WO2004013207A1 - Amine de polymethylene, son procede de production et son utilisation - Google Patents

Amine de polymethylene, son procede de production et son utilisation Download PDF

Info

Publication number
WO2004013207A1
WO2004013207A1 PCT/EP2003/007682 EP0307682W WO2004013207A1 WO 2004013207 A1 WO2004013207 A1 WO 2004013207A1 EP 0307682 W EP0307682 W EP 0307682W WO 2004013207 A1 WO2004013207 A1 WO 2004013207A1
Authority
WO
WIPO (PCT)
Prior art keywords
branched
groups
linear
substituted
optionally
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/EP2003/007682
Other languages
German (de)
English (en)
Inventor
Rainer Dyllick-Brenzinger
Ulrich Steuerle
Volker Braig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AU2003250069A priority Critical patent/AU2003250069A1/en
Publication of WO2004013207A1 publication Critical patent/WO2004013207A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F34/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • the present invention relates to polymethylene amine, a process for its production and its use.
  • Cationic polymers with high charge densities are mainly used in the paper industry. They often serve as fixatives, drainage agents, flocculants and / or retention agents and are added to the paper pulp before or during its manufacture. As a retention agent, they reduce the entrainment of the fibers and fillers that form the paper pulp (retention) when the solids are separated from the water. The yield of the solid / liquid separation is thus improved by these retention agents. Wood pulp, thermo-mechanical material, chemo-thermo-mechanical material, pressure sanding as well as sulphite and sulphate pulp in short and long-fiber form, if necessary also, are basically used as raw material components for the production of paper
  • Suitable fillers are, for example, clay, kaolin, precipitated and natural, ground chalk, talc, titanium dioxide, calcium sulfate, barium sulfate, aluminum oxide and satin white, as well as mixtures of the fillers mentioned.
  • Typical cationic polymers that are used as retention or fixing agents are, for example, cationic polyacrylamide (cPAM) polyethyleneimine (PEI), poly-diallyldimethylammonium chloride (poly-DADMAC) and polyvinylamine (PVAm).
  • cPAM cationic polyacrylamide
  • PEI polyethyleneimine
  • poly-DADMAC poly-diallyldimethylammonium chloride
  • PVAm polyvinylamine
  • Polymers containing vinylamine units are known, cf. US-A-4,421,602, US-A-5, 334, 287, EP-A-0 216 387, US-A-5, 981, 689, WO-A-00/63295 and US-A-6, 121, 409. They are prepared by hydrolysis of open-chain polymers containing N-vinylcarboxamide units. These polymers are e.g. B. available by polymerizing N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide and N-vinyl propionamide. The monomers mentioned can be polymerized either alone or together with other monomers.
  • the monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms, vinyl ethers such as C ⁇ to C 6 -alkyl vinyl ether and esters, amides and nitriles of ethylenically unsaturated C 3 - to C ß- carboxylic acids.
  • carboxylic acid esters of unsaturated carboxylic acids are derived from glycols or polyalkylene glycols, in each of which only one OH group is esterified, and acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000 are also suitable.
  • Other suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols.
  • the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form.
  • Suitable comonomers are amides of ethylenically unsaturated carboxylic acids, such as acrylamide, methacrylamide and N-alkylmono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, and basic (meth) acrylamides.
  • comonomers are dimethylaminoalkyl (meth) acrylate CH 3 Cl, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles.
  • polyethyleneimines which can be prepared, for example, by polymerizing ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids as a catalyst.
  • Polyethyleneimines have molar masses of up to 50,000; after further crosslinking measures, molasses of up to 2 million, preferably from 200 to 1,000,000, can be achieved.
  • Polyethyleneimines with molecular weights of> 1,000,000, which are obtainable by ultrafiltration, are particularly preferably used.
  • the polyethyleneimines can optionally be modified, e.g. B. alkoxylated, alkylated or amidated. They can also be subjected to Michael addition or stretcher synthesis.
  • Polyamidoamines grafted with ethyleneimine are also suitable, which can be obtained, for example, by condensing dicarboxylic acids with polyamines and then grafting ethyleneimine. Higher molecular weights can be achieved through further crosslinking.
  • Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids having 4 to 10 carbon atoms with polyalkylene polyamines which contain 3 to 10 basic nitrogen atoms in the molecule. Mixtures of dicarboxylic acids can also be used in the preparation of the polyamidoamines, as can mixtures of several polyalkylene polyamines. Lactones or lactae of carboxylic acids having 4 to 8 carbon atoms can optionally also be used in the condensation. For example, 0.8 to 1.4 moles of a polyalkylene polyamine are used per mole of a dicarboxylic acid. These polyamidoamines are grafted with ethyleneimine.
  • water-soluble crosslinked polyethyleneimines are suitable, which can be obtained by reacting polyethyleneimines with crosslinking agents such as
  • Epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols with 2 to 100 ethylene oxide and / or propylene oxide units are available and still have free primary and / or secondary amino groups.
  • Amidic polyethyleneimines are also suitable, which are obtainable, for example, by amidating polyethyleneimines with C 1 -C 2 -monocarboxylic acids.
  • Other suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. In the alkoxylation z. B. per NH unit in polyethyleneimine 1 to 5 ethylene oxide or propylene oxide units.
  • the charge density of a particular polymer affects its retention properties.
  • the retention behavior of a polymer can be optimized for certain paper materials. Fixing agents with the highest charge density are particularly preferred. For this reason, the development aims to develop cationic polymers with high charge density.
  • the object of the present invention is to provide polymethylene amine or a process for its synthesis.
  • the present invention further relates to methods for producing PMAm.
  • the starting material for the synthesis of PMAm is a compound of the general formula (II).
  • R 1 and R 2 are substituents which may optionally be present and are selected independently of one another from the group consisting of: hydrogen, saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted C 1 -C 4 o -alkyl groups; Formyl groups and saturated and unsaturated, linear and branched, unsubstituted and optionally aryl-substituted aliphatic C x -C 40 acyl groups; Groups of the type R0C (0) -, in which R5 is a saturated or unsaturated, linear or branched, unsubstituted or optionally aryl-substituted C 1 -C 4 -alkyl group; Groups of Types -C (0) NR 6 R 7 , in which R 6 and R 7 are independently selected from hydrogen, saturated and unsaturated, linear and
  • R 3 and R 4 are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted C 1 -C 4 -alkyl groups and hydroxyl groups; or
  • R 1 and R 2 are independently selected from the group consisting of: hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted C 1 -C 2 -alkyl groups; Formyl groups and saturated linear and branched, unsubstituted and optionally aryl-substituted aliphatic C 1 -C 8 acyl groups; Groups of the type R 5 0C (0) -, in which R 5 is a saturated linear or branched, unsubstituted or optionally aryl-substituted C 1 -C 30 -alkyl group; Groups of the type -C (0) NR 6 R 7 , in which R 6 and R 7 are independently selected from hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted C 1 -C 4 -alkyl groups; and optionally substituted aromatic C ⁇ acyl groups;
  • R 3 and R 4 are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted C 1 -C 2 -alkyl groups and hydroxyl groups; or
  • R 1 and R 2 are independently selected from the group consisting of: hydrogen, saturated linear and branched, unsubstituted and optionally aryl-substituted Ci-Cs-alkyl groups; Formyl groups and saturated linear and branched, unsubstituted "and optionally aryl-substituted aliphatic C-Cs-acyl groups; groups of the type R 5 OC (0) -, in which R 5 is a saturated linear or branched, unsubstituted or optionally aryl-substituted C 1 -C 2 alkyl group; and optionally substituted aromatic C ⁇ acyl groups;
  • R 3 and R 4 are substituents which are optionally present and are selected independently of one another from the group consisting of hydrogen, saturated and unsaturated, linear and branched, substituted and unsubstituted C 1 -C 2 -alkyl groups and hydroxyl groups; or
  • the molecule of formula (II) is imidazole.
  • a 1,3-diacyl-4-imidazolin-2-one or a 1,3-diacyl-4-imidazol-2-thione is used as the starting monomer.
  • Polymerization gives poly (1, 3-diacyl-4-imidazolin-2- (thi) on) (II), the repeating units of the general formula III
  • R is hydrogen, a linear or branched C 1 -C 4 -alkyl group, a linear or branched C 1 -C 4 o -alkoxy group, or phenyl, preferably hydrogen or a linear or branched C 1 -C 4 -alkyl group, in particular a methyl group;
  • X is 0 or S, preferably 0.
  • the degree of polymerization n of PMAm Ia is> 2, preferably> 10. It is more preferred if the degree of polymerization n is from 1000 to 1,000,000, in particular from 10,000 to 100,000.
  • the molecular weight of the PMAm is> 100,000 D, preferably> 300,000 D, more preferably 300,000 D to 10,000,000 D, in particular 300,000 D to approx. 2,000,000 D.
  • the PMAm according to the present invention may contain only units of the formula (I), that is to say be present as a homopolymer. However, one or more further monomer units different from (I) can also be incorporated. There are then copolymers, for example bi- or terpolymers. These can be in the form of block or statistical polymers.
  • all monomer units compatible therewith can be present as further units in addition to the methylene amine units.
  • Comonomers which can be copolymerized with the monomers of the formula (II) or (IV) are preferably used in the copolymerization. Examples of these are vinyl esters of saturated carboxylic acids with 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as Ci to C 6 alkyl vinyl ether, for example methyl or ethyl inyl ether.
  • Suitable comonomers are esters, amides and nitriles of ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile.
  • esters, amides and nitriles of ethylenically unsaturated C 3 -C 6 -carboxylic acids for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile.
  • ethylenically unsaturated ones for example methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylamide and methacrylamide, and
  • C 3 -C 6 carboxylic acids are suitable, for example acrylic acid and methacrylic acid.
  • carboxylic acid esters are derived from glycols or polyalkylene glycols, only one OH group being esterified in each case, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate acrylate, hydroxybutyl methacrylate and acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000.
  • esters of ethylenically unsaturated carboxylic acids with amino alcohols such as, for example, dimethylaminoethyl acrylate, dimethylamino methyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylate, dimethylaminopropyl methacrylate, diethylaminopropylacrylate acrylate, dimethyl aminobutyl acrylate, dimethyl amine acrylate.
  • amino alcohols such as, for example, dimethylaminoethyl acrylate, dimethylamino methyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylate, dimethylaminopropyl methacrylate, diethylaminopropylacrylate acrylate, dimethyl aminobutyl acrylate, dimethyl
  • the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form.
  • Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
  • Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl residues of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-dimethyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert.
  • Butylacrylamide and basic (meth) acrylic amides e.g.
  • N-vinylpyrrolidone N-vinylcaprolactam
  • acrylonitrile methacrylonitrile
  • N-vinylimidazole substituted N-vinylimidazoles
  • N-vinyl-2-methylimidazole N-vinyl-4-methylimidazole
  • N-vinyl-5-methylimidazole N-vinyl-2-ethylimidazole
  • N-vinylimidazolines such as N-vinylimidazoline, N-vinyl- 2-methylimidazoline and N-vinyl-2-ethylimidazoline.
  • N-vinyllimidazoles and N-vinylimidazolines are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with methyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.
  • Diallyldialkylammonium halides such as e.g. Diallyldimethylammonium chloride.
  • vinyl formamide, styrene, butadiene, maleic anhydride (MA), fumaric acid and maleic acid are also suitable.
  • the hydrolysis can be carried out in solution or in bulk, using conditions and reagents known to the person skilled in the art. This hydrolysis is preferably carried out with strong bases. Suitable are the alcoholates of the known lower and higher alcohols, for example methanolates or ethanolates. Particularly suitable bases include NaOH, KOH, LiOH, CaOH and mixtures thereof. Particularly suitable as a base is a eutectic mixture or a mixture of NaOH and KOH lying close to the eutectic.
  • copolymers contain, for example
  • Poly (1, 3-diacyl-4-imidazolin-2- (thi) on) is prepared by radical or ionic, preferably radical polymerization from 1, 3-diacyl-4-imidazolin-2-one or -thione.
  • the polymerization can be carried out in bulk, in solution, suspension, emulsion or dispersion. It is preferably carried out in bulk.
  • the usual radical initiators known to those skilled in the art are used.
  • initiators which can be used as initiators are those by which free-radical polymerization of ethylenically unsaturated monomers can be achieved.
  • examples include azo compounds, organic or inorganic peroxides, salts of peroxodisulfuric acid and redox initiator systems.
  • the initiator is used in the process according to the invention in an amount of 0.1 to 5% by weight, based on the amount of the monomers to be polymerized.
  • the amount of initiator used depends in a known manner on the effectiveness with which the radical polymerization of the monomers is triggered. Small amounts of initiator will often be used in the polymerization in a water-in-oil emulsion, especially if hydrophobic initiators are used.
  • the polymerization can also be triggered by actinic radiation, microwave radiation or ⁇ , ⁇ or ⁇ radiation.
  • azo initiators examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride (V50) and 2.2 '-Azo- bis (2- (2-rmidazolin-2-yl) propane) dihydrochloride.
  • organic peroxides are hydrogen peroxide and percarbonates
  • examples of organic peroxides include alkyl hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, and furthermore peroxycarboxylic acid esters such as tert.
  • Suitable salts of peroxodisulfuric acid are in particular the sodium, potassium and ammonium salts.
  • redox initiator systems include systems which use one of the abovementioned organic or inorganic peroxides, in particular hydrogen peroxide, as the oxidation component and at least one further reduction component such as ascorbic acid, hydroxylamine or adducts of the sulfurous acid with aldehydes, for example the bisulfite adduct with acetone or hydroxymethanesulfinic acid sodium salt contain.
  • Both the aforementioned peroxides and the redox initiator systems can be used in the presence of redox-active transition metals such as iron, vanadium or copper, preferably in the form of water-soluble salts.
  • Examples of further initiator systems include hydrogen peroxide, tert. -Butyl peroxide and salt-like azo compounds, e.g. B. the aforementioned hydrochlorides.
  • Examples are bisazo (alkylnitriles) such as 2,2 'azobis (valeronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2-4-dimethylvaleronitrile) ), 2, 2 'azobis (isobutyronitrile); Alkyl and cycloalkyl percarbonates such as dicyclohexyl peroxodicarbonate, di-2-ethylhexyl peroxide carbonate, tert.
  • -Butylperoxoisopropylcarbonat Diacyl peroxides such as acetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide; Peroxy esters, especially tert-butyl peroxy carboxylic acid esters such as tert. Butyl perpivalate, per-2-ethylhexanoate, perneodecanoate; Hydroperoxides such as cumene hydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide and tert. -Butyl hydroperoxide and peroxides such as dicumol peroxide, di-tert-butyl peroxide and di-tert. -amylperoxid.
  • Diacyl peroxides such as acetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, dibenzoyl
  • chain transfer agents In radical polymerization, chain transfer agents (regulators) are generally used.
  • chain transfer agents are: aliphatic mercaptans such as C 6 -C-alkyl mercaptans such as n-hexyl mercaptan; n-octyl mercaptan, tert-octyl mercaptan, 2-ethylhexyl mercaptan, n-decyl mercaptan, 2-propylheptyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan; water-soluble mercaptans such as 2-mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropi
  • the polymerization temperature generally depends on the initiator system used and is frequently in the range from 20 to 160 ° C. and in particular in the range from 130 to 150 ° C.
  • the polymerization time is usually in the range from 1 min to 24 h.
  • the pH of the reaction medium is preferably in the range from 3 to 10.
  • the implementation can be carried out as a batch process.
  • the monomers to be polymerized are initially introduced into the aqueous reaction medium and the polymerization initiator is fed in under polymerization conditions, preferably depending on its consumption, or is introduced together with the monomers in the polymerization vessel and then heated to the polymerization temperature.
  • Tert-butyl hydroperoxide is preferably used as the radical initiator.
  • Poly (1, 3-diacyl-4-imidazolin-2- (thi) on) polymers are a further subject of the present invention.
  • 1,3-diacyl-4-imidazolin-2-ones and -thiones can be obtained by conventional acylation of 4-imidazolin-2-one or -2-thione known to the person skilled in the art.
  • Another object of the present invention is the preparation of PMAm by polymerizing 1,2-diaminoethene derivatives of the following formula IV, which are obtainable from imidazole.
  • R 1 and R 2 are independently a radical of the formula R 5 , OR 6 or NR 7 R 8 , where R 5 , R 6 , R 7 and R 8 are selected independently of one another from the group consisting of hydrogen, linear and branched C ⁇ -C 4 o-alkyl groups, which optionally have one or more substituents from the group of optionally alkyl-substituted C ⁇ -aromatics, and Cg-aromatics, which optionally have one or more substituents from the group consisting of -C-C 4 o- Have alkyl groups; R 3 and R 4 are independently selected from the group consisting of hydrogen, -CC 4 o-alkyl groups and aromatics.
  • the diaminoethene derivatives of the formula (IV) can be in the ice or trans form or can be used in the polymerization reaction.
  • Polymerization can be used to obtain substituted polymethylene amines from the monomers of the formula IV in which a hydrogen of the amino group has been replaced by a —C (0) R group, as shown in formula IV.
  • the polymerization is carried out cationically or radically.
  • the polymerization is preferably carried out cationically, it being possible to use the customary Lewis acids.
  • the polymerization can also be triggered by actinic radiation, microwave radiation or ⁇ , ⁇ or ⁇ radiation.
  • the polymerization temperature generally depends on the initiator system used and is frequently in the range from -10 to 110 ° C. and in particular in the range from 0 to 40 ° C.
  • the polymerization time is generally in the range from 1 to 10 h, but in individual cases can also be above or below these values.
  • the pH of the reaction medium is preferably in the range from 3 to 10.
  • the implementation can be carried out as a batch process.
  • the monomers to be polymerized are initially introduced into the reaction medium and the polymerization initiator is fed in under polymerization conditions, preferably depending on its consumption, or is introduced together with the monomers in the polymerization vessel and then heated to the polymerization temperature.
  • Lewis acids for example BF 3 diethyl ether, SnCl 4 , TiCl 3 , or C0, are preferably used for the polymerization.
  • the polymerization is preferably carried out cationically, in which case advantageous results have been achieved with BF 3 / diethyl ether as Lewis acid.
  • R 1 and R 2 are OR 6 and R 6 are Ci-C ⁇ -alkyl, benzyl or phenyl.
  • R 3 and R 4 are preferably hydrogen.
  • the cationic polymerization of the compounds of the formula (IV) is preferably carried out in homogeneous solution in an organic solvent.
  • Solvents which dissolve the compounds of the formula (IV) and are known to the person skilled in the art are preferred, preferably dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), dimethylformamide (DMF), formamide or hexamethylphosphorus triamide (HMPTA) ).
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • HMPTA hexamethylphosphorus triamide
  • the resulting polymers which are composed of the molecular units with the formula IV, are hydrolyzed to produce PMAm in a manner known to the person skilled in the art.
  • a part of the substituted 1, 2-diaminoethenes of the general formula IV can be obtained by a so-called Bamberger cleavage (E. Bamberger, Ann. 273, 267 (1893)) from imidazole.
  • Bamberger cleavage E. Bamberger, Ann. 273, 267 (1893)
  • the reaction is shown in equation (2) below, where X is Cl, Br or I, preferably Cl or Br.
  • 1,2-diaminoethenes which are not obtained from imidazole can also be used.
  • the polymers according to the invention are particularly suitable as dewatering, flocculating and retention agents and as fixing agents in the manufacture of paper.
  • they are added to the respective pulp in an amount of 0.01 to 2 and preferably in an amount of 0.01 to 0.5% by weight, e.g.
  • the polymers according to the invention in particular lead to improved retention of fine substances compared to the polymers of the prior art. They have particularly advantageous effects for the retention of fillers such as calcium carbonate.
  • the polymers are particularly characterized by good fixing properties.
  • the polymers according to the invention are particularly suitable for fixing impurities, coated rejects and stickies.
  • the polymers according to the invention can be used for the production of all paper, cardboard and cardboard qualities, for example for the production of papers for newspaper printing (high-pressure / offset printing), so-called medium-fine writing and printing papers, natural gravure papers and also lightweight coating base papers.
  • wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding (PGW), and sulphite and sulphate pulp are used as the raw material component.
  • the substances mentioned can be both short and long-fiber. Waste paper, pulp and wood pulp are also considered as raw materials for the production of the paper stock, which are further processed into paper in the so-called integrated factories in more or less moist form without prior thickening or drying. Some of these substances still contain residues of impurities. Inclusions that arise during the digestion and that strongly disrupt the normal paper manufacturing process. These impurities are fixed in a particularly good manner on the paper by the polymers according to the invention.
  • filler-free and filler-containing papers can be produced.
  • the filler content of filler-containing papers can be up to a maximum of 40% by weight and is preferably in the range from 5 to 30% by weight.
  • Suitable fillers are, for example, clay, kaolin, chalk, talc, titanium dioxide, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the aforementioned fillers.
  • Examples of the use of the polymethylene amines or copolymers according to the invention are their use as retention agents in the manufacture of paper, cardboard and cardboard, as fixatives for rendering harmful substances in the paper manufacture, as fixatives for anionic stabilized sizing agents, as fixatives for the fixation of anionic dyes, as a primary for adhesion to anionic surfaces, as an aid in oil production, as a textile and leather aid, as a component in detergents, as an emulsifier for emulsions / dispersions, as a crosslinker in the manufacture of PUR, as Catcher of formaldehyde and higher aldehydes, as a binder for fiberboard, as an aid for sludge dewatering, and as a vector in cancer therapy.
  • 10 drops of a 70% aqueous solution of tert are first added.
  • the monomer reacts to form a solid polymer block.
  • the temperature is kept at 140 ° C. for 1 hour. After cooling to room temperature, 9.5 g of a colorless, brittle polymer, which can be easily pulverized, is isolated. The polymer dissolves in THF and chloroform, it is insoluble in water.
  • the polymer has repeat units made from 1,3-diacetyl-4-imidazolin-2-one.
  • the softening point of the polymer was> 260 ° C, the charge density of the polymer was determined to be 1.94 mmol / g. A molecular mass of 300,000 D was determined using static light scattering.
  • the filtrate which according to HPLC did not yet contain a fully reacted monoadduct, was slowly reacted with a further 7.0 g of benzoyl chloride (0.05 mol) at 20-25 ° C. while maintaining a pH of 7-8 in 2.75 hours.
  • Post-reaction time 1 hour at 20-25 ° C.
  • 3.4 g of NaOH 50% were required to adjust the pH.
  • the reaction mixture was a glass suction filter G 3 sucked.
  • the filtrate was reacted again slowly at 20-25 ° C.
  • the ethyl chloroformate was added dropwise for 10 minutes. The experiment was stopped after a further 30 minutes. The product was suctioned off through a glass suction filter G 3 and washed three times with cold water, sucked dry, and then dried on a rotary evaporator at 40-45 ° C./15 mbar for 2 hours. The solid became out
  • the sample is a mixture of the eis and trans isomers.
  • the mixture was suctioned off through a G 3 glass filter, the aqueous phase was discarded.
  • the solid, kneaded mass is washed with cold water and then dissolved in ethanol, anhydrously dried with Na S0 4 and filtered off.
  • the solution is rotated in at 50-55 ° C / 15 mbar on a rotary evaporator.
  • reaction solution becomes cloudy.
  • the pH has reached 7-8, it is kept with 50% sodium hydroxide solution.
  • the chloroformate is added dropwise after about 3.5 hours at 20-25 ° C.
  • the Temperature is raised to 30-35 ° C. After 3 hours at this temperature, this is increased again to 60-65 ° C. After a further 6.5 hours at 60-65 ° C, the pH is constant at 7.55. 10.8 g (0.14 mol) of 50% sodium hydroxide solution were required to adjust the pH.
  • the mixture was sucked off through a G 4 glass filter.
  • the white precipitate was washed with a little m-xylene. Residue 3.1 g water-soluble.
  • the aqueous phase was separated off in a separating funnel.
  • the organic phase is diluted with 100 ml of THF and dried anhydrous with sodium sulfate, then filtered off. M-xylene and THF were rotated off on a rotary evaporator at 50-55 ° C./11 mbar. 21.9 g of a yellowish oil containing about 90% of product were obtained.
  • the chloroformate is added dropwise at 30-25 ° C. for 3 hours.
  • the temperature is kept at 20-25 ° C for 3 hours.
  • the temperature is increased again to 40-45 ° C.
  • the pH is constant at 8.2. 11 g (0.14 mol) 50% sodium hydroxide solution were required to adjust the pH. to
  • the organic phase is not completely soluble in THF.
  • the insoluble part was sucked off through a glass suction filter G 3 and 45 was 4.4 g (NaCl).
  • the THF phase was dried anhydrous with sodium sulfate and on a rotary evaporator at 35-40 ° C / ll Rotated in mbar and dried at 65-70 ° C / 9 mbar on a rotary evaporator. The yield was 15 g.
  • the entire batch was taken up in 40 about 600 ml of THF, dried anhydrous with sodium sulfate and then suctioned off through a G 4 glass filter. The solution is rotated in at 60-65 ° C / 13 mbar on a rotary evaporator. The crude yield was 31.5 g.
  • reaction mixture was analyzed using GPC (eluent THF) and MALDI-TOF up to approx. 800 D.
  • the molar mass is around 1,000 D.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une amine de polyméthylène contenant des unités récurrentes de la formule générale (I). L'amine de polyméthylène est produite à partir d'imidazol ou de ces dérivés, par exemple par hydrolyse de poly(1,3-diacyl-4-imidazolin-2-thione), contenant des unités récurrentes de la formule générale (III), où R est sélectionné dans le groupe composé d'hydrogène, de groupes alkyle C1-C8 linéaires et ramifiés, de groupes alcoxy C1-C40 linéaires et ramifiés, et phényle, de préférence d'hydrogène et de groupes alkyle linéaires et ramifiés C1-C3, notamment R représente un groupe méthyle; X représente oxygène ou soufre, de préférence de l'oxygène. L'amine de polyméthylène peut également être produite par hydrolyse de dérivés de poly(1,2-diaminoéthène) et dans des conditions appropriées. L'amine de polyméthylène a une densité de chargement très élevée et convient notamment comme agent de rétention/fixation lors de la fabrication de papier.
PCT/EP2003/007682 2002-07-25 2003-07-16 Amine de polymethylene, son procede de production et son utilisation Ceased WO2004013207A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003250069A AU2003250069A1 (en) 2002-07-25 2003-07-16 Polymethylene amine, method for the production and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10233930A DE10233930A1 (de) 2002-07-25 2002-07-25 Polymethylenamin, Verfahren zu seiner Herstellung und seine Verwendung
DE10233930.9 2002-07-25

Publications (1)

Publication Number Publication Date
WO2004013207A1 true WO2004013207A1 (fr) 2004-02-12

Family

ID=30010377

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/007682 Ceased WO2004013207A1 (fr) 2002-07-25 2003-07-16 Amine de polymethylene, son procede de production et son utilisation

Country Status (3)

Country Link
AU (1) AU2003250069A1 (fr)
DE (1) DE10233930A1 (fr)
WO (1) WO2004013207A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102392255A (zh) * 2011-10-10 2012-03-28 南昌航空大学 聚丙烯酸钠分散咪唑啉缓蚀剂的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107223171A (zh) 2014-12-16 2017-09-29 巴斯夫欧洲公司 制造纸和纸板的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421602A (en) * 1981-07-18 1983-12-20 Basf Aktiengesellschaft Linear basic polymers, their preparation and their use
DE19631350A1 (de) * 1996-08-02 1998-02-05 Basf Ag Vernetzte, hydrolysierte, lineare Polymere von N-(2-(1'-Aziridino)ethyl)formamid, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19850817A1 (de) * 1998-11-04 2000-05-11 Basf Ag Modifizierte kationische Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Papierherstellung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421602A (en) * 1981-07-18 1983-12-20 Basf Aktiengesellschaft Linear basic polymers, their preparation and their use
DE19631350A1 (de) * 1996-08-02 1998-02-05 Basf Ag Vernetzte, hydrolysierte, lineare Polymere von N-(2-(1'-Aziridino)ethyl)formamid, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19850817A1 (de) * 1998-11-04 2000-05-11 Basf Ag Modifizierte kationische Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Papierherstellung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102392255A (zh) * 2011-10-10 2012-03-28 南昌航空大学 聚丙烯酸钠分散咪唑啉缓蚀剂的制备方法
CN102392255B (zh) * 2011-10-10 2013-04-03 南昌航空大学 聚丙烯酸钠分散咪唑啉缓蚀剂的制备方法

Also Published As

Publication number Publication date
DE10233930A1 (de) 2004-02-05
AU2003250069A1 (en) 2004-02-23

Similar Documents

Publication Publication Date Title
EP0071050B1 (fr) Des polymères linéaires, basiques, procédé pour leur préparation et leur utilisation
DE69720455T2 (de) Verfahren zur herstellung von wässrigen dispersionspolymeren
DE3721426C2 (de) N-Vinylformamidcopolymere und Verfahren zu ihrer Herstellung
EP0256312B1 (fr) Polymères amphotères solubles dans l'eau, leur procédé de préparation et leur usage comme agent auxiliaire de dispersion
DE68929209T2 (de) Mikroemulgierte funktionalisierte Polymere
DE68921598T2 (de) Kationische Acrylamidpolymere, Verfahren zu deren Herstellung und Verwendung.
DE3720194C2 (de) Vinylamincopolymere, Verwendung als Ausflockungsmittel und Verfahren zu ihrer Herstellung
DE602004012973T2 (de) Hochmolekulare polymere mit seitenständigen salicylsäuregruppen zur klärung von laugen aus dem bayer-verfahren
DE4339193C2 (de) Modifizierung von Polyvinylamin
EP1274652B1 (fr) Procede de clarification de l'eau a l'aide de polymeres cationiques de dispersion de faible poids moleculaire
DE2823830A1 (de) Amphotere polyelektrolyte und verfahren zu ihrer herstellung
US5281340A (en) Cationic polymer flocculating agents
EP0418343B1 (fr) Procede de fabrication de papier, de carton-pate et de carton en presence de copolymeres contenant des unites de n-vinylformamide
EP0703972A1 (fr) Polyamidoamines greffees et imines de polyethylene greffees, leur procede de preparation et leur utilisation comme additifs d'agents de lavage
EP0464043B1 (fr) Utilisation de copolymeres non hydrolyses d'unites de n-vinylformamide comme floculants et deshydratants
EP1522556A1 (fr) Dispersion polymere hydrosoluble, son procede de production et d'utilisation
DE3128478A1 (de) Verfahren zur herstellung von linearen, basischen polymerisaten
DE69603789T2 (de) Ungesättigte Alkylbernsteinsäure-Halbester, Polymere daraus, und Verwendung dieser Polymere
DE68923725T2 (de) Verfahren zur Herstellung von Sulfonierungsprodukten von konjugierten Dienen, Polymere des Sulfonierungsproduktes sowie dispergierende Zusammensetzung, die das Sulfonierungsprodukt und/oder das Polymer enthält.
DE68926946T2 (de) Copolymere von 3-Methacryloyloxy-2-hydroxypropyltrimethylammoniumchloridmonomer und einem Vinylmonomer
WO2004013207A1 (fr) Amine de polymethylene, son procede de production et son utilisation
DE10305807A1 (de) Polymethylenamine und Verfahren zu deren Herstellung
EP0735061B1 (fr) Utilisation de dispersions aqueuses de polymère, stabilisées cationiquement en tant que liants pour articles moulés, à base de fine particules ayant une charge de surface négative
DE69501988T2 (de) Amidmonomer und dessen Polymer
DE102005025739A1 (de) Copolymerisierbare Polyalkylenglykol-Makromonomere, deren Herstellung und Verwendung

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP