This program can also be first to add title complex, optionally, in thinner, then adds monomer.Now think polymerization to start be that all reactants are present in the moment in reaction vessel.
In order to prepare isobutylene copolymers, program can be first to add monomer, optionally, in thinner, then adds title complex.Temperature of reaction can produce before or after adding title complex.Program can also be first only to add one of monomer, optionally in thinner, then adds title complex and only after certain hour, for example, when at least 60%, at least 80% or at least 90% monomer has transformed, add other monomers.Or can first add title complex, optionally, in thinner, then can simultaneously or add successively monomer, then can produce desired reaction temperature.Now think polymerization to start be that title complex and at least one monomer are present in the moment in reaction vessel.
Except batch program described herein, polymerization in the methods of the invention also can be designed to continuation method.Now, by raw material, treat polymerization single polymerization monomer, optional diluent and optionally feeding in polyreaction continuously as the effective title complex of polymerizing catalyst, and take out reaction product continuously, thus make to produce the more or less polymerizing condition of stable state in this reactor.Until polymerization single polymerization monomer, can directly feed, with infeed after thinner or solvent cut or as the hydrocarbon flow that contains monomer, feed.
As the effective title complex of polymerizing catalyst, conventionally with dissolving, dispersion or suspension form, be present in polymerisation medium.Title complex load in conventional carrier material is also possible.The type of reactor that is applicable to polymerization process of the present invention is generally stirred-tank reactor, loop reactor and tubular reactor, but also have fluidized-bed reactor (fluidized bed reactor), containing or not solvent-laden stirred-tank reactor, fluid bed reactor (fluid bed reactor), fixed-bed reactor and fixed-bed reactor (batch mode) in batches continuously.
In the methods of the invention, as the effective title complex of polymerizing catalyst conventionally so that the element in the element halide preferably using as Lewis acid or alkyl element halide and iso-butylene in iso-butylene homopolymerization situation or with the mol ratio of polymerisable monomer total amount in iso-butylene copolymerization situation be 1:5-1:5000, preferred 1:10-1:5000, especially the amount of 1:15-1:1000, particularly 1:20-1:250 is used.
For this reaction is stopped, preferred passivation reaction mixture, for example, by adding protic compound, especially by adding water, alcohols is as the mixture of methyl alcohol, ethanol, n-propyl alcohol and Virahol or itself and water, or by adding aqueous bases, for example basic metal or alkaline earth metal hydroxides be as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, and basic metal or alkaline earth metal carbonate are if sodium carbonate, potassium, magnesium or calcium or basic metal or alkali metal bicarbonates are as the aqueous solution of sodium bicarbonate, potassium, magnesium or calcium.
Two key (α-bis-keys) content of end vinylidene that the inventive method has for the preparation of each polyisobutene end of the chain is 50mol% at least, preferred 60mol% at least, preferred 70mol% at least, preferred 80mol% at least, preferred 85mol% at least, more preferably 90mol% at least, more preferably greater than 91mol%, especially at least 95mol%, for example, be highly reactive isobutylene homo or the multipolymer of 100mol% substantially.More specifically, it is also for the preparation of by iso-butylene and at least one vi-ny l aromatic monomers, especially two key (α-bis-keys) content of end vinylidene that vinylbenzene forms and each polyisobutene end of the chain has is 50mol% at least, preferred 60mol% at least, preferred 70mol% at least, preferred 80mol% at least, preferred 80mol% at least, preferred 85mol% at least, more preferably 90mol% at least, more preferably greater than 91mol%, especially at least 95mol%, for example, be the highly reactive isobutylene multipolymer of 100mol% substantially.In order to prepare iso-butylene and at least one vi-ny l aromatic monomers, especially cinnamic this analog copolymer, making iso-butylene or isobutylene type hydrocarbon-fraction and at least one vi-ny l aromatic monomers take the weight ratio of iso-butylene and vinyl-arene is 5:95-95:5, especially 30:70-70:30 copolymerization.
Polymolecularity (the PDI=M that the highly reactive isobutylene homo of being prepared by the inventive method or multipolymer, especially isobutylene homo preferably have w/ M n) be 1.05 to being less than 3.5, preferably 1.05 to being less than 3.0, and preferably 1.05 to being less than 2.5, preferably 1.05-2.3, more preferably 1.05-2.0, especially 1.1-1.85.Typical PDI value is 1.2-1.7 in optimum process scheme situation.
The number-average molecular weight M that the highly reactive isobutylene homo of being prepared by the inventive method or multipolymer preferably have n(passing through gel permeation chromatography) is preferably 500-250000, more preferably 500-100000, even more preferably 500-25000, especially 500-5000.Isobutylene homo even more preferably has 500-10000, especially 500-5000, for example approximately 1000 or approximately 2300 number-average molecular weight M n.
There are the two keys of end vinylidene, comprise and be the organic sulfonic acid as initiator molecule of the form of mixing and the isobutene polymer being present in as main ingredient in the isobutylene homo of preparing according to the present invention is new compound.Therefore, the present invention also provides the isobutene polymer of general formula I:
Figure BDA0000464856840000191
Wherein
R 10for general formula-O-SO 2the sulfo group structure division of Z, wherein variable Z represents C 1-C 20alkyl, C 1-C 20haloalkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20arylalkyl, and R 11and R 12be hydrogen, C independently of one another 1-C 20alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20alkylaryl, and
N is the number of 9-4500.
In preferred embodiments, R 11and R 12be hydrogen independently of one another, C 1-C 4alkyl, especially methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, or can also be with 1 or 2 C 1-C 4alkyl or C 1-C 4alkoxyl group is as substituent phenyl, and n is 9-4500, preferably the number of 9-180, especially 9-90, particularly 15-45.
The inventive method successfully under positively charged ion condition to be generally 20-100%, especially the satisfactory of 35-90% is being generally 5-120 minute to high conversion, especially polymerization iso-butylene or containing the monomer mixture of iso-butylene in the short reaction time of 5-60 minute, obtain end vinylidene double bond content that each polyisobutene end of the chain has in nearly all situation for 90mol% at least and there is highly reactive isobutylene homo or the multipolymer of narrow molecular weight distributions.
The following example is used for being described in more detail and does not limit the present invention.
Embodiment 1: catalyzer-initiator mixture of preparing initiated polymerization
Preparation as the Lewis acid (some comprise donor) of polymerizing catalyst and can Isobutylene Initiated or containing the following mixture of the initiator of the polyreaction of the present invention of isobutylene monomer mixture or its precursor the Typical Representative as such system:
(a) 1.4g (0.015mol) methanesulfonic is dissolved in 75ml methylene dichloride, then adds 0.77g (5.9mmol) di-n-butyl ether;
(b) 1.4g (0.015mol) methanesulfonic is scattered in 125ml toluene, then adds 0.77g (5.9mmol) di-n-butyl ether;
(c) 2.0g (0.015mol) aluminum chloride is suspended in 75ml methylene dichloride, then adds 0.77g (5.9mmol) di-n-butyl ether and 1.4g (0.015mol) methanesulfonic;
(d) 2.0g (0.015mol) aluminum chloride is suspended in 125ml toluene, then adds 0.77g (5.9mmol) di-n-butyl ether and 1.4g (0.015mol) methanesulfonic;
(e) 2.4g (0.015mol) iron(ic) chloride (III) is suspended in 75ml methylene dichloride, then adds 0.77g (5.9mmol) di-n-butyl ether;
(f) 2.4g (0.015mol) iron(ic) chloride (III) is suspended in 125ml toluene, then adds 0.77g (5.9mmol) di-n-butyl ether;
(g) 2.4g (0.015mol) iron(ic) chloride (III) is suspended in 75ml methylene dichloride, then adds 0.77g (7.5mmol) diisopropyl ether and 1.4g (0.015mol) methanesulfonic;
(h) 2.0g (0.015mol) zinc chloride is suspended in 75ml methylene dichloride, then adds 0.77g (7.5mmol) diisopropyl ether and 1.4g (0.015mol) methanesulfonic;
(i) 2.0g (0.015mol) zinc chloride is suspended in 75ml methylene dichloride, then adds 0.77g (5.9mmol) di-n-butyl ether and 1.4g (0.015mol) methanesulfonic;
(j) 2.0g (0.015mol) zinc chloride is suspended in 75ml methylene dichloride, then adds 1.4g (0.015mol) methanesulfonic;
(k) 2.4g (0.015mol) iron(ic) chloride (III) is suspended in 75ml methylene dichloride, then adds 1.4g (0.015mol) methanesulfonic;
(l) 2.0g (0.015mol) aluminum chloride is suspended in 75ml methylene dichloride, then adds 1.4g (0.015mol) methanesulfonic;
(m) 1.4g (0.015mol) methanesulfonic is scattered in 75ml methylene dichloride, then introduces 1.0g (0.015mol) boron trifluoride;
(n) 1.4g (0.015mol) methanesulfonic is dissolved in 125ml toluene, then introduces 1.0g (0.015mol) boron trifluoride;
(o) 2.6g (0.015mol) tosic acid is dissolved in 75ml methylene dichloride, then introduces 1.0g (0.015mol) boron trifluoride;
(p) 2.6g (0.015mol) tosic acid is dissolved in 125ml toluene, then introduces 1.0g (0.015mol) boron trifluoride.
Embodiment 2: at-20 ℃, in methylene dichloride, use FeCl 3bu 2o and as the methanesulfonic polymerization " raffinate 1 " of initiator
" raffinate 1 " that used catalyst complexes (being 1M dichloromethane solution form) that 0.53mmol comprises Anhydrous Ferric Chloride (III) that mol ratio is 1:1 and di-n-butyl ether to comprise the pure iso-butylene of 5.94g (106.0mmol) with 68% transformation efficiency polymerization 14.86g at-20 ℃ in 30 minutes in 130ml methylene dichloride under 0.015mol exists as the methanesulfonic of initiator, obtains number-average molecular weight M nbe 2285, polymolecularity is 2.34 and the end double bond content polyisobutene that is 91.7mol%.
Embodiment 3: at+20 ℃, in methylene dichloride, use FeCl 3bu 2o and as the methanesulfonic polymerization " raffinate 1 " of initiator
" raffinate 1 " that used catalyst complexes (being 1M dichloromethane solution form) that 0.53mmol comprises Anhydrous Ferric Chloride (III) that mol ratio is 1:1 and di-n-butyl ether to comprise the pure iso-butylene of 2.97g (53.0mmol) with 92% transformation efficiency polymerase 17 .43g at+20 ℃ in 30 minutes in 65.0ml methylene dichloride under 0.015mol exists as the methanesulfonic of initiator, obtains number-average molecular weight M nbe 822, polymolecularity is 1.81 and the end double bond content polyisobutene that is 93.1mol%.
Embodiment 4: at+20 ℃, in toluene, use FeCl 3bu 2o and as the methanesulfonic polymerization " raffinate 1 " of initiator
" raffinate 1 " that used catalyst complexes (being 1M dichloromethane solution form) that 0.53mmol comprises Anhydrous Ferric Chloride (III) that mol ratio is 1:1 and di-n-butyl ether to comprise the pure iso-butylene of 2.97g (53.0mmol) with 20% transformation efficiency polymerase 17 .43g at+20 ℃ in 30 minutes in 65.0ml toluene under 0.015mol exists as the methanesulfonic of initiator, obtains number-average molecular weight M nbe 1000, polymolecularity is 2.20 and the end double bond content polyisobutene that is 85.0mol%.
Embodiment 5: at+20 ℃, in methylene dichloride, use AlCl 3bu 2o and as the methanesulfonic polymerization " raffinate 1 " of initiator
" raffinate 1 " that used catalyst complexes (being 1M dichloromethane solution form) that 1.0mmol comprises Aluminum chloride anhydrous that mol ratio is 1:1 and di-n-butyl ether to comprise the pure iso-butylene of 5.79g (103.4mmol) with 73% transformation efficiency polymerization 14.49g at+20 ℃ in 5 minutes in 125ml methylene dichloride under 0.03mol exists as the methanesulfonic of initiator, obtains number-average molecular weight M nbe 2491, polymolecularity is 2.97 and the end double bond content polyisobutene that is 90.0mol%.

Claims (16)

1. prepare end vinylidene double bond content that each polyisobutene end of the chain has at least highly reactive isobutylene homo of 50mol% or the method for multipolymer for one kind, by be suitable as at least one Lewis acid of polymerizing catalyst or as polymerizing catalyst polymerization iso-butylene or carry out containing the monomer mixture of iso-butylene under the existence effectively and under the existence of the title complex being formed by least one Lewis acid and at least one donor and at least one initiator, described method comprises use general formula Z-SO 3the organic sulfonic acid of H is as at least one initiator, and wherein variable Z represents C 1-C 20alkyl, C 1-C 20haloalkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20arylalkyl.
2. according to the process of claim 1 wherein that at least one initiator used is the organic sulfonic acid that is selected from methanesulfonic, trifluoromethayl sulfonic acid, trichloromethane sulfonic acid and toluenesulphonic acids or its mixture.
3. according to the method for claim 1 or 2, wherein for the Lewis acid as the effective title complex of polymerizing catalyst at least one is selected from the binary chlorine of element and the compound of fluorine cpd or its mixture of periodic table of elements 1-8 transition group and 3-5 main group.
4. according to the method for claim 3, wherein Lewis acid used is for being selected from BCl 3, AlCl 3, TiCl 4, FeCl 2, FeCl 3, ZnCl 2, BF 3, AlF 3, TiF 4, FeF 2, FeF 3and ZnF 2binary chlorine or fluorine cpd.
5. according to the method for any one in claim 1-4, be wherein used as polymerizing catalyst effectively and comprise the title complex as the organic compound with at least one ether functional group or carboxylicesters functional group of donor.
6. according to the method for claim 5, wherein the organic compound as donor is general formula R 1-O-R 2dialkyl ether, variable R wherein 1and R 2be C independently of one another 1-C 20alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20arylalkyl, or general formula R 3-COOR 4hydrocarbyl carboxylic ester, variable R wherein 3and R 4be C independently of one another 1-C 20alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20arylalkyl.
7. according to the method for claim 6, the total carbon number wherein having as the organic compound of donor is 3-16.
8. according to the method for any one in claim 1-7, wherein said being aggregated under at least one other initiator of extra use carried out, and described other initiators are for single-or polyfunctional and be selected from organic hydroxy compounds, organohalogen compound, protonic acid and water.
9. method according to Claim 8, wherein at least one other initiator is selected from water, one or more protonic acids, methyl alcohol, ethanol, 1-phenylethyl alcohol, 1-(p-methoxyphenyl) ethanol, n-propyl alcohol, Virahol, 2-phenyl-2-propyl alcohol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, 1-phenyl-1-monochloroethane, 2-phenyl-2 cbloropropane isopropyl chloride, tertiary butyl chloride and 1,3-or Isosorbide-5-Nitrae-bis-(1-hydroxyl-1-methylethyl) benzene and composition thereof.
10. according to the method for any one in claim 1-9, under existing, the nitrogenous basic cpd of the wherein said 0.01-10mmol of being aggregated in carries out, in each case the 1mol isobutylene monomer based on using in iso-butylene homopolymerization situation or the 1mol polymerisable monomer total amount based on using in iso-butylene copolymerization situation.
11. according to the method for claim 10, and wherein nitrogenous basic cpd used is pyridine or pyridine derivate.
12. according to the method for any one in claim 1-11, and it is for the preparation of number-average molecular weight M nhighly reactive isobutylene homo or multipolymer for 500-250000.
13. according to the method for any one in claim 1-12, and it is 1.05 to the highly reactive isobutylene homo or the multipolymer that are less than 3.5 for the preparation of polymolecularity.
14. according to the method for any one in claim 1-13, and carry out to the temperature of+50 ℃ wherein said being aggregated in-30 ℃.
15. according to the method for any one in claim 1-14, the wherein said aliphatic series as inert diluent, the alicyclic or aromatic hydrocarbon of being aggregated in, halogenated aliphatic hydrocarbon, or the mixture of aliphatic, alicyclic and/or aromatic hydrocarbon or halogenated aliphatic hydrocarbon, or carry out in the mixture of at least one halogenated aliphatic hydrocarbon and at least one aliphatic series, alicyclic or aromatic hydrocarbon.
The isobutene polymer of 16. general formula Is:
Figure FDA0000464856830000021
Wherein
R 10for general formula-O-SO 2the sulfo group structure division of Z, wherein variable Z represents C 1-C 20alkyl, C 1-C 20haloalkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20arylalkyl, and R 11and R 12be hydrogen, C independently of one another 1-C 20alkyl, C 5-C 8cycloalkyl, C 6-C 20aryl or C 7-C 20alkylaryl, and
N is the number of 9-4500.
CN201280039216.8A 2011-08-11 2012-08-10 Process for preparing high-reactivity isobutene homo- or copolymers Pending CN103764695A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11177300.8 2011-08-11
EP11177300 2011-08-11
PCT/EP2012/065751 WO2013021058A1 (en) 2011-08-11 2012-08-10 Process for preparing high-reactivity isobutene homo- or copolymers

Publications (1)

Publication Number Publication Date
CN103764695A true CN103764695A (en) 2014-04-30

Family

ID=46642554

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280039216.8A Pending CN103764695A (en) 2011-08-11 2012-08-10 Process for preparing high-reactivity isobutene homo- or copolymers

Country Status (10)

Country Link
EP (1) EP2742073A1 (en)
JP (1) JP6099648B2 (en)
KR (1) KR20140049024A (en)
CN (1) CN103764695A (en)
AR (1) AR087514A1 (en)
BR (1) BR112014002551A2 (en)
MY (1) MY166046A (en)
RU (1) RU2608510C2 (en)
SG (2) SG2014004303A (en)
WO (1) WO2013021058A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107033260A (en) * 2017-04-14 2017-08-11 上海欧勒奋生物科技有限公司 A kind of method that PAO9 base oils are synthesized based on the Aluminium Trichloride as Catalyst that Loprazolam is modified
CN107586248A (en) * 2016-07-08 2018-01-16 上海纳克润滑技术有限公司 A kind of method that alhpa olefin oligomerisation should be carried out based on microchannel plate
CN110183560A (en) * 2019-06-14 2019-08-30 华东理工大学 A method of middle-molecular-weihydroxyethyl polyisobutene is prepared using ferrotitanium composite catalyst
CN110997737A (en) * 2017-08-17 2020-04-10 巴斯夫欧洲公司 Method for producing highly reactive isobutene homo-or copolymers
CN113698514A (en) * 2016-02-16 2021-11-26 巴斯夫欧洲公司 Method for producing highly reactive isobutene homo-or copolymers

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9156924B2 (en) * 2013-03-12 2015-10-13 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9631038B2 (en) 2013-10-11 2017-04-25 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9771442B2 (en) 2015-05-13 2017-09-26 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
JP6839004B2 (en) * 2017-03-21 2021-03-03 株式会社カネカ Method for Producing Isobutylene Polymer
US10047174B1 (en) 2017-06-28 2018-08-14 Infineum International Limited Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10167352B1 (en) 2017-06-28 2019-01-01 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10174138B1 (en) 2018-01-25 2019-01-08 University Of Massachusetts Method for forming highly reactive olefin functional polymers
KR102203006B1 (en) * 2019-04-24 2021-01-13 대림산업 주식회사 Method for producing highly reactive polybutene
US10829573B1 (en) 2019-05-21 2020-11-10 Infineum International Limited Method for forming highly reactive olefin functional polymers
WO2023232613A1 (en) * 2022-06-03 2023-12-07 Basf Se Process for manufacturing of higher functional polyisobutenes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2045592A (en) * 1932-08-11 1936-06-30 Phillips Petroleum Co Resinous products
US5169914A (en) * 1988-05-03 1992-12-08 Edison Polymer Innovation Corporation Uniform molecular weight polymers
CN1304418A (en) * 1998-06-05 2001-07-18 巴斯福股份公司 Method for producing highly reactive polyisobutenes
CN1972974A (en) * 2004-06-25 2007-05-30 埃克森美孚化学专利公司 Polymerization processes using hydrofluorocarbons

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2702604C2 (en) 1977-01-22 1984-08-30 Basf Ag, 6700 Ludwigshafen Polyisobutenes
GB8329082D0 (en) 1983-11-01 1983-12-07 Bp Chem Int Ltd Low molecular weight polymers of 1-olefins
BE1006694A5 (en) * 1991-06-22 1994-11-22 Basf Ag PREPARATION PROCESS EXTREMELY REACTIVE polyisobutenes.
US5340881A (en) 1992-11-16 1994-08-23 The University Of Akron Aldehyde-telechelic polyisobutylenes, catalytic method for preparing the same with high conversion and selectivity, and block copolymers made thereform
JPH06345821A (en) * 1993-04-12 1994-12-20 Kanegafuchi Chem Ind Co Ltd Production of isobutylene-based polymer having unsaturated group
US5448000A (en) * 1994-02-17 1995-09-05 New Mexico Tech Research Foundation End-quenching the living polymerization of isobutylene with acetyl sulfate
DE10211418A1 (en) * 2002-03-15 2003-09-25 Bayer Ag Process for the production of highly reactive polyisobutenes
JP5365913B2 (en) * 2009-04-02 2013-12-11 株式会社カネカ Continuous production method of living cationic polymer
CN101955558B (en) 2009-07-15 2013-03-13 北京化工大学 Initiating system for preparing high-reaction activity polyisobutene and copolymer of polyisobutene

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2045592A (en) * 1932-08-11 1936-06-30 Phillips Petroleum Co Resinous products
US5169914A (en) * 1988-05-03 1992-12-08 Edison Polymer Innovation Corporation Uniform molecular weight polymers
CN1304418A (en) * 1998-06-05 2001-07-18 巴斯福股份公司 Method for producing highly reactive polyisobutenes
CN1972974A (en) * 2004-06-25 2007-05-30 埃克森美孚化学专利公司 Polymerization processes using hydrofluorocarbons

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113698514A (en) * 2016-02-16 2021-11-26 巴斯夫欧洲公司 Method for producing highly reactive isobutene homo-or copolymers
CN113698514B (en) * 2016-02-16 2023-11-10 巴斯夫欧洲公司 Process for preparing highly reactive isobutylene homo-or copolymers
CN107586248A (en) * 2016-07-08 2018-01-16 上海纳克润滑技术有限公司 A kind of method that alhpa olefin oligomerisation should be carried out based on microchannel plate
CN107033260A (en) * 2017-04-14 2017-08-11 上海欧勒奋生物科技有限公司 A kind of method that PAO9 base oils are synthesized based on the Aluminium Trichloride as Catalyst that Loprazolam is modified
CN110997737A (en) * 2017-08-17 2020-04-10 巴斯夫欧洲公司 Method for producing highly reactive isobutene homo-or copolymers
CN110997737B (en) * 2017-08-17 2023-03-14 巴斯夫欧洲公司 Method for producing highly reactive isobutene homo-or copolymers
CN110183560A (en) * 2019-06-14 2019-08-30 华东理工大学 A method of middle-molecular-weihydroxyethyl polyisobutene is prepared using ferrotitanium composite catalyst
CN110183560B (en) * 2019-06-14 2020-08-28 华东理工大学 Method for preparing medium molecular weight polyisobutylene by using iron-titanium composite catalyst

Also Published As

Publication number Publication date
WO2013021058A1 (en) 2013-02-14
SG10201606556WA (en) 2016-09-29
AR087514A1 (en) 2014-03-26
MY166046A (en) 2018-05-22
JP2014524492A (en) 2014-09-22
JP6099648B2 (en) 2017-03-22
RU2608510C2 (en) 2017-01-18
RU2014108711A (en) 2015-09-20
BR112014002551A2 (en) 2017-03-14
KR20140049024A (en) 2014-04-24
EP2742073A1 (en) 2014-06-18
SG2014004303A (en) 2014-03-28

Similar Documents

Publication Publication Date Title
CN103764695A (en) Process for preparing high-reactivity isobutene homo- or copolymers
CN102762610A (en) Method for producing highly reactive isobutene homo or copolymers
US8697820B2 (en) Process for preparing high-reactivity isobutene homo- or copolymers
US8637619B2 (en) Process for preparing high-reactivity isobutene homo- or copolymers
EP2860206B1 (en) Polymerization initiating system and method to produce highly reactive olefin functional polymers
EP2778181B1 (en) Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9034998B2 (en) Polymerization initiating system and method to produce highly reactive olefin functional polymers
EP3098246B1 (en) Polymerization initiating system and method to produce highly reactive polybutenes
CN108602914A (en) The method for preparing highly reactive isobutylene homo or copolymer
KR101992080B1 (en) Method for forming highly reactive olefin functional polymers
US5703183A (en) Carbocationic catalysts and process for using said catalysts
CN109134718A (en) Polymerization initiation system and the method for preparing high-activity olefin functional polymer
CN108602913A (en) The method for preparing highly reactive isobutylene homo or copolymer
CN111978439B (en) Improved process for forming highly reactive olefin functional polymers

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20140430