DD247455A1 - PROCESS FOR PREPARING POLYMERS WITH FUNCTIONAL END GROUPS - Google Patents
PROCESS FOR PREPARING POLYMERS WITH FUNCTIONAL END GROUPS Download PDFInfo
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- DD247455A1 DD247455A1 DD28852986A DD28852986A DD247455A1 DD 247455 A1 DD247455 A1 DD 247455A1 DD 28852986 A DD28852986 A DD 28852986A DD 28852986 A DD28852986 A DD 28852986A DD 247455 A1 DD247455 A1 DD 247455A1
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- German Democratic Republic
- Prior art keywords
- lithium
- primary amino
- end groups
- polymers
- polymerization
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- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000007822 coupling agent Substances 0.000 claims abstract description 4
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 4
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims abstract description 4
- SEGOZRIBJLSKOO-UHFFFAOYSA-N n-phenylmethanesulfinamide Chemical compound CS(=O)NC1=CC=CC=C1 SEGOZRIBJLSKOO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 3
- 230000008878 coupling Effects 0.000 claims abstract description 3
- 238000010168 coupling process Methods 0.000 claims abstract description 3
- 125000001979 organolithium group Chemical group 0.000 claims abstract 2
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 4
- 238000006698 hydrazinolysis reaction Methods 0.000 abstract description 4
- QQXVZGWCVOCPDR-UHFFFAOYSA-N 4-ethylisoindole-1,3-dione Chemical compound CCC1=CC=CC2=C1C(=O)NC2=O QQXVZGWCVOCPDR-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920006250 telechelic polymer Polymers 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 1
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene 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
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung von Polymeren mit funktionellen Endgruppen, insbesondere mit primaeren Aminoendgruppen, durch anionische Polymerisation von konjugierten Dienen und/oder vinylaromatischen Monomeren mit lithiumorganischen Initiatoren, die eine geschuetzte funktionelle Gruppe enthalten. Als Initiator wird Lithium-N,N-bis(trimethylsilyl)amid, p-Lithiummethyl-sulfinylanilin oder 2-Lithiumethyl-phthalimid verwendet. Nach Funktionalisierung der lebenden Polymeren mit elektrophilen Reagenzien bzw. Kupplung mit bi- oder mehrfunktionellen Kupplungsmitteln ist eine Freisetzung der primaeren Aminogruppen durch Hydrolyse mit Wasser oder durch Hydrazinolyse moeglich.The invention relates to a process for the preparation of polymers having functional end groups, in particular with primary amino end groups, by anionic polymerization of conjugated dienes and / or vinylaromatic monomers with organolithium initiators which contain a protected functional group. The initiator used is lithium N, N-bis (trimethylsilyl) amide, p-lithium methylsulfinylaniline or 2-lithium ethyl-phthalimide. After functionalization of the living polymers with electrophilic reagents or coupling with bi- or polyfunctional coupling agents, a release of the primary amino groups by hydrolysis with water or by hydrazinolysis is possible.
Description
Li - GH2 - CH2 - FLi - GH 2 - CH 2 - F
C ·——C · -
i! 0i! 0
durchgeführt wird und die Freisetzung der primären Aminogrüppe nach der Funktionalisierungs- bzw. Kupplungsreaktion durch Hydrolyse mit Wasser oder durch Hydrazinolyse erfolgt.is carried out and the release of the primary amino group after the functionalization or coupling reaction by hydrolysis with water or by hydrazinolysis.
Die Erfindung ist anwendbar zur Herstellung von Polymeren, die eine oder mehrere primäre Aminogruppen enthalten, durch anionische Polymerisation. Diese Polymeren sind als makromolekulare Initiatoren für die Polymerisation von Aminosäuren, als Präpolymere für die Polyurethansynthese, als hochmolekulare Vernetzungsmittel für Epoxidharze und zur Herstellung von Blockcopolymeren, z. B. Nylon-, Harnstoff-Aldehyd-, Epoxid-, Urethan- und Imid-Blockcopolymere, verwendbar.The invention is applicable to the preparation of polymers containing one or more primary amino groups by anionic polymerization. These polymers are useful as macromolecular initiators for the polymerization of amino acids, as prepolymers for polyurethane synthesis, as high molecular weight crosslinking agents for epoxy resins, and for the preparation of block copolymers, e.g. Nylon, urea-aldehyde, epoxide, urethane and imide block copolymers.
Aus der US-PS 4015061 ist bekannt, daß telechelische Polymere, die mindestens eine primäre Aminogrüppe enthalten, durch anionische Polymerisation von Diolefinen mit einem Lithiuminitiator, der eine durch Trialkylsilylsubstituenten geschützte Aminogrüppe enthält, hergestellt werden können. Als Initiator wird ein p-Lithium-N,N-bis(trialkylsilyl)arylamin, vorzugsweise p-Lithium-N,N-bis(trimethyisilyl)anilin, in Diethylether verwendet. Die resultierenden Polymere enthalten an einem Kettenende eine geschützte Aminogrüppe und am anderen Kettenende ein Lithiumatom. Durch Umsetzung mit einem bifunktionellen Kupplungsmittel sind Polymere darstellbar, die an jedem Kettenende eine geschützte Aminogrüppe tragen. Zur Freisetzung der primären Aminogruppen muß das p-N,N-bis(trimethylsilyl)aminophenyl-terminierte Polymere einer sauren Hydrolyse unterworfen werden, d.h. die Lösung des Polymeren muß mehrere Stunden mit einer wäßrigen Säure unter Rückfluß behandelt werden.From US-PS 4015061 it is known that telechelic polymers containing at least one primary amino group can be prepared by anionic polymerization of diolefins with a lithium initiator containing an amino group protected by trialkylsilyl substituents. The initiator used is a p-lithium-N, N-bis (trialkylsilyl) arylamine, preferably p-lithium-N, N-bis (trimethylsilyl) aniline, in diethyl ether. The resulting polymers contain a protected amino group at one end of the chain and a lithium atom at the other end of the chain. By reaction with a bifunctional coupling agent, polymers can be prepared which carry a protected amino group at each end of the chain. To release the primary amino groups, the p-N, N-bis (trimethylsilyl) aminophenyl-terminated polymer must be subjected to acid hydrolysis, i. the solution of the polymer has to be refluxed for several hours with an aqueous acid.
Nach diesem Verfahren sind nur Polymere mit aromatischen primären Aminoendgruppen darstellbar. Nachteilig ist die zur Freisetzung der primären Aminogrüppe notwendige saure Hydrolyse, da sie lange Reaktionszeiten erfordert und aufgrund von Salzbildung der Aminogrüppe zur Ausfällung des Polymeren führen kann. Es muß deshalb in jedem Fall eine Neutralisation der Säure durchgeführt werden.Only polymers with aromatic primary amino end groups can be prepared by this process. A disadvantage is the acidic hydrolysis necessary for the release of the primary amino group, since it requires long reaction times and can lead to precipitation of the polymer due to salt formation of the amino group. It must therefore be carried out in any case neutralization of the acid.
Ziel der Erfindung- K Object of the invention - K
Ziel der Erfindung ist es, ein ökonomisches und rationelles Verfahren zur Herstellung von Homo- und Copolymeren konjugierter Diene mitfunktionellen Endgruppen, insbesondere mit primären Aminogruppen, zu entwickeln.The aim of the invention is to develop an economical and rational process for the preparation of homopolymers and copolymers of conjugated dienes with functional end groups, in particular with primary amino groups.
Der Erfindung liegt die Aufgabe zugrunde, 1,3-Dienhomo- und -copolymere mit funktioneilen Endgruppen, insbesondere mit primären Aminogruppen, durch anionische Polymerisation mittels solcher Lithiuminitiatoren herzustellen, die eine geschützte Amiriogruppe enthalten, wobei die Freisetzung der primären Aminogruppe nach der Polymerisation durch Hydrolyse mit Wasser oder durch Hydrazinolyse möglich sein soll.The invention has for its object to produce 1,3-diene homo- and copolymers with functional end groups, especially with primary amino groups, by anionic polymerization by means of such lithium initiators containing a protected Amiroiogruppe, wherein the release of the primary amino group after the polymerization by hydrolysis should be possible with water or by hydrazinolysis.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß anionisch polymerisierbare Monomere mit Hilfe vonThe object is achieved in that anionically polymerizable monomers with the aid of
(I) Lithium-N,N-bis(trimethylsilyl)amid ' . (I) Lithium N, N-bis (trimethylsilyl) amide '.
Li-N-(Si(CH3)3)2,Li-N- (Si (CH 3 ) 3 ) 2,
(II) p-Lithiummethyl-sulfinylanilin Li-CH2-C6H4-N=S=O(II) p-Lithium methylsulfinylaniline Li-CH 2 -C 6 H 4 -N = S = O
(III) 2-Lithiumethyl-phthalimid(III) 2-Lithium ethyl phthalimide
als Initiatoren in lebende Dienhomo- oder -copolymere überführt werden, die an einem Kettenende eine C-Li-Gruppe und am anderen Kettenende die aus dem Initiator resultierende geschützte Aminogruppe enthalten.are converted as initiators into living diene homo- or copolymers containing at one end of a chain a C-Li group and at the other chain end the protected amino group resulting from the initiator.
Die erfindungsgemäß einzusetzenden Initiatoren liegen als Lösung in einem Ether, z. B. Diethylether, Methyl-tert.butylether, Tetrahydrofuran oder Dioxan vor.The inventively used initiators are as a solution in an ether, for. As diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane before.
Die Monomeren, die in Gegenwart dieser Initiatoren polymerisiert werden können, sind konjugierte Diene, wie 1,3-Butadien oder Isopren, und/oder vinylsubstituierte aromatische Verbindungen, wie Styren, alpha-Methylstyren oder Divinylbenzen. Die Polymerisation wird unter solchen Bedingungen durchgeführt, wie sie für die anionische Lösungspolymerisation mit alkalimetallorganischen Initiatoren bekannt sind.The monomers that can be polymerized in the presence of these initiators are conjugated dienes, such as 1,3-butadiene or isoprene, and / or vinyl-substituted aromatic compounds, such as styrene, alpha-methylstyrene, or divinylbenzene. The polymerization is carried out under conditions known for anionic solution polymerization with alkali metal organic initiators.
Als Lösungsmittel eignen sich aliphatische, cycloaliphatische und aromatische Kohlenwasserstoffe, wie Benzen, Toluen, η-Hexan, n-Heptan, Benzinfraktionen oder Cyclohexan, sowie lineare oder cyclische Ether, wie Diethylether, Methyltert.butylether, Tetrahydrofuran oder Dioxan. VSuitable solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons, such as benzene, toluene, η-hexane, n-heptane, gasoline fractions or cyclohexane, and linear or cyclic ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane. V
Die Polymerisationstemperatur beträgt 203 bis 423 K, vorzugsweise 273 bis 323 K.The polymerization temperature is 203 to 423 K, preferably 273 to 323 K.
Die aktiven Kettenenden der resultierenden lebenden Polymeren können in bekannter Weise mit endgruppenbildenden, efektrophilen Reagenzien, wie Kohlendioxid, Alkylenoxide, Epichlorhydrin oder gamma-Butyrolacton, umgesetzt werden, so daßtelechelische Polymere mit einer Aminogruppe und einer beliebigen anderen Endgruppe darstellbar sind. Die lebenden Polymeren können aber auch mit bi- oder mehrfunktionellen Kupplungsmitteln, wie organische Dihalogenide oder SiCI4, behandelt werden, so daß Polymere mit zwei oder mehr primären Aminogruppen resultieren.The active chain ends of the resulting living polymers can be reacted in a known manner with end group-forming, efectrophilic reagents such as carbon dioxide, alkylene oxides, epichlorohydrin or gamma-butyrolactone, so that telechelic polymers having an amino group and any other end groups can be prepared. However, the living polymers can also be treated with bi- or polyfunctional coupling agents, such as organic dihalides or SiCl 4 , so that polymers with two or more primary amino groups result.
Nach der Funktionalisierungs- bzw. Kupplungsreaktion erfolgt die Freisetzung der primären Aminoendgruppe durch Hydrolyse mit Wasser oder durch Hydrazinolyse mit Hydrazin oder Hydrazinsulfat und Salzsäure.After the functionalization or coupling reaction, the primary amino end group is released by hydrolysis with water or by hydrazinolysis with hydrazine or hydrazine sulfate and hydrochloric acid.
Die angeführten Beispiele sollen das erfindungsgemäße Verfahren erläutern, ohne es dadurch in irgendeiner Weise einzuschränken.The examples given are intended to illustrate the process according to the invention without thereby restricting it in any way.
40mmol Lithium-N,N-bis(trimethylsilyl)amid, gelöst in 100 ml Diethylether, werden unter Argonatmosphäre mit 250 ml Cyclohexan verdünnt. Zu dieser Lösung werden innerhalb 1 Stunde 80g Butadien bei 308K zudosiert. Anschließend wird noch 0,5 Stunden gerührt und dann die Polymerisation mit 44mmol Ethylenoxid abgebrochen. Die Polymerlösung wird mit 50 ml Wasser hydrolysiert, die wäßrige Phase abgetrennt und das Lösungsmittel im Vakuumrotationsverdampfer entfernt. Man erhält in 100%iger Ausbeute ein flüssiges Polybutadien mit einer mittleren Molmasse Mn von 2050g/mol. Die Bestimmung der primären Aminogruppe erfolgte durch Umsetzung mit 1-Fluor-2,4-dinitrobenzen und anschließender Colorimetrie und ergab eine Funktionalität von 0,9840 mmol of lithium N, N-bis (trimethylsilyl) amide, dissolved in 100 ml of diethyl ether, are diluted under argon atmosphere with 250 ml of cyclohexane. 80 g of butadiene are added to this solution at 308K within 1 hour. The mixture is then stirred for 0.5 hours and then stopped the polymerization with 44mmol ethylene oxide. The polymer solution is hydrolyzed with 50 ml of water, the aqueous phase separated and the solvent removed in a vacuum rotary evaporator. A liquid polybutadiene having an average molecular weight M n of 2050 g / mol is obtained in 100% yield. The determination of the primary amino group was carried out by reaction with 1-fluoro-2,4-dinitrobenzene and subsequent colorimetry and gave a functionality of 0.98
Die durch NMR-Spektroskopie ermittelte OH-Funktionalität beträgt 0,96. The OH functionality determined by NMR spectroscopy is 0.96.
Zu einer Lösung von lOOmmol p-Lithiummethyl-sulfinylanilin (Initiator II) in 150 ml Tetrahydrofuran werden unter Argon 400 ml Benzen hinzugefügt und zu dieser Initiatorlösung 150g Isopren unter Rühren bei 278K innerhalb von 1,5 Stunden zugetropft.400 ml of benzene are added to a solution of 100 mmol of p-lithium methylsulfinylaniline (initiator II) in 150 ml of tetrahydrofuran under argon, and 150 g of isoprene are added dropwise to this initiator solution with stirring at 278K over a period of 1.5 hours.
Nach beendeter Polymerisation werden 52mmol Dibromethan zur Kupplung des lebenden Polymeren zugesetzt. Die Hydrolyse der Endgruppen erfolgt mit 100ml Wasser. Das Polymere wird mit Methanol ausgefällt und anschließend im Vakuum bei 323 K getrocknet.After the polymerization has ended, 52 mmol of dibromoethane are added for coupling the living polymer. The hydrolysis of the end groups is carried out with 100 ml of water. The polymer is precipitated with methanol and then dried in vacuo at 323 K.
Das isolierte Polyisopren weist eine mittlere Mol masse von 3050 und eine Funktionalität für primäre Aminogruppen von 1,98 auf.The isolated polyisoprene has an average molecular weight of 3050 and a functionality for primary amino groups of 1.98.
Die theoretische Molmasse beträgt 3060.The theoretical molecular weight is 3060.
Claims (2)
Li-N-(Si(CH3W2,(I) Lithium N, N-bis (trimethylsilyl) amide
Li-N- (Si (CH 3 W 2 ,
Li-CH2-C6H4-N =S=0(II) p-Lithium methylsulfinylaniline
Li-CH 2 -C 6 H 4 -N = S = 0
U0
U
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD28852986A DD247455A1 (en) | 1986-03-31 | 1986-03-31 | PROCESS FOR PREPARING POLYMERS WITH FUNCTIONAL END GROUPS |
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| DD28852986A DD247455A1 (en) | 1986-03-31 | 1986-03-31 | PROCESS FOR PREPARING POLYMERS WITH FUNCTIONAL END GROUPS |
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| DD247455A1 true DD247455A1 (en) | 1987-07-08 |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5238893A (en) * | 1991-12-30 | 1993-08-24 | Bridgestone Corporation | Method of preparing an anionic polymerization initiator |
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| US5574109A (en) * | 1995-02-01 | 1996-11-12 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
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| US5932662A (en) * | 1995-02-01 | 1999-08-03 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
| US6080835A (en) * | 1995-02-01 | 2000-06-27 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
| US6349753B1 (en) | 1995-02-01 | 2002-02-26 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
| US7196141B2 (en) | 1998-08-20 | 2007-03-27 | Kaneka Corporation | Polymer and epoxy resin compositions |
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