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WO2000073262A1 - Monomeres polymerisables olefiniquement insatures - Google Patents

Monomeres polymerisables olefiniquement insatures Download PDF

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Publication number
WO2000073262A1
WO2000073262A1 PCT/EP2000/004419 EP0004419W WO0073262A1 WO 2000073262 A1 WO2000073262 A1 WO 2000073262A1 EP 0004419 W EP0004419 W EP 0004419W WO 0073262 A1 WO0073262 A1 WO 0073262A1
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WO
WIPO (PCT)
Prior art keywords
monomers
general formula
integer
preparation
homopolymers
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.)
Ceased
Application number
PCT/EP2000/004419
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German (de)
English (en)
Inventor
Wolfgang Podszun
Rainer Neumann
Joachim Krüger
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.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AU53944/00A priority Critical patent/AU5394400A/en
Publication of WO2000073262A1 publication Critical patent/WO2000073262A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C275/24—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen

Definitions

  • the invention relates to new polymerizable, olefinically unsaturated monomers with basic groups of the general formula (I)
  • R 1 represents H or methyl
  • L j , L- 2 independently of one another represent alkylene with 1 to 6 C atoms
  • A represents oxygen or NR 3 ,
  • R 3 represents H or C, -C 4 alkyl
  • n stands for an integer from 0 to 10 and
  • R 2 represents NH 2 or a secondary or tertiary amino group or a 5- or 6-membered ring with at least one N atom
  • Anion exchangers as chromatography resins or as aids in medical diagnostics for the separation of nucleic acids.
  • Such polymers can be obtained, for example, from non-basic polymers by polymer-analogous reaction. be fathered. However, it is also possible to produce basic polymers directly by polymerizing basic monomers.
  • This monomer can be converted into water-soluble polymers by homo- or copolymerization.
  • the monomer is used to synthesize crosslinked spherical basic polymers, especially those with a high specific surface area
  • the invention relates to monomers of the general formula (I)
  • R 1 represents H or methyl
  • L j , 1_ 2 independently of one another represent alkylene with 1 to 6 C atoms
  • A represents oxygen or NR 3
  • R 3 represents H or C, -C 4 alkyl
  • n stands for an integer from 0 to 10 and
  • R 2 represents NH2 or a secondary or tertiary amino group or a 5- or 6-membered ring with at least one N atom.
  • the monomers according to the invention with basic groups according to the general formula (I) are particularly suitable for the preparation of anion exchangers which, in turn, can be used as chromatography resins or as aids in medical diagnostics for separating nucleic acids.
  • the invention therefore also relates to ion exchangers, in particular anion exchangers, which are prepared from the monomers of the general formula (I), and to their use as chromatography resins or as auxiliaries in medical diagnostics, in particular for separating nucleic acids.
  • the present invention relates to a method for separating nucleic acids, characterized in that anion exchangers constructed from monomers according to claim 1 are used.
  • Preferred monomers for the purposes of the present invention are monomers of the general formula (Ia)
  • L- 2 represents alkylene with 1 to 6 carbon atoms
  • A represents oxygen or NR 3 , R 3 for H or C ! -C 4 - alkyl
  • n stands for a 5 whole number from 0 to 10 and
  • R 2 represents NH 2 or a secondary or tertiary amino group or a 5- or 6-membered ring with at least one N atom.
  • Both Li in formula (I) and L 2 independently of one another, preferably represent divalent straight-chain or branched alkylene radicals having 1 to 6 carbon atoms.
  • the radical A is preferably oxygen, NH, or with a C1-C 4 - alkyl group substituted nitrogen.
  • n is an integer from 0 to 10, preferably from 0 to 6, particularly preferably from 0 to 4.
  • R 2 preferably denotes NH 2 or a secondary or tertiary amino group or a 5- or 6-membered ring with at least one N atom.
  • R 2 particularly preferably represents a radical from the series NH 2 , methylamino, dimethylamino, ethylamino,
  • Diethylamino Hydroxyethylamino, bis (hydroxyethyl) amino, propylamino, dipropylamino, bis (hydroxypropyl) amino, n-butylamino or tert-butylamino, N-imidazolyl, methylimidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyridazinyl, Pyrimidyl, pyrazolyl, N-piperidyl, oxazolyl, isoxazolyl, triazolyl. Also preferred for the purposes of the present invention are monomers of the general formula (Ib)
  • R 4 represents a radical of the series H, methyl, ethyl or 2-hydroxyethyl.
  • n stands for an integer from 0 to 6.
  • the present invention further relates to a process for the preparation of the monomers of the general formulas (I), (Ia), (Ib), (Ic) or (Id) according to the invention by stoichiometric conversion of hydroxyl or amine compounds according to the general formula (II)
  • R i and L j have the meanings given above.
  • Said reaction of the hydroxyl or amine compounds according to the general formula (II) with isocyanates of the general formula (III) is preferably carried out in an inert solvent in the presence of a catalyst at temperatures of, for example, from -20 ° C. to 60 ° C.
  • inert solvents which may be mentioned are acetone, 2-butanone, tetrahydrofuran, methylene chloride, chloroform, toluene and acetonitrile.
  • catalysts which can be used in the process according to the invention are metal salts higher fatty acids, such as dibutyltin laurate, triaryl compounds such as triphenylstibine or triphenylphosphate, or tertiary amines such as triethylamine.
  • the catalysts are usually used in amounts of 50 to 5000 ppm, based on the starting materials.
  • a polymerization inhibitor is added to the monomers according to the invention during the synthesis.
  • Suitable polymerization inhibitors are, for example, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol or 2,6-di-octadecyl-4-methylphenol.
  • the amount of inhibitor used is 5 to 1000 ppm, preferably 10 to 500 ppm, based on the monomer.
  • the monomers according to the invention can be converted into copolymers by polymerization in homopolymers or in a mixture with comonomers.
  • crosslinked polymers from the monomers according to the invention are polymerized in a mixture with multifunctional, olefinically unsaturated monomers as crosslinkers.
  • a very suitable crosslinker is, for example, divinylbenzene.
  • radical formers are, for example, peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (p-chlorobenzoyl peroxide), dicyclohexyl peroxidicarbonate, tert.-butyl peroctoate, 2,5-bis (2-ethylhexanoyl peroxy) -2,5-dimethylhexane or tert.-amylperox 2-ethylhexane, further azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (2-methylisobutyronitrile).
  • peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (p-chlorobenzoyl peroxide), dicyclohexyl peroxidicarbonate, tert.-butyl peroctoate, 2,5-bis (2-
  • the radical formers are generally used in amounts of 0.05 to 2.5% by weight, preferably 0.2 to 1.5% by weight, based on the monomer or on the monomer mixture.
  • the monomers according to the invention are particularly suitable for the preparation of bead polymers, in particular for the preparation of macroporous bead polymers by the suspension polymerization procedure.
  • suspension polymerization is understood to mean a process in which a monomer or a monomer-containing mixture which contains an initiator soluble in the monomer (s) in a phase which is essentially immiscible with the monomer (s), preferably in an aqueous phase, the one Contains dispersant, is divided into droplets and is cured by increasing the temperature with stirring. Further details of suspension polymerization are described, for example, in H. Green's "Polymerization Processes", in: Ullmanns Encyclopedia of Industrial Chemistry, Vol. A21, 5th ed. (B. Elvers, S. Hawkins, G. Schulz, ed.), VCH, Weinheim 1992, pp. 363-373.
  • Porogens are liquid, water-immiscible compounds that dissolve the monomers used and precipitate the polymer that is formed. Examples include aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, isododecane and alcohols such as octanol.
  • the porogen is used in amounts of 10 to 150% by weight, preferably 20 to 100% by weight, based on the sum of the monomers and crosslinking agents used.
  • DMAE dimethylaminoethanol
  • EO ethylene oxide
  • 2031 g of a colored viscous mixture of ethylene oxide-extended dimethylaminoethanol were obtained.
  • the mixture was then purified by distillation over a 1.5 m long silver-jacketed column with a column top in a high vacuum at a bath temperature of 70 to 240 ° C. 3 fractions with constant boiling points were obtained.
  • SP 112 WS (H-Form) ® was filled. After the products had been applied, they were rinsed with 2 l of deionized water. The column was then eluted with 1.5 1 6.5% ammonia solution. The eluate running off was collected and then concentrated on a rotary evaporator at 55 ° C. and 15 mbar. About 12 g of purified fractions 1 to 3 were obtained.
  • Example 3 was repeated using 12 g of purified fraction 2 from Example 2 and 13.63 g of 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate. 24.2 g of monomer 3 from Table 1 were obtained.
  • Example 3 was repeated, using 12 g of purified fraction 3 from Example 2 and 10.91 g of 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate. 21.6 g of monomer 4 from Table 1 were obtained.
  • a solution of 42.5 g of polyvinyl alcohol (Moviol 40-88®) and 12.75 g of disodium hydrogen sulfate in 1240 g of deionized water was placed in a 2 liter reaction vessel with a blade stirrer, reflux condenser, thermometer, gas inlet and gas outlet tube.
  • An organic solution of 23.71 g of monomer from Example 1, 13.04 g of styrene, 10.67 g of divinylbenzene, 0.71 g of 2,2'- was added to this aqueous solution at 20 ° C. while stirring at 280 revolutions per minute.
  • Azobis (2,4-dimethylvaleronitrile) and 35 g of hexane were added within 30 minutes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des monomères polymérisables oléfiniquement insaturés contenant des groupes basiques, de formule générale (I) dans laquelle: R<1> est H ou méthyle; L1 et L2 sont indépendamment l'un de l'autre des alkyles contenant 1 à 6 atomes de C; A est oxygène ou N-R<3>; R<3> est H ou un alkyle en C1-C4; n est un nombre entier compris entre 0 et 10; et R<2> est NH2 ou un groupe amino secondaire ou tertiaire ou un composé cyclique à 5 ou 6 éléments contenant au moins un atome de N. Cette invention concerne également un procédé de préparation de ces monomères ainsi que les polymères qu'ils permettent de constituer.
PCT/EP2000/004419 1999-05-29 2000-05-16 Monomeres polymerisables olefiniquement insatures Ceased WO2000073262A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53944/00A AU5394400A (en) 1999-05-29 2000-05-16 Polymerizable, olefinically unsaturated monomers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999124790 DE19924790A1 (de) 1999-05-29 1999-05-29 Polymerisierbare, olefinisch ungesättigte Monomere
DE19924790.0 1999-05-29

Publications (1)

Publication Number Publication Date
WO2000073262A1 true WO2000073262A1 (fr) 2000-12-07

Family

ID=7909688

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/004419 Ceased WO2000073262A1 (fr) 1999-05-29 2000-05-16 Monomeres polymerisables olefiniquement insatures

Country Status (3)

Country Link
AU (1) AU5394400A (fr)
DE (1) DE19924790A1 (fr)
WO (1) WO2000073262A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4429096A (en) * 1983-06-01 1984-01-31 American Cyanamid Company Quaternary amine carbamate or urea compounds based on isopropenyl-α,α-dimethylbenzyl isocyanate
US4990575A (en) * 1989-09-20 1991-02-05 Texaco Chemical Co. Novel olefin-terminated ureas from polyoxyalkylene amines and isocyanates
WO1991012282A1 (fr) * 1990-02-14 1991-08-22 H.B. Fuller Licensing & Financing Inc. Copolymeres avec action anti-microbienne inherente
WO1991012243A2 (fr) * 1990-02-14 1991-08-22 H.B. Fuller Licensing & Financing Inc. Monomere d'imidazolidinone copolymerisable
US5094765A (en) * 1990-04-30 1992-03-10 Texaco Inc. Lubricating oil composition
WO1992012965A1 (fr) * 1991-01-22 1992-08-06 Ppg Industries, Inc. Composes d'aziridine, polymeres acryliques contenant lesdits composes et compositions de revetement contenant lesdits polymeres
WO1992013907A1 (fr) * 1991-02-07 1992-08-20 H.B. Fuller Lincensing & Financing Inc. Composition a base d'isocyanate a empechement sterique et a base d'oxazolidine, durcissable et thermiquement stable
US5319101A (en) * 1990-04-30 1994-06-07 The B. F. Goodrich Company Reactive imide monomers and radiation curable polymers derived therefrom
US5334310A (en) * 1991-10-21 1994-08-02 Cornell Research Foundation, Inc. Column with macroporous polymer media
US5693702A (en) * 1996-02-16 1997-12-02 Westvaco Corporation Rosin-supported urea- and urethane-modified emulsion polymers

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4429096A (en) * 1983-06-01 1984-01-31 American Cyanamid Company Quaternary amine carbamate or urea compounds based on isopropenyl-α,α-dimethylbenzyl isocyanate
US4990575A (en) * 1989-09-20 1991-02-05 Texaco Chemical Co. Novel olefin-terminated ureas from polyoxyalkylene amines and isocyanates
WO1991012282A1 (fr) * 1990-02-14 1991-08-22 H.B. Fuller Licensing & Financing Inc. Copolymeres avec action anti-microbienne inherente
WO1991012243A2 (fr) * 1990-02-14 1991-08-22 H.B. Fuller Licensing & Financing Inc. Monomere d'imidazolidinone copolymerisable
US5094765A (en) * 1990-04-30 1992-03-10 Texaco Inc. Lubricating oil composition
US5319101A (en) * 1990-04-30 1994-06-07 The B. F. Goodrich Company Reactive imide monomers and radiation curable polymers derived therefrom
WO1992012965A1 (fr) * 1991-01-22 1992-08-06 Ppg Industries, Inc. Composes d'aziridine, polymeres acryliques contenant lesdits composes et compositions de revetement contenant lesdits polymeres
WO1992013907A1 (fr) * 1991-02-07 1992-08-20 H.B. Fuller Lincensing & Financing Inc. Composition a base d'isocyanate a empechement sterique et a base d'oxazolidine, durcissable et thermiquement stable
US5334310A (en) * 1991-10-21 1994-08-02 Cornell Research Foundation, Inc. Column with macroporous polymer media
US5693702A (en) * 1996-02-16 1997-12-02 Westvaco Corporation Rosin-supported urea- and urethane-modified emulsion polymers

Also Published As

Publication number Publication date
AU5394400A (en) 2000-12-18
DE19924790A1 (de) 2000-11-30

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