EP2545101A2 - Oligomères à fonction multi-amine et procédé de production desdits oligomères par réduction - Google Patents

Oligomères à fonction multi-amine et procédé de production desdits oligomères par réduction

Info

Publication number
EP2545101A2
EP2545101A2 EP11706826A EP11706826A EP2545101A2 EP 2545101 A2 EP2545101 A2 EP 2545101A2 EP 11706826 A EP11706826 A EP 11706826A EP 11706826 A EP11706826 A EP 11706826A EP 2545101 A2 EP2545101 A2 EP 2545101A2
Authority
EP
European Patent Office
Prior art keywords
oligomers
functional oligomers
pentyl
functional
amine
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.)
Withdrawn
Application number
EP11706826A
Other languages
German (de)
English (en)
Inventor
Christoph Gürtler
Thomas Ernst Müller
Ewa Gebauer
Henning Vogt
Yevgen Berezhanskyy
Burkhard KÖHLER
Walter Leitner
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.)
Covestro Deutschland AG
Original Assignee
Bayer Intellectual Property GmbH
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
Priority claimed from DE201010011350 external-priority patent/DE102010011350A1/de
Priority claimed from DE201010018785 external-priority patent/DE102010018785A1/de
Application filed by Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Publication of EP2545101A2 publication Critical patent/EP2545101A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/36—General preparatory processes using carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to multi-amine-functional oligomers which are accessible by free-radical copolymerization of carbon monoxide with olefins, subsequent reaction of the keto groups with hydroxylamine to give oximes and subsequent reduction to amines.
  • Multiamine functional oligomers are interesting reactants, e.g. for isocyanates or epoxides.
  • Molecules containing more than two amine groups are interesting crosslinkers that can be linked to three-dimensional networks along with amine-reactive compounds such as polyisocyanates or polyepoxides.
  • the primary amino groups can also be reacted with maleic acid esters to aspartic acid esters or with ketones or aldehydes to ketamines or aldimines.
  • the amine groups can be reacted with phosgene to form isocyanates.
  • These multiisocyanate-functional oligomers are also interesting polymer building blocks.
  • Jeffamines are polyoxyalkylene amines, polyethers that contain primary amine groups at the end of the polyether backbone.
  • the ether groups complicate a reaction with phosgene to form isocyanates, since the liberated HCl degrades the ether groups.
  • the ether groups are susceptible to photodegradation.
  • the object of the present invention was to synthesize multi-amine-functional oligomers which have a low content of secondary amino groups and which are advanced as little as possible by formation of secondary amino groups.
  • the oligomers to be hydrogenated can be obtained, for example, by free-radical copolymerization of carbon monoxide with olefins and subsequent reaction with hydroxylamine.
  • the invention relates to a process for the preparation of multi-amine-functional oligomers, characterized in that first
  • Carbon monoxide and at least one olefin are radically co-polymerized, the carbonyl groups of the resulting co-polymers are then reacted with hydroxylamine to multioxim- functional oligomers, and the multioximfunktionelle oligomers are then reduced to multi-amine functional oligomers.
  • the invention also provides a process for the preparation of multi-amine-functional Olig mers, characterized in that multioximfunktionelle oligomers are hydrogenated. Another object of the invention are obtainable by the two methods described multiamine-functional oligomers.
  • the invention also provides a process corresponding to the latter process, wherein the multioxime-functional oligomers to be used are compounds of the following formula 1:
  • R 1 Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH 3 C 6 H 4 or 4-CH 3 C 6 H 4 ,
  • R 2 H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH 3 C 6 H 4 or 4-CH 3 C 6 H 4 ,
  • multioxime functional oligomers also includes mixtures of oligomers of formula 1.
  • Another object of the invention are multi-amine-functional oligomers of the formula 2:
  • R 1 Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH 3 C 6 H 4 or 4-CH 3 C 6 H 4 ,
  • R 2 H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH 3 C 6 H 4 or 4-CH 3 C 6 H 4 ,
  • multi-amine functional oligomers also includes mixtures of oligomers of formula 2.
  • Higher terminal or internal olefins are e.g. 1-butene, 2-butene, butadiene, the isomers of pentene, hexene, heptene, octene, isooctene, nonene, decene, undecene, dodecene, higher terminal or internal alkenes, styrene, alpha-methylstyrene, 3- and 4-methylstyrene.
  • olefin mixtures comprising A) ethylene and
  • the copolymerization is initiated by radical initiators, such as azo compounds or peroxides, preferably azo compounds.
  • radical initiators such as azo compounds or peroxides, preferably azo compounds.
  • the copolymerization takes place at temperatures such that the half-life of the initiators used is in the range of 1 minute to 1 hour.
  • the reaction is preferably carried out at a temperature of 50 to 250 ° C, preferably at 70 to 180 ° C.
  • the reaction temperature depends on the decomposition temperature of the starter used and is at least above it.
  • the temperatures are when using 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile) preferably 30 to 140 ° C, with 2,2'-azobis (2.4 dimethyl valeronitrile) preferably 50 to 160 ° C, at 2,2'-azobis (2-methylbutyronitrile) preferably 70 to 180 ° C.
  • the temperatures are preferably 70 to 130 ° C.
  • the partial pressure of ethylene is preferably between 10 and 2000 bar, more preferably between 30 and 100 bar and the partial pressure of CO between 1 and 30% of the partial pressure of ethylene.
  • the copolymerization can be carried out in the presence or absence, preferably in the absence of solvents. Suitable solvents include tetrahydrofuran, methylcyclohexane or pentane.
  • the molecular weight can be adjusted by the amount of radical initiator used and / or by addition of a suitable regulator, such as hydrogen or mercaptans, and by suitable choice of reaction conditions, such as temperature and partial pressures.
  • a suitable regulator such as hydrogen or mercaptans
  • hydroxylamine is used in one to ten times molar amounts based on the carbonyl groups.
  • hydroxylamine is used as an aqueous solution or in bulk.
  • salts of hydroxylamine such as hydrochloride or sulfate
  • the reaction of the multicarbonyl-functional oligomers with hydroxylamine can be carried out in a two-phase mixture.
  • a biphasic mixture formed from the multicarbonyl-functional oligomer or a solution of the multicarbonyl-functional oligomer in an inert solvent such as benzene, toluene, chlorobenzene or chloroform and the aqueous hydroxylamine solution is used.
  • hydroxylamine-inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, dioxane, THF, DMF, NMP or dimethylacetamide can be used as a solubilizer.
  • the reaction is carried out at temperatures of 0 to 100 ° C, preferably 15 to 40 ° C.
  • the multifunctional oxime can be isolated by phase separation or / and distilling off the volatiles of the reaction mixture.
  • An object of the invention is also a process for the preparation of multioximfunktionieller oligomers, characterized in that by free radical copolymerization of carbon monoxide with ethylene and / or propylene and one or more higher terminal or internal olefins, such as 1-butene, 2-butene, butadiene, pentene , Hexene, heptene, octene, isooctene, nonene, decene, undecene, dodecene or higher terminal or internal alkenes, styrene, alpha-methylstyrene, 3- and 4-methylstyrene copolymers can be reacted with hydroxylamine to form multioxime functional oligomers.
  • olefins such as 1-butene, 2-butene, butadiene, pentene , Hexene, heptene, octene, isooctene, nonene, decen
  • An object of the invention are also available by this method multioximfunktionel- len oligomers.
  • the reduction of the multioxime-functional oligomers is carried out using a suitable reducing agent, preferably molecular hydrogen, using a selective homogeneous or heterogeneous hydrogenation catalyst.
  • the hydrogenation with hydrogen is carried out at temperatures of 20 to 200 ° C, preferably from 80 to 180 ° C, more preferably from 120 to 160 ° C, at pressures of 10 to 200 bar, preferably 10 to 100 bar, particularly preferably 10 to 50 bar in the presence of 0.1 to 20 wt .-% of hydrogenation catalysts, such as cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum.
  • the catalysts can be used as Raney catalysts or on suitable supports.
  • Raney cobalt Preference is given to using Raney cobalt, Raney nickel, supported cobalt, nickel or ruthenium catalysts.
  • support materials are particularly suitable carbon and oxides, such as silica, alumina, mixed oxides of silica and alumina and titanium oxide.
  • the hydrogenation is preferably carried out in the presence of ammonia, particularly preferably in equimolar amounts, based on oxime groups.
  • the hydrogenation can be carried out in the presence or absence of solvents.
  • Suitable solvents are THF, dioxane, or C 1 -C 4 alcohols.
  • Other reducing agents are alkali metals or their hydrides, alanates or boranates.
  • nitrile group-containing free-radical initiators such as azodiisobutyronitrile, or 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile) are used, incorporated into the polymer nitrile groups can also be reduced under the conditions of oxime reduction to primary amine groups, and contribute to the functionality of the inventive multi-amine oligomers. If alkene groups or aryl groups are contained in the multioxime-functional oligomers, these can also be reduced under the conditions of oxime reduction.
  • the multiamine-functional oligomers according to the invention have a molecular weight M n of 500 to 20,000, preferably of 800 to 8,000 g / mol.
  • the multi-amine functional oligomers contain at least 2, and on average 3 to 20 amine groups, preferably 3 to 10 amine groups.
  • the amine number, corresponding to the amount of KOH in mg equivalent to the amine content contained in one g substance, is 8 to 967, preferably 20 to 120.
  • the ratio of primary to secondary amine groups is at least 7: 3, preferably at least 9 : 1, more preferably at least 19: 1.
  • the multifunctional oximes to be used have a molecular weight M n of 500 to 20,000, preferably from 800 to 8,000 g / mol.
  • the multioxime-functional oligomers contain at least 2, and on average 3 to 20 oxime groups, preferably 3 to 10 oxime groups.
  • the oxime equivalent is 71 to 6700, preferably 500 to 2800 g / eq.
  • the multiamine-functional oligomers according to the invention are particularly suitable as reactants for isocyanates and epoxides, as starting materials for the phosgenation to form multi-isocyanate-functional oligomers and for the production of elastic coatings or moldings.
  • the secondary products with maleic acid dialkyl esters (polyaspartates) and with ketones or aldehydes (polyketamines or polyaldimines) are particularly suitable as reactants for polyisocyanates.
  • the invention therefore also relates to the use of the inventive multi-amine functional oligomers as reactants for isocyanates and epoxides, as starting materials for the phosgenation to form multi-isocyanate-functional oligomers and for the production of elastic coatings or moldings.
  • the determination of the CO content of the polyketones was carried out from the integration of the signals obtained in the corresponding 1H NMR spectrum.
  • the 1H NMR spectra were measured at 400 MHz in CDCl 3 with a Bruker AV400.
  • the 1H NMR signals of the polyketones were assigned as follows: ⁇ ⁇ 2.6 (COCt £ _2-Ct £ _2-CO, integral A), 2.4 (CO-CH (CH 2 ) > 2 , integral B), 1.7 (CO -CH 2 -CH ⁇ -CH 2 +
  • n (CH a 2 ) A / 2
  • n (CH a ' 2 ) B / 2
  • n (CH ali 2 ) D / 2
  • M n and M w were determined by gel permeation chromatography (GPC) on a SECurity GPC system from PSS Polymer Service against polystyrene standards (THF as eluent for polyketones and polyoximes, 0.1% DEAEA in THF for polyamines, flow rate 1.0 ml / min, columns : 2xPSS SDV linear S, 8x300 mm, 5 ⁇ ; RID detector; BHT as internal standard).
  • GPC gel permeation chromatography
  • Viscosities were determined with a MCR 51 rheometer from Anton Paar (measuring system: cone-plate principle, heating range 23-60 ° C, heating rate 0.1 ° C / s, shear rate 250 / s (constant), measuring cone: CP 25.1 (25 mm diameter ), Angle of the cone: 1 °).
  • the glass transition temperatures (Tg) were determined using a DSC Pyris 6 from Perkin Elmer. Heating method: (-70) ° C (3 min) - (+ 10) ° C / min - (+180) ° C - (-10) ° C / min - (-70) ° C (3 min) - ( +10) ° C / min - (+180) ° C.
  • Viscosity (23 ° C): mPa * s

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne des oligomères à fonction multi-amine et des oligomères à fonction multi-oxime ainsi qu'un procédé de production desdits oligomères par copolymérisation de supports carbonyle comme des oléfines ou des diènes, suivie d'une réaction avec de l'hydroxylamine et pour finir, d'une hydrogénation catalytique sélective.
EP11706826A 2010-03-12 2011-03-08 Oligomères à fonction multi-amine et procédé de production desdits oligomères par réduction Withdrawn EP2545101A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE201010011350 DE102010011350A1 (de) 2010-03-12 2010-03-12 Multiaminfunktionelle Oligomere und Verfahren zur Herstellung dieser durch Reduktion entsprechender Oxime
DE201010018785 DE102010018785A1 (de) 2010-04-29 2010-04-29 Multiaminfunktionelle Oligomere und Verfahren zur Herstellung dieser durch Reduktion entsprechender Oxime
PCT/EP2011/053411 WO2011110535A2 (fr) 2010-03-12 2011-03-08 Oligomères à fonction multi-amine et procédé de production desdits oligomères par réduction

Publications (1)

Publication Number Publication Date
EP2545101A2 true EP2545101A2 (fr) 2013-01-16

Family

ID=44563919

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11706826A Withdrawn EP2545101A2 (fr) 2010-03-12 2011-03-08 Oligomères à fonction multi-amine et procédé de production desdits oligomères par réduction

Country Status (5)

Country Link
US (1) US9200113B2 (fr)
EP (1) EP2545101A2 (fr)
JP (1) JP2013522381A (fr)
CN (1) CN102803343B (fr)
WO (1) WO2011110535A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013034532A1 (fr) * 2011-09-09 2013-03-14 Bayer Intellectual Property Gmbh Procede de préparation de polyamines
EP2778188A1 (fr) 2013-03-12 2014-09-17 Bayer MaterialScience AG Procédé de fabrication de terpolymères oléfine-CO

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US2495255A (en) * 1948-01-28 1950-01-24 Du Pont Polymeric polyamines
US2495286A (en) 1949-06-08 1950-01-24 Du Pont Interpolymers of carbon monoxide and method for preparing the same
US2595225A (en) * 1950-02-09 1952-05-06 Du Pont Polymeric poly-quaternary ammonium salts
US2846406A (en) 1954-05-15 1958-08-05 Bayer Ag Process for the production of polymeric amines and ammonium salts from olefin-carbonmonoxide polymers
US3069468A (en) * 1959-03-16 1962-12-18 Union Carbide Corp Diamino tricyclodecane
US3780140A (en) * 1971-08-06 1973-12-18 Du Pont Ethylene/carbon monoxide polymer compositions
EP0372602B1 (fr) * 1988-11-10 1996-04-10 Shell Internationale Researchmaatschappij B.V. Résines thermodurcissables
US5300690A (en) * 1992-10-14 1994-04-05 Akzo N.V. Polyoxime derived from carbon monoxide-propylene polyketone
JPH08215344A (ja) 1995-02-10 1996-08-27 Sumitomo Rubber Ind Ltd ゴルフボール
JPH1087573A (ja) * 1996-09-11 1998-04-07 Kuraray Co Ltd 一級ジアミンの製造法
DE19654058A1 (de) * 1996-12-23 1998-06-25 Basf Ag Polymere Polyamine aus alternierenden Polyketonen
US6541586B2 (en) 1999-01-19 2003-04-01 Exxonmobil Research And Engineering Company Polymerization processes for using dilute multicomponent feeds (LAW624)
DE19906019A1 (de) 1999-02-16 2000-08-17 Basf Ag Verfahren zur Herstellung von funktionalisierten alternierenden Kohlenmonoxidcopolymeren
US20020042475A1 (en) 2000-07-18 2002-04-11 Patil Abhimanyu Onkar Novel polyvinyl chloride resins
AU2001272999A1 (en) * 2000-07-18 2002-01-30 Exxonmobil Research And Engineering Company Olefin-carbon monoxide copolymers derived from synthesis gas
JP2009286820A (ja) * 2008-05-27 2009-12-10 Asahi Kasei E-Materials Corp 変性ポリケトン成形体、及び熱変性ポリケトン成形体

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Also Published As

Publication number Publication date
US9200113B2 (en) 2015-12-01
CN102803343A (zh) 2012-11-28
WO2011110535A3 (fr) 2011-12-22
US20130066112A1 (en) 2013-03-14
JP2013522381A (ja) 2013-06-13
WO2011110535A2 (fr) 2011-09-15
CN102803343B (zh) 2015-08-19

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