CN1610705A - Transition metal-free initiator for the preparation of isobutylene-based polymers - Google Patents
Transition metal-free initiator for the preparation of isobutylene-based polymers Download PDFInfo
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- CN1610705A CN1610705A CN 02826457 CN02826457A CN1610705A CN 1610705 A CN1610705 A CN 1610705A CN 02826457 CN02826457 CN 02826457 CN 02826457 A CN02826457 A CN 02826457A CN 1610705 A CN1610705 A CN 1610705A
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- acid
- group
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- alkyl
- initiator system
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims description 37
- 229920000642 polymer Polymers 0.000 title description 9
- 238000002360 preparation method Methods 0.000 title description 3
- 239000003828 free initiator Substances 0.000 title 1
- 230000007704 transition Effects 0.000 title 1
- 239000012190 activator Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000002841 Lewis acid Substances 0.000 claims abstract description 21
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims abstract description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 150000008282 halocarbons Chemical class 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000004820 halides Chemical group 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 claims 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- 150000003623 transition metal compounds Chemical class 0.000 abstract 1
- 235000021355 Stearic acid Nutrition 0.000 description 32
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 32
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 description 5
- -1 cyclopentadienyl transition metal compounds Chemical class 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- GRHQDJDRGZFIPO-UHFFFAOYSA-N 4-bromobutanoic acid Chemical compound OC(=O)CCCBr GRHQDJDRGZFIPO-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001787 chalcogens Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
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
- 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
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
There is disclosed a process for polymerizing a cationically polymerizable olefin comprising the step of polymerizing at least one cationically polymerizable olefin, preferably at subatmospheric pressure, in the presence of an initiator system which comprises a Lewis acid and an activator which is a proton source, such as an alcohol, a thiol, a carboxylic acid, a thiocarboxylic acid and the like. The initiator system does not contain a transition-metal compound.
Description
Technical field
The present invention relates to a kind of alternative initiator system that is used to prepare isobutylene-based polymers.
Technical background
The cationoid polymerisation of alkene is known in the art.
Usually, the catalyst system of cationic polymerization use comprises: (1) Lewis acid; (2) contain the tertiary alkyl initiator molecule of halogen, ester, ether, acid or alcohol groups and (3) electron donor molecule of choosing wantonly, as ethyl acetate.This catalyst system has been used for so-called alkene " activity " and " nonactive " carbon cation polymerization.
Based on halogen and/or contain the Lewis acid of alkyl such as the catalyst system of boron trichloride and titanium tetrachloride uses the various combinations of said components, and has similar operational characteristic usually.For so-called " activity " paradigmatic system, the 16-40 that common lewis acidic concentration surpasses initiator site (site) concentration doubly so that (polymerization degree based on 890) reach 100% conversion under-75 to-80 ℃, in 30 minutes.
In so-called " nonactive " paradigmatic system, high molecular weight polyisobutylene is in practice only at low temperature (60 to-100 ℃), and catalyst concentration prepares above under the situation of a catalyst molecule initiator molecule.In practice, many above-mentioned catalyst systems only use in specific narrow temperature scope and concentration profile.
In recent years, developed the new catalyst system that a class utilizes compatible weakly coordinating anion to be used in combination with cyclopentadienyl transition metal compounds (also claiming " metallocene " in this area).For example, referring to any one piece among EP-A-0277003, EP-A-0277004, US-A-5198401 and the WO-92/00333-A1.
The use that does not contain the ionization compound of active proton also is known.For example, referring to EP-A-0426637 and EP-A-0573403.
Disclose a kind of use among the US-A-5448001 and contained carbocation method just like the catalyst system polymerization iso-butylene of metallocene catalyst and boron.
WO-00/04061-A1 discloses a kind of as Cp*TiMe
3(" initiator ") and B (C
6F
5)
3The catalyst system of (" activator ") exists down, the cationic polymerization process of carrying out under pressure below atmospheric pressure.This system produces " active cation " and " weakly coordinating anion ".Utilize above-mentioned catalyst system, can obtain having the polymkeric substance of desired molecular weight characteristics, it has higher yields and comparatively high temps with respect to traditional method, therefore, has reduced the fund and the running expense of the enterprise for preparing this polymkeric substance.
But the catalyzer that adopts in the aforesaid method has many disadvantageous aspects, comprises expense and operational issue.
Iso-butylene prepares isoprene-isobutylene rubber with a small amount of isoprene polymerization, faces special difficulty.Particularly, as known in the art, this polyreaction is high thermopositive reaction, and needs reaction mixture is cooled to closely-95 ℃ in scale operation.In the art, although in design of research novel reactor and/or raw catalyst system aspects many progress are arranged, above-mentioned needs still exist.
Wish and under relatively-high temperature (with respect to method of the prior art), under more eco-friendly condition, to obtain the isobutylene-based polymers, particularly isobutylene based copolymer of high yield in the mode of calculating.Also do not accomplish this point so far.
Summary of the invention
We find, utilize and contain Lewis acid and activator, but the initiator system that does not contain any transistion metal compound can carry out isobutene polymerisation.Described initiator system prepares the very high polymkeric substance of output under high relatively temperature, this polymkeric substance has high molecular, narrow polydispersity index.The feature of described activator maximum is as proton source.Suitable activator comprises alcohol, mercaptan, carboxylic acid, thiocarboxylic acid etc.
This system can not only prepare the polymkeric substance with high molecular and narrow molecular weight distributions, can also produce higher monomer conversion.Described polyreaction is preferably carried out under pressure below atmospheric pressure, and has further advantage, carries out under the higher temperature that can imagine before surpassing.
In addition, described reaction can be carried out in than the more eco-friendly solvent of the solvent of prior art.
Detailed Description Of The Invention
Therefore, the present invention relates to a kind of method of alkene of polymerization cationically polymerizable, it is included in the initiator system that contains following material and has the step of the alkene of at least a cationically polymerizable of polymerization down:
A) at least a Lewis acid with following formula:
(R
1R
2R
3)M
Wherein, M is selected from B, Al, Ga and In;
R
1, R
2And R
3Bridging or non-bridged, and be independently selected from alkyl, halo carbon back (halocarbyl) and the halo carbon back that replaces of halide group, dialkyl group amido, alkoxide and aryl oxide group, alkyl and replacement and the organic non-metal group of alkyl and the replacement of halo carbon back;
And b) at least a activator, described activator is a proton source;
Condition is that described initiator system does not further contain transistion metal compound.
Method of the present invention is particularly conducive to the preparation butyl rubber polymer.The term of Shi Yonging " isoprene-isobutylene rubber " means the polymkeric substance by main component and submember prepared in reaction in this manual, described main component is isomonoolefin such as iso-butylene, described submember is a polyene hydrocarbon, for example conjugated diene such as isoprene or divinyl, for the monomer that the participation of per 100 weight parts is reacted, described main component accounts for the 70-99.5 weight part usually, preferred 85-99.5 weight part, described submember accounts for the 30-0.5 weight part usually, preferred 15-0.5 weight part.Described isoolefine is generally C
4-C
8Compound is as iso-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene and 4-methyl-1-pentene.The monomer mixture that preferably is used to prepare isoprene-isobutylene rubber comprises iso-butylene and isoprene.Optional olefinic monomer that one or more are extra such as vinylbenzene, alpha-methyl styrene, p-methylstyrene, chloro-styrene, pentadiene etc. add in the butyl rubber polymer.It will be obvious to those skilled in the art that and to adjust above-mentioned composition in the case so that total amount is 100%.Preferably form in US-A-2631984, US-A-5162445 and US-A-5886106 openly, be introduced into as a reference with regard to the execution aspect of judicial process.
Lewis-acidic components in the described initiator system is the compound with following formula:
(R
1R
2R
3)M
Wherein, M is selected from B, Al, Ga and In, preferred B;
R
1, R
2And R
3Be independently selected from the organic non-metal base that the halo carbon back of alkyl, halo carbon back and replacement of bridging or non-bridged halide group, dialkyl group amido, alkoxide and aryl oxide group, alkyl and replacement and alkyl and halo carbon back replace; Preferably a R group is represented halide group at the most;
Activator component in the described catalyst system is preferably alcohol, mercaptan, carboxylic acid, thiocarboxylic acid etc.Particularly preferred activator is the top listed material that contains at least 8 carbon atoms, for example nonyl alcohol, Stearyl alcohol and octadecanoic acid.
One preferred embodiment in, M is B, R
1And R
2Identical or different, be to contain the aryl of 6-20 carbon atom or the aryl of replacement, and can interconnect (stable referring at the polymerization process jackshaft is not destroyed) by stable bridging group; And R
3Be selected from the halo carbon back, alkyl of alkyl, halo carbon back and the replacement of hydride group, alkyl and replacement-and the chalcogen group and the halide group of the organic non-metal base that replaces of halo carbon back, dibasic nitrogen base, replacement.
In a particularly preferred embodiment, R
1, R
2And R
3Be respectively (C
6F
5) base.
Do not wish to be bound to any specific theory, Lewis acid and activator are considered to form together the bridging thing with following structure:
[(R
1R
2R
3)M]
2-μZ]
-H
+
Wherein Z represent from promoting agent capture acid proton and the group that produces (as, if promoting agent is a kind of alcohol (ROH), Z represents alkoxyl group (OR)).Proton in this structure is acid strong (the proving by NMR) of expection, in fact can be considered to " superacidity ", its acidity reach at least under situation about existing without any transistion metal compound can initiated polymerization degree.
Preferably, one mole of Lewis acid uses at least 0.01 mole of activator, and the maximum amount of employed activator is preferably every mole of Lewis acid and uses 1 mole.More preferably, activator and lewis acidic ratio range are 0.01: 1-1: 1, even preferred scope is 0.25: 1-1: 1, and further preferred scope is 0.5: 1-1: 1.Most preferably be every mole of Lewis acid and use 0.5 mole of activator, because this is the theoretical amount that all Lewis acids that exist is originally changed into the required activator of bridging thing.
It should be noted that when activator and lewis acidic ratio during less than theoretical amount, described bridging thing will still form (under equilibrium conditions), but less than optimal amount.
Present method can be implemented under pressure below atmospheric pressure.The preferred pressure of present method of implementing is less than 100kPa, be more preferably less than 90kPa, even more preferably in the scope of 0.00001-50kPa, even more preferably in the scope of 0.0001-40kPa, even more preferably in the scope of 0.0001-30kPa, most preferably in the scope of 0.0001-15kPa.
Present method can be higher than under-100 ℃ the temperature to be implemented, and preferred range is-80-25 ℃, and preferred temperature range is-60-10 ℃, and most preferred temperature ranges is-40-0 ℃.
Adopt the initiator system that is used in particular for preparing isobutylene-based polymers disclosed herein to have some beyond thought advantage.Prepared polymkeric substance has high molecular.This also is correct for isobutylene-based polymers.Usually, introduce second monomer (as isoprene (IP)) and produce the much lower multipolymer of homopolymer that molecular weight ratio under equal conditions prepares, but here be not this situation, though the molecular weight of isobutylene copolymers still is lower than the under equal conditions homopolymer of preparation, the reduction of molecular weight is markedly inferior to desired value surprisingly.In addition, these polyreactions are very fast, and yield is very high, and monomeric transformation efficiency is 100% in homopolymerization.In polar solvent, copolyreaction can reach proximate transformation efficiency.Further embodiment of the present invention will be described with reference to following examples, and described embodiment only is used for explanation, and should not be used for limiting the scope of the invention.
Embodiment
Before installing, all glasswares all will be 120 ℃ of following heat dryings at least 12 hours.Nitrogen is carried out purifying by hot BASF catalyzer and molecular sieve successively.Methylene dichloride carries out drying by refluxing on hydrolith under argon gas, toluene is by carrying out drying at sodium-benzophenone stream last time under argon gas, two kinds of all existing before use distillations of solvent are carried out freezing-pump then and are taken out-melt (freeze-pump-thaw) degassing.If desired, solvent is kept on the activatory molecular sieve under the argon gas.
With described diolefinic monomer, isoprene (IP) to remove p-ten.-butylcatechol, is used n-Buli (the 1.6M solution in normal hexane) titration and vacuum distilling by a column purification before using.Then it is kept in the loft drier that is full of nitrogen under-30 ℃.
Iso-butylene (IB) is carried out purifying by two molecular sieve columns, and be condensate in being with in the graduated pipe in the immersion liquid nitrogen.With described IB fusing, recording volume (about 8-24 milliliter), immerse then carry out in the liquid nitrogen bath freezing.System is evacuated to 10
-3Holder is isolated IB and is managed and system is positioned under the nitrogen atmosphere.
All activators all will distill in argon gas before use.
With (B (the C for example of the Lewis acid in 5 milliliters of solvents respectively
6F
5)
3, common 25 milligrams, 0.05 mmole, sublimed) and the mixture of 18 carbonic acid (common 13 milligrams, 0.06 mmole, sublimed) add, and freezing in liquid nitrogen, make initiator and monomeric ratio be about 1: 1500.The solution of initiator and IB was transferred to the temperature (utilizing-30 ℃ cooling bath) that needs before adding IB.
In certain embodiments, adding the diolefine that quantity is about 1-3mol% of IB amount before the IB condensation in the IB pipe, this operates in the loft drier that is full of nitrogen and finishes.
The solution of described alkene and initiator system stirs (" static vacuum " system that refers to seals at this moment, and pressure is residue IB and the vapour pressure of solvent under temperature of reaction basically) usually in static vacuum and under predetermined cooling bath temperature.When methylene dichloride was used as solvent, the number of polymers 15-90 after adding IB/IP usually began precipitation after second.When toluene is solvent, form viscous solution, need to continue to stir.After about 1 hour, enter methyl alcohol (greater than 1L) and termination reaction by precipitation.Sedimentable matter is dissolved in the normal hexane, and solvent flash distillation is under reduced pressure removed.Obtain the white solid polymkeric substance, be dried to constant weight.
Table 1 illustrates the result of series of isobutylene homopolymerisation reactions.
Table 2 illustrates series and utilizes octadecanoic acid to carry out the result of iso-butylene/isoprene copolymer reaction.
Table 3 illustrates series and utilizes various different acid to carry out the result of iso-butylene/isoprene copolymer reaction.
The test of table 1-homopolymerization
Unless indicate in addition, all tests in 15 milliliters of methylene dichloride, use 60 micromole's initiators to carry out, vacuum reaction is 1 hour under-30 ℃ bath temperature.
| Embodiment | Lewis acid | Activator | Lewis acid: activator | ?????IB ????(mL) | Transformation efficiency (%) | ???????Mw ????(g/mol) | ???M W/M N |
| ???1a | ????B(C 6F 5) 3 | ???- | ????- | ????11.8 | ????9 | ????660249 | ????1.4 |
| ???1b | ????- | Octadecanoic acid | ????- | ????10.9 | ????0 | ????- | ????- |
| ???1c | ????B(C 6F 5) 3 | Octadecanoic acid | ????1∶1 | ????10.4 | ????21.8 | ????962108 | ????3.8 |
| ???1d | ????B(C 6F 5) 3 | Octadecanoic acid | ????1∶1 | ????10.3 | ????23.4 | ????516601 | ????2.7 |
| ???1e | ????B(C 6F 5) 3 | Octadecanoic acid | ????1∶1 | ????11.5 | ????40 | ????511317 | ????1.5 |
| ???1f | ????B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.4 | ????100 | ????426021 | ????3.9 |
| ???1g | ????B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.3 | ????100 | ????539030 | ????4.2 |
| ???1h | ????B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????11.2 | ????100 | ????202927 | ????2.4 |
| ???1j | ????B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????11.6 | ????100 | ????371531 | ????5.4 |
Table 2-utilizes the copolyreaction test of octadecanoic acid
Unless indicate in addition, all tests in 15 milliliters of methyl chloride, use 60 micromole's initiators to carry out, vacuum reaction is 1 hour under-30 ℃ bath temperature.
| Embodiment | Lewis acid | Activator | Lewis acid: activator | ?????IB ????(mL) | ?????IP ????(mg) | Transformation efficiency (%) | ???????Mw ?????(g/mol) | ???MWD |
| ???2a | ??B(C 6F 5) 3 | Octadecanoic acid | ????1∶1 | ????11.3 | ????148 | ????22.3 | ?????405837 | ????2.4 |
| ???2b | ??B(C 6F 5) 3 | Octadecanoic acid | ????1∶1 | ????10.8 | ????108 | ????26.3 | ?????396771 | ????2.1 |
| ???2c a | ??B(C 6F 5) 3 | Octadecanoic acid | ????1∶1 | ????10.8 | ????100 | ????18 | ?????538908 | ????2.9 |
| ???2d | ??B(C 6F 5) 3 | Octadecanoic acid | ????0.5∶1 | ????10.5 | ????126 | ????4.2 | ?????178100 | ????2.4 |
| ???2e | ??B(C 6F 5) 3 | Octadecanoic acid | ????1∶1 | ????10 | ????118 | ????14 | ?????142479 | ????2.6 |
| ???2f | ??B(C 6F 5) 3 | Octadecanoic acid | ????1.5∶1 | ????10 | ????124 | ????80 | ?????225706 | ????1.6 |
| ???2g | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????11 | ????120 | ????80 | ?????259829 | ????1.9 |
| ???2h | ??B(C 6F 5) 3 | Octadecanoic acid | ????3∶1 | ????9.7 | ????115 | ????85 | ?????210554 | ????1.9 |
| ???2i | ??B(C 6F 5) 3 | Octadecanoic acid | ????3∶1 | ????10.5 | ????118 | ????75 | ?????164368 | ????1.7 |
| ???2j | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.5 | ????114 | ????88 | ?????211097 | ????1.7 |
| ???2k d | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????11 | ????114 | ????85 | ?????250034 | ????1.7 |
| ???2l d | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.5 | ????117 | ????88 | ?????279539 | ????2.1 |
| ???2m f | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10 | ????110 | ????20 | ?????272276 | ????1.7 |
| ???2n c | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.5 | ????115 | ????90 | ?????217317 | ????1.7 |
| ????2o | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.3 | ????130 | ????100 | ????161383 | ????4.8 |
| ????2p | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.3 | ????116 | ????100 | ????403245 | ????2.7 |
| ????2q a | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????11.8 | ????114 | ????100 | ????743333 | ????3.1 |
| ????2r b | ??B(C 6F 5) 3 | Octadecanoic acid | ????1.5∶1 | ????10.5 | ????120 | ????85 | ????218039 | ????1.9 |
| ????2s e | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????11.5 | ????114 | ????90 | ????267442 | ????1.9 |
| ????2t g | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????10.5 | ????114 | ????47 | ????320407 | ????1.5 |
| ????2u | ??B(C 6F 5) 3 | Octadecanoic acid | ????2∶1 | ????12 | ????130 | ????100 | ????209000 | ????1.5 |
A) T=-50 ℃; B) the 10 minutes reaction times; C) the 15 minutes reaction times; D) 40 micromole's Lewis acids; E) the 10 minutes reaction times, 40 micromole's Lewis acids; F) 20 micromole's Lewis acids; G) the 20 minutes reaction times.
Table 3-utilizes the copolyreaction test of various acid
Unless indicate in addition, all tests in 15 milliliters of methyl chloride, use 60 micromole's initiators to carry out, vacuum reaction is 1 hour under-30 ℃ bath temperature.
| Embodiment | Lewis acid | Activator | Lewis acid: activator | ?????IB ????(mL) | ?????IP ????(mg) | Transformation efficiency (%) | ??????Mw ????(g/mol) | ???MWD |
| ??3a | ????B(C 6F 5) 3 | Phenylformic acid | ????1.5∶1 | ????10.5 | ????120 | Trace | ????413152 | Bimodal |
| ??3b | ????B(C 6F 5) 3 | Phenylformic acid | ????2∶1 | ????10.5 | ????112 | ???” | ????199197 | ???1.5 |
| ??3c | ????B(C 6F 5) 3 | Thiobenzoic acid | ????1∶1 | ????11 | ????108 | ???12 | ????108161 | ???4.6 |
| ??3d | ????B(C 6F 5) 3 | Thiobenzoic acid | ????2∶1 | ????12 | ????130 | ???65 | ????165469 | ???2 |
| ??3e | ????B(C 6F 5) 3 | Pentafluorobenzoic acid | ????1∶1 | ????11 | ????122 | ???14 | ????188655 | ???6.5 |
| ??3f | ????B(C 6F 5) 3 | Pentafluorobenzoic acid | ????1∶1 | ????10 | ????111 | ???14 | ????225024 | ???1.7 |
| ??3g | ????B(C 6F 5) 3 | Pentafluorobenzoic acid | ????2∶1 | ????10 | ????105 | ???4 | ????230896 | ???1.6 |
| ??3h | ????B(C 6F 5) 3 | Pentafluorobenzoic acid | ????1∶1 | ????10 | ????117 | ???40 | ????272735 | ???2 |
| ??3I | ????B(C 6F 5) 3 | Pentafluorobenzoic acid | ????2∶1 | ????10.5 | ????125 | ???43 | ????235631 | ???2.2 |
| ??3j | ????B(C 6F 5) 3 | Trifluoroacetic acid | ????1∶1 | ????10 | ????120 | ???15 | ????38799 | ???302 |
| ??3k | ????B(C 6F 5) 3 | Trifluoroacetic acid | ????2∶1 | ????11 | ????120 | ???5 | ????41424 | ???3.5 |
| ??3l | ????B(C 6F 5) 3 | Trifluoroacetic acid | ????2∶1 | ????11 | ????120 | ???14 | ????109958 | ???3.1 |
| ??3m | ????- | Trifluoroacetic acid | ????10 | ????118 | ???0 | ????- | ???- | |
| ??3n | ????- | Trifluoroacetic acid | ????10 | ????124 | ???0 | ????- | ???- |
| ??3o | ????B(C 6F 5) 3 | Trifluoroacetic acid | ????2∶1 | ????12 | ????100 | ????100 | ????410000 | ????1.6 |
| ??3p | ????B(C 6F 5) 3 | Butyric acid | ????1∶1 | ????10 | ????118 | Trace | Low | |
| ??3q | ????B(C 6F 5) 3 | Butyric acid | ????2∶1 | ????9.5 | ????120 | ????82 | ????196301 | ????2.2 |
| ??3r | ????B(C 6F 5) 3 | Trimethylacetic acid | ????2∶1 | ????10.5 | ????100 | ????10 | ????51170 | ????3.8 |
| ??3s | ????B(C 6F 5) 3 | Trimethylacetic acid | ????2∶1 | ????11 | ????120 | ????8 | ????83570 | ????4.3 |
| ??3t | ????B(C 6F 5) 3 | 2 Ethylbutanoic acid | ????2∶1 | ????9.9 | ????122 | ????70 | ????129619 | ????1.95 |
| ??3u | ????B(C 6F 5) 3 | The 4-bromo-butyric acid | ????2∶1 | ????10.3 | ????120 | ????5.9 | ????94954 | ????1.90 |
| ??3v | ????B(C 6F 5) 3 | The 4-bromo-butyric acid | ????2∶1 | ????9.8 | ????119 | ????2.3 | ????54277 | ????3.26 |
| ??3w | ????B(C 6F 5) 3 | Hyptafluorobutyric acid | ????2∶1 | ????4.3 | ????119 | ????84 | ????9294 | ????1.82 |
| ??3x | ????B(C 6F 5) 3 | Hyptafluorobutyric acid | ????2∶1 | ????8.9 | ????118 | ????86 | ????14482 | ????2.06 |
| ??3y | ????B(C 6F 5) 3 | Hyptafluorobutyric acid | ????2∶1 | ????9.8 | ????128 | ????95 | ????19363 | ????2.31 |
The above results is supported following conclusion: the polymkeric substance that utilizes initiator system to carry out the isobutene polymerisation prepared in reaction under pressure below atmospheric pressure disclosed herein has high Mw, and does not have any transistion metal compound.Similarly, the The above results support is to draw a conclusion: with compare there not being to carry out under the condition of activator isobutene polymerisation reaction (or copolyreaction), the copolyreaction of carrying out iso-butylene/isoprene under simulated condition generates a kind of multipolymer with higher Mw sometimes.
The disclosed detailed experiment embodiment of the invention described above is implemented under pressure below atmospheric pressure.Do not plan to be bound to any specific theory, think that carrying out these reactions under pressure below atmospheric pressure causes reaction mixture refluxed, mixes better and have fabulous heat passage in mixture inside, therefore make the generation of " focus " and/or increase minimizedly, known described " focus " is disadvantageous.Therefore, any method (for example, reactor design is optimized in efficient cooling) that helps carrying out excellent heat transfer all is included among the present invention disclosed herein.
Claims (13)
1. the method for the alkene of a polymerization cationically polymerizable, it is included in initiator system and has the step of the alkene of at least a cationically polymerizable of polymerization down, and described initiator system comprises:
A) at least a Lewis acid with following formula:
(R
1R
2R
3)M
Wherein, M is selected from B, Al, Ga and In;
R
1, R
2And R
3Bridging or non-bridged, and be independently selected from the organic non-metal group that the halo carbon back of alkyl, halo carbon back and replacement of halide group, dialkyl group amido, alkoxide and aryl oxide group, alkyl and replacement and alkyl and halo carbon back replace;
And b) at least a activator, described activator is a proton source;
Condition is that described initiator system does not further contain transistion metal compound.
2. according to the process of claim 1 wherein that a R group is a halide group at the most.
3. according to the method for claim 2, wherein M is B.
4. according to the method for claim 2, wherein said proton source is selected from alcohol, mercaptan, carboxylic acid, thiocarboxylic acid.
5. according to the method for claim 2, wherein said being reflected under the pressure below atmospheric pressure carried out.
6. according to the method for claim 4, wherein the ratio range of coinitiator and boron compound is 0.01: 1-1: 1.
7. according to the method for claim 6, wherein the ratio range of coinitiator and boron compound is about 0.5: 1-1: 1.
8. according to the process of claim 1 wherein R
1, R
2And R
3Be independently selected from the aryl that contains 6-20 carbon atom or the aryl of replacement, and can interconnect by stable bridging group.
9. according to each method of claim 1-8, wherein R
1, R
2And R
3Be respectively C
6F
5Base.
10. according to the method for claim 2, wherein said coinitiator is a carboxylic acid.
11., wherein be reflected under the temperature that is higher than-100 ℃ and carry out according to each method of claim 1-10.
12. according to each method of claim 1 11, wherein pressure is lower than 100kPa.
13. according to each method of claim 1-12, wherein the alkene of at least a cationically polymerizable comprises the mixture of iso-butylene and isoprene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2360611 CA2360611C (en) | 2001-10-30 | 2001-10-30 | Transition metal-free initiator for the preparation of isobutylene-based polymers |
| CA2,360,611 | 2001-10-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1610705A true CN1610705A (en) | 2005-04-27 |
| CN1294162C CN1294162C (en) | 2007-01-10 |
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ID=4170386
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP2005507029A (en) |
| CN (1) | CN1294162C (en) |
| CA (1) | CA2360611C (en) |
| GB (1) | GB2397822B (en) |
| HK (1) | HK1077308A1 (en) |
| RU (1) | RU2308463C2 (en) |
| WO (1) | WO2003037940A1 (en) |
Cited By (1)
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| CN101602823B (en) * | 2008-06-13 | 2011-04-20 | 中国石油化工股份有限公司 | Cationic polymerization initiation system and application thereof |
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| US7893176B2 (en) * | 2007-03-23 | 2011-02-22 | Exxonmobil Chemical Patents Inc. | Polydispersity-controlled isoolefin polymerization with polymorphogenates |
| EP2930192A1 (en) * | 2014-04-11 | 2015-10-14 | LANXESS Deutschland GmbH | Initiator system for the production of synthetic rubbers |
| CN113490692B (en) | 2019-08-26 | 2023-03-28 | 株式会社Lg化学 | Catalyst composition and process for preparing hydrocarbon resin using the same |
| EP4095169A1 (en) * | 2021-05-26 | 2022-11-30 | ARLANXEO Canada Inc. | Substituted aluminum chlorides in the production of unsaturated isoolefin copolymers |
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|---|---|---|---|---|
| DE2328541C2 (en) * | 1973-06-05 | 1983-09-08 | Natalja Vasiljevna Ščerbakova | Process for the production of high molecular weight butyl rubber |
| CA1019095A (en) * | 1973-06-25 | 1977-10-11 | Lev N. Vladykin | Method for preparing butyl rubber |
| JPH01108203A (en) * | 1987-10-20 | 1989-04-25 | Toshinobu Higashimura | Manufacture of polyalkenyl ether |
| US4935576A (en) * | 1988-11-25 | 1990-06-19 | Exxon Chemical Patents Inc. | Polybutene process |
| DE4033195A1 (en) * | 1990-10-19 | 1992-04-23 | Basf Ag | METHOD FOR PRODUCING POLYISOBUTES |
| JPH10204111A (en) * | 1997-01-22 | 1998-08-04 | Nof Corp | Latent acid catalyst |
| EP1124865A1 (en) * | 1998-07-17 | 2001-08-22 | Bayer Inc. | Process for polymerizing cationically polymerizable olefin |
| CA2252295C (en) * | 1998-10-30 | 2007-07-17 | Bayer Inc. | Improved process for preparation of butyl rubber utilizing activated alkylaluminum halides |
| JP2000191714A (en) * | 1998-12-25 | 2000-07-11 | Bridgestone Corp | Catalyst for polymerization and production of isobutylene-styrene copolymer using the same |
| JP2000319312A (en) * | 1999-05-06 | 2000-11-21 | Maruzen Petrochem Co Ltd | Polymerization initiator for vinylphenol or vinylphenol derivative and polymerization method using the same |
| JP4040792B2 (en) * | 1999-06-01 | 2008-01-30 | 株式会社日本触媒 | Cationic polymerization method and catalyst used therefor |
| JP4843838B2 (en) * | 2000-09-07 | 2011-12-21 | 東ソー株式会社 | Cyclopentadiene random copolymer and process for producing the same |
-
2001
- 2001-10-30 CA CA 2360611 patent/CA2360611C/en not_active Expired - Fee Related
-
2002
- 2002-10-28 JP JP2003540220A patent/JP2005507029A/en active Pending
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- 2002-10-28 WO PCT/CA2002/001619 patent/WO2003037940A1/en active Application Filing
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| CN101602823B (en) * | 2008-06-13 | 2011-04-20 | 中国石油化工股份有限公司 | Cationic polymerization initiation system and application thereof |
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| Publication number | Publication date |
|---|---|
| RU2308463C2 (en) | 2007-10-20 |
| GB0411385D0 (en) | 2004-06-23 |
| HK1077308A1 (en) | 2006-02-10 |
| CA2360611C (en) | 2010-08-17 |
| CA2360611A1 (en) | 2003-04-30 |
| JP2005507029A (en) | 2005-03-10 |
| GB2397822B (en) | 2005-09-14 |
| GB2397822A (en) | 2004-08-04 |
| CN1294162C (en) | 2007-01-10 |
| WO2003037940A1 (en) | 2003-05-08 |
| RU2004116348A (en) | 2005-11-10 |
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