EP1594905A2 - Acide phosphonique de polyisobutylene et ses derives - Google Patents

Acide phosphonique de polyisobutylene et ses derives

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Publication number
EP1594905A2
EP1594905A2 EP04709595A EP04709595A EP1594905A2 EP 1594905 A2 EP1594905 A2 EP 1594905A2 EP 04709595 A EP04709595 A EP 04709595A EP 04709595 A EP04709595 A EP 04709595A EP 1594905 A2 EP1594905 A2 EP 1594905A2
Authority
EP
European Patent Office
Prior art keywords
acid
polyisobutenephosphonic
polyisobutene
reaction
phosphonic acid
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Withdrawn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
EP04709595A
Other languages
German (de)
English (en)
Inventor
Arno Lange
Darijo Mijolovic
Ulrich Karl
Georg Josef DÖRING
Helmut Witteler
Ralf NÖRENBERG
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1594905A2 publication Critical patent/EP1594905A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/16—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-nitrogen bond
    • 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
    • C08F8/14—Esterification
    • 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
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/063—Ammonium or amine salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • the present invention relates to polyisobutenephosphonic acids and their derivatives, a process for their preparation and their use.
  • Amphiphilic polyalkenyl derivatives which are used to modify the surface properties or the interface behavior e.g. are known as corrosion inhibitors, friction reducers, emulsifiers or dispersants.
  • the international patent application PCT / EP 02/09608 describes a polymer composition which on the one hand contains a component containing polyisobutene and on the other hand contains a different polymer.
  • the polyisobutene-containing component can be selected from derivatized polyisobutenes. These derivatives are, for example, epoxidized, hydroformylated, hydroxylated, halogenated, silylated or polyisobutenes functionalized with thio groups or sulfonic acid groups. These compositions are said to have good mechanical properties and / or good interface properties on iron.
  • No. 4,578,178 describes the use of polyalkenylthiophosphonic acids or their esters to prevent the formation of deposits in petroleum or petrochemical products.
  • No. 4,778,480 describes polyalkenyl-substituted thiophosphonic acids which are used for color stabilization in diesel fuels.
  • the thiophosphonic acids are obtained by reacting a polyalkene with phosphorus pentasulfide and subsequent hydrolysis and ethoxylation.
  • the thiophosphonic acid could possibly also be hydrolyzed to the phosphonic acid in the hydrolysis, according to the technical teaching of this document, only sulfur-containing products are desired.
  • such a hydrolysis product always contain sulfur in not negligible amounts, from which it will generally be difficult to get rid of.
  • a disadvantage of the sulfur-containing phosphonic acids of the four aforementioned US documents is their smell and their color, which make them appear unsuitable for certain applications. Furthermore, the storage stability and the effectiveness of this class of compounds is unsatisfactory. In particular, the use of such sulfur-containing products in fuel oil compositions, such as diesel, ot-to-fuels and heating oil, is inconceivable for environmental reasons in view of the combustion products of the sulfur contained, in particular sulfur dioxide.
  • the object of the present invention was to provide new amphiphilic polyalkenyl derivatives with good performance properties. In particular, these should be odorless, have sufficient storage stability and / or have good surface-active properties.
  • R 1 and R 2 are independently halogen, OR 3 , SR 3 or NR 3 R 4 ;
  • R 3 and R 4 independently of one another are H r -CC-alkyl or C 2 -C 40 oo-alkyl which is interrupted by at least one group selected from 0, S and NR 11 , where R 3 and R 4 can also form a ring together with the nitrogen atom to which they are attached, R 3 and R 4 continue to represent aryl, aralkyl or cycloalkyl; and
  • R 11 is defined as R 3 and R 4 ,
  • Preferred polyisobutenephosphonic acids contain no thioester groups, ie in formula I, R 1 and R 2 independently of one another are preferably halogen, OR 3 or NR 3 R 4 , where R 3 and R 4 are as defined above. Particularly preferably, R 3 and R 4 independently of one another preferably H, C ⁇ -C 2 o alkyl or C 2 -C 400 Q ⁇ alkyl which is interrupted by at least one moiety selected from O and NR 11, wherein R 3 and R 4 can also form a ring together with the nitrogen atom to which they are attached; R 3 and R 4 also represent aryl, aralkyl or cycloalkyl. R 11 is defined as R 3 and R 4 . In particular, the radicals R 3 and R 4 contain no sulfur-containing groups. Salts thereof are also preferred.
  • polyisobutenephosphonic acid is intended to mean both the phosphonic acid itself and its derivatives.
  • the phosphonic acid residue I is preferably bound to one or more chain ends of the polyisobutene group.
  • chain ends are understood to be the three outer carbon atoms of the polymer backbone at each end of the polymer chains.
  • the phosphonic acid residue I is preferably bound to one of the three outer carbon atoms of the polymer backbone, particularly preferably to the last carbon atom of the polymer backbone.
  • the chain end which carries the phosphonic acid group I can be saturated or unsaturated.
  • the phosphonic acid group is preferably bonded to a carbon atom which is part of a carbon-carbon double bond, and particularly preferably to the outer carbon atom of a methylidene group.
  • the phosphonic acid residue I is bound to a saturated carbon atom »
  • a polyisobutenephosphonic acid according to the invention can be represented, for example, by the following, non-limiting structural formula II
  • A represents a residue derived from a polymerization initiator
  • M represents a polymer chain which contains repeating units of the formula CH 2 -C (CH 3 ) 2 ⁇ - (III), B stands for a chain end which carries a phosphonic acid residue of the formula I covalently bonded and
  • n stands for a number from 1 to 6.
  • the structure of the term B depends on a. on the structure of the polyisobutene from which the polyisobutenephosphonic acids according to the invention are obtainable, in particular on the chain end thereof.
  • the structure of the chain end is in turn dependent on the type, the conditions and the termination of the polymerization reaction by means of which this polyisobutene is produced.
  • the structure of the terminus B is also determined by the reaction with which the polyisobutenephosphonic acids according to the invention can be obtained from the polyisobutene.
  • B can stand for one of groups a to e, these structural formulas not being a restrictive list:
  • R 1 and R 2 are as defined above and Hai is halogen.
  • the structure of the chain start A also depends on the type of polymerization by means of which the polyisobutene on which the polyisobutenephosphonic acid according to the invention is based is produced. If the cationic polymerization is terminated hydrolytically, A can stand for the hydrolysis product of the chain start group formed in the course of the polymerization, for example for a tert-butyl radical. If the polyisobutene is produced, for example, under the conditions of living cationic polymerization in the presence of an initiator molecule (“Tnifer”), A can also represent a residue derived from the initiator molecule. In addition, the chain start A can also contain a phosphonic acid residue I covalently bound.
  • n stands for a number greater than 1 if the polyisobutene is subjected to living cationic polymerization in the presence of an initiator molecule which is at least bifunctional, ie. H. from which at least two polymer chains can be produced.
  • C 1 -C 2 -alkyl represents a linear or branched alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl and their positional isomers.
  • alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-buty
  • CC 24 alkyl also stands for heneicosyl, docosyl, tricosyl and tetracosyl and their positional isomers.
  • the alkyl group is from cycloalkyl, halogen, OR 5, SR 5 and NR 5 R 6 wherein R 5 and R 6 are optionally substituted by at least one group that is selected independently of each other H or Ci-C ß alkyl substituted ,
  • the alkyl radical is preferably not substituted by an SR 5 radical. This applies in particular if the polyisobutenephosphonic acid according to the invention is to be used in fuel and lubricant compositions.
  • the C 2 -C 4 ooo radical which is interrupted by at least one group 0, S and / or NR 11 can also be replaced by at least one group which is selected from cycloalkyl, halogen, OR 5 , SR 5 and NR 5 R 6 , may be substituted, where R 5 and R 6 are independently H or Ci-Cg-alkyl.
  • the C 2 -C 4 ooo alkyl radical is preferably not interrupted by an S group. In addition, it is preferably also not substituted by an SR 5 radical. This applies in particular if the polyisobutenephosphonic acid according to the invention is to be used in fuel and lubricant compositions.
  • the C 2 -C 4 ooo alkyl radical is preferably a radical of the formula IV
  • R 7 'R 8 , R 9 and R 10 independently of one another are H or -CC 4 alkyl
  • X represents O, S or NR 11
  • Y stands for H, OR 12 , SR 12 or NR 12 R 13 ,
  • R 11 represents H or C 1 -C 4 alkyl
  • R 12 and R 13 are independently H or Ci-Cg-alkyl
  • k represents a number from 1 to 6
  • n a number from 0 to 5, the sum of k and m being 1 to 6, and
  • 1 stands for a number from 1 to 1000.
  • the alkylene group (CR 7 R 8 ) k (CR 9 R 10 ) m stands for example for 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 2,3-butylene or 1 , 4-butylene. It is preferably 1,2-ethylene or 1,2-propylene, in particular 1,2-ethylene.
  • k and m preferably represent a number from 1 to 3, especially 1.
  • the sum of k and m is preferably a number from 2 to 4 and particularly preferably 2.
  • 1 preferably stands for a number from 1 to 300, particularly preferably from 1 to 40 and especially from 1 to 4.
  • C ⁇ -C 4 alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
  • Ci-C ß- alkyl also stands for pentyl, hexyl and their positional isomers.
  • Aryl preferably represents optionally substituted phenyl or naphthyl. Suitable substituents are, for example, halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy.
  • Aralkyl is preferably benzyl or 2-phenylethyl.
  • Cycloalkyl is preferably C 3 -C ⁇ o-cycloalkyl, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl or cycl ⁇ decyl, and particularly preferably C 3 -C 6 -cycloalkyl.
  • the cycloalkyl radical can be substituted by at least one group selected from 0, S and NR 11 , interrupted and / or substituted by at least one group which is selected from C 1 -C 2 -alkyl, halogen, OR 5 , SR 5 and NR 5 R 6 .
  • Cycloalkyl interrupted by at least one group 0, S and / or NR 11 represents, for example, pyrrolidyl, tetrahydrofurany1, tetrahydrothienyl, oxazolidinyl, piperidinyl, piperazinyl or morpholinyl, the cycloalkyl radical of course not passing through the ring heteroatom to the oxygen, Sulfur or nitrogen atom of the radicals R 1 or R 2 may be bound.
  • the cycloalkyl radical is preferably not interrupted by an S group. In addition, it is preferably also not substituted by an SR 5 radical. This applies in particular if the polyisobutenephosphonic acid according to the invention is to be used in fuel and lubricant compositions.
  • Halogen is preferably Cl or Br and particularly preferably Cl.
  • R 1 and / or R 2 represent a radical 0- "M n + ⁇ / n or SM" ** 1 "1 " ! / -, where M stands for a cation and n denotes its charge number.
  • Suitable cations are the cations of alkali metals, such as lithium, sodium or potassium, of alkaline earth metals, such as magnesium or calcium, and of heavy metals, such as iron, zinc or silver, and furthermore ammonium cations [NR a R b R c R d ] + , wherein R a to R d independently of one another are H, Ci-Cg-alkyl, Ci-Cg-alkoxy or aryl.
  • Preferred cations are alkali and alkaline earth metal cations and ammonium cations.
  • R 3 and R 4 are preferably H.
  • R 3 and R 4 are preferably optionally substituted C 1 -C 6 -alkyl.
  • R 3 and R 4 preferably represent a radical of the formula IV in which X represents 0 and Y represents OR 12 or in which X represents NR 11 and Y represents NR 1 R 13 , that is to say a polyether or Polyamine residue.
  • R 7 and R 9 are H and R 8 and R 3 - 0 are H or C 1 -C 4 -alkyl, in particular H or methyl and especially H.
  • k and m are preferably a number of 1 to 3, in particular for 1.
  • the sum of k and m preferably stands for a number from 2 to 4- 1 preferably stands for a number from 1 to 300, particularly preferably from 1 to 40, in particular from 1 to 10 and especially from 1 to 4.
  • Preferred polyether radicals are those of the formula IV.a.
  • 1 stands for a number from 1 to 1000, preferably from 1 to 300, particularly preferably from 1 to 40, in particular 1 to 10 and specifically from 1 to 4 and
  • R 12 represents H or -CC 6 alkyl, in particular H, methyl or ethyl, is »
  • Preferred residues IV. A are correspondingly di, tri, tetra or pentaethylene glycol residues as well as polyethylene glycol residues with up to 1000 repeating units. Examples of such higher polyethylene glycol residues are residues which are derived from the Pluronic, Pluriol and Lutensol brands from BASF AG.
  • C 2 -C 4 ooo alkyl radicals are polyether-containing radicals which are derived from block copolymers of alkylene oxides and alkanes as monomers.
  • Suitable alkylene oxides are, for example, ethylene oxide and propylene oxide.
  • Suitable alkenes are, for example, ethylene, propylene and isobutene.
  • Preferred polyamine residues are those of the formula IV.b.
  • 1 represents a number from 1 to 1000, particularly preferably from 1 to 300, in particular from 1 to 40 and especially from 1 to 4,
  • R 11 is H or C ⁇ -C 4 alkyl, preferably H or methyl and in particular for H, and
  • R 12 and R 13 independently of one another represent H or -CC 6 alkyl and in particular H.
  • R 12 and R 13 are particularly preferably the same radical.
  • radicals NR 3 R 4 , R 3 and R 4 either represent the same radical or one of the radicals R 3 or R 4 represents H and the other radical represents a radical other than H.
  • Preferred radicals different from H are unsubstituted or by a radical OR 5 or NR 5 R 6 substituted -CC- 0 alkyl or radicals of the formula IV.b.
  • the radicals R 1 and R 2 independently of one another represent halogen, OH, NH 2 .
  • R 3 stands for C 1 -C 20 -alkyl
  • NR 3 R 4 wherein R 3 is H or C ⁇ -C is 20 alkyl and R 4 is alkyl of 20 C ⁇ -C, or a radical of Formula Va or Vb
  • R 12 and R 13 are each as defined for the residues IV.a and IV.b.
  • radicals R 1 and R 2 stand for halogen, OH, NH 2 , OR 3 or NR 3 R 4 , in which R 3 represents C 1 -C 10 -alkyl, in particular C ⁇ -C 6 -alkyl, which is formed by a radical, which is selected from NH 2 , dimethylamine, diethylamine, OH, methoxy or ethoxy, and R 4 is H or as R 3 is defined, or they are a radical of the formula Va or Vb
  • the salts of the polyisobutenephosphonic acids according to the invention are also particularly preferred.
  • the polyisobutene residue in the polyisobutenephosphonic acid according to the invention preferably has a number average molecular weight M n of 100 to 1,000,000, particularly preferably from 100 to 100,000, in particular from 200 to 60,000 and especially from 200 to 40,000.
  • M n number average molecular weight
  • the choice of polyisobutene residues with specific molecular weights depends on the application medium and intended use of the respective polyisobutenephosphonic acid according to the invention and is determined by the person skilled in the art in individual cases.
  • Amphiphilic substances usually consist of a polar head group and a lipophilic tail.
  • the lipology of the compounds is essentially determined by the tail group (essentially corresponds to the polyisobutene radical).
  • the molecular weight of this group correlates with the HLB value (hydrophilic lipophilic balance) of the compound and thus determines its suitability for special applications for surface modification.
  • the HLB value is a measure of the water or oil solubility of surface-active substances and the stability of emulsions.
  • substances with an HLB value of 3 to 8 are suitable for use in W / O emulsions, those with an HLB value of 8.5 to 11 in W / O microemulsions, those with an HLB value of 7 to 8 9 as wetting agent, those with an HLB value of 8 to 18 in O / W emulsions, those with an HLB value of 13 up to 15 as detergents and those with an HLB value of 12 to 18 as solubilizers (cf. Römpp Chemie-Lexikon, 9th edition, G. Thieme Verlag, p. 1812 and the literature cited therein).
  • polyisobutenephosphonic acid according to the invention as corrosion inhibitors for metals or for the hydrophobization of basic surfaces, such as gypsum, cement or calcium carbonate, is not subject to any stringent requirements for the HLB value, so that polyisobutene residues with a number average molecular weight of 500 to 40,000 are suitable here. If the polyisobutenephosphonic acid is to be used as a detergent or dispersant in fuel and lubricant compositions, then narrower HLB ranges must be adhered to and accordingly polyisobutene residues with a number average molecular weight of 100 to 3000 are suitable. This molecular weight range is also suitable for use as an emulsifier, for example in W / 0 emulsions, O / W emulsions or microemulsions.
  • the molecular weight of the tail group correlates with the viscosity for a given head group.
  • a higher molecular weight of a polymer within a polymer-homologous series results in a higher viscosity of the solution which contains it (cf. Römpp Chemie-Lexikon, 9th edition, G. Thieme Verlag, p. 4939 and the literature cited therein).
  • polyisobutenephosphonic acid according to the invention in emulsions, dispersions or for hydrophobicizing basic inorganic material, such as Gypsum, cement or calcium carbonate, so you choose in particular polyisobutene residue with an M n of 500 to 60,000, preferably> 1000 to 50,000, z. B.> 1000 to 10000.
  • polyisobutene residues with an M n of 2300 to 1000000, preferably from> 10000 to 100000 are particularly suitable.
  • the polyisobutenephosphonic acid according to the invention can be obtained by customary methods of the prior art for the production of organic phosphonic acid derivatives. Such procedures are for example in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume XII / 1, pages 338 to 619 (1963) and in Volume E 2, pages 300 to 418 (1982). Reference is hereby made in full to this and to the literature cited therein.
  • Another object of the present invention is a process for the preparation of the polyisobutenephosphonic acid according to the invention, in which
  • step bl the reaction product obtained in step a) is reacted with a halogen scavenger
  • step b1) reacting the reaction product obtained in step b1) with water, at least one alcohol, at least one thiol and / or at least one amine, or
  • step b2) the reaction product obtained in step a) is reacted with water, at least one alcohol, at least one thiol and / or at least one amine.
  • Preferred phosphorus pentahalides are phosphorus (V) chloride and phosphorus (V) bromide, with phosphorus (V) chloride being particularly preferred.
  • the phosphorus pentahalides can be used as such in the reaction.
  • phosphorus (V) chloride can be prepared in situ from phosphorus (III) chloride and chlorine.
  • the polyisobutene and phosphorus (III) chloride are introduced and chlorine gas is introduced, with phosphorus (V) chloride being formed successively.
  • polyisobutene Any common and commercially available polyisobutene can be used as the polyisobutene.
  • polyisobutene also includes oligomeric isobutenes, such as dimeric, trimeric or tetrameric isobutene.
  • polyisobutenes are also understood to mean all polymers obtainable by cationic polymerization, which preferably contain at least 60% by weight of isobutene, particularly preferably at least 80% by weight, more preferably at least 90% by weight and in particular at least 95% by weight. -% copolymerized isobutene included.
  • polyisobutenes may contain copolymerized further butene isomers, such as 1- or 2-butene and various olefinically unsaturated monomers which are copolymerizable with isobutene under cationic polymerization conditions.
  • suitable isobutene starting materials for the production of polyisobutenes which are suitable as educts for the process according to the invention, are both isobutene itself and also C 4 -hydrocarbon streams containing isobutene, for example C 4 raffinates, C 4 cuts from the isobutane Dehydration, C 4 cuts from steam crackers, FCC crackers (FCC: Fluid Catalyzed Cracking), provided that they are largely freed of 1,3-butadiene contained in them.
  • Particularly suitable C 4 hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, of butadiene. When using C 4 cuts as the feed material, the hydrocarbons other than isobutene assume the role of an inert solvent.
  • Copolymerizable monomers are vinylaromatics such as styrene and ⁇ -methylstyrene, C 1 -C 4 -alkylstyrenes such as 2-, 3- and 4-methylstyrene, and 4-tert-butylstyrene, isoolefins with 5 to 10 C atoms such as 2 -Methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1 into consideration.
  • olefins which have a silyl group, such as 1-trimethoxysilylethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) silyl ] ethene, l- [tri (methoxyethoxy) silyl] propene, and l- [tri (methoxyethoxy) silyl] -2-methylpropene-2.
  • silyl group such as 1-trimethoxysilylethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) silyl ] ethene, l- [tri (methoxyethoxy) silyl] propene, and l- [tri (methoxyethoxy) silyl] -2-methylpropene-2.
  • Suitable polyisobutenes are all polyisobutenes obtainable by conventional cationic or living cationic polymerization. However, so-called "reactive" polyisobutenes which differ from low-reactive polyisobutenes in the content of terminally arranged double bonds are preferred. Reactive polyisobutenes differ from low-reactive ones in that they have at least 50 mol%, based on the total number of polyisobutene macromolecules, of terminally arranged double bonds. The reactive polyisobutenes preferably have at least 60 mol% and particularly preferably at least 80 mol%, based on the total number of polyisobutene macromolecules, of terminally arranged double bonds.
  • Preferred reactive polyisobutenes are those in which at least 60 mol%, particularly preferably at least 70 mol% and in particular at least 75 mol%, based on the total number of polyisobutene macromolecules, of the terminally arranged double bonds vinylidene double bonds ( ⁇ -olefins) are.
  • polyisobutenes with a terminal vinyl double bond ( ⁇ -olefins) are also suitable.
  • Suitable polyisobutenes are, for example, the Glissopal brands from BASF AG, e.g. Glissopal 550, Glissopal 100 and Glissopal 2300, as well as the Oppanol brands from BASF-AG, such as Oppanol BIO, B12, B15, B7 and BV.
  • Polymers from living cationic polymerization generally have a PDI of about 1.05 to 2.0.
  • the molecular weight distribution of the polyisobutenes used in the process according to the invention has a direct effect on the molecular weight distribution of the polyisobutenephosphonic acid according to the invention.
  • polyisobutenes with a low, a medium or a broad molecular weight distribution are selected.
  • the PDI value of a compound or a residue for a given M n correlates with its viscosity. Accordingly, for applications in which easy miscibility or processability with the application medium and thus a low viscosity is required, a polyisobutene residue with a PDI of preferably ⁇ 3.0 is selected. On the other hand, a higher viscosity is often desired for surface modifications in the form of coatings, so that in this case polyisobutene residues with a PDI in the range from 1.5 to 10 are preferred.
  • Polyisobutenephosphonic acid derivatives with a narrow molecular weight distribution (PDI about 1.05 to about 2.0) of the polyisobutene radical are suitable, for example, for use as detergents and dispersants in fuel and lubricant compositions, as additives in printing systems, in polymers or in monolayers for hydrophobization.
  • Polymers with an average molecular weight distribution (PDI about 1.6 to about 2 r 5) are suitable, for example, for use in certain emulsions or dispersions and for hydrophobizing basic materials, such as calcium carbonate (for example in the form of mortar), gypsum or cement, while such with a broad molecular weight distribution (PDI from about 2.1 to about 10) are suitable for use as corrosion inhibitors or also for the hydrophobization of basic materials.
  • the reaction of the polyisobutene with the phosphorus pentahalide is preferably carried out in a suitable solvent.
  • suitable solvents are aprotic solvents which are inert under the given reaction conditions and in which the reactants are at least partially soluble.
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cyclooctane
  • aromatic hydrocarbons such as benzene, Toluene and the xylenes
  • chlorinated hydrocarbons such as chloromethane, methylene chloride, chloroform, carbon tetrachloride, di- and trichloroethane and chlorobenzene
  • ethers such as diethyl ether, dimethyl ether and tert-butyl methyl ether
  • cyclic ethers such as tetrahydrofuran and dioxane
  • ketones such as acetone and ethyl methyl ketone, dimethyl sulfoxide, dimethylformamide, CS 2 and phosphorus (III) chloride and mixtures of these solvents.
  • the reaction is preferably carried out at a temperature of from -20 ° C. to the boiling point of the solvent, particularly preferably from 0 ° C. to 100 ° C. and in particular from 10 ° C. to 80 ° C.
  • the process according to the invention is preferably suitable as a starting material for polyisobutenes with terminal vinyl or vinylidene double bonds ( ⁇ -olefin) which are easily attacked by phosphorus (V) halides. Under stricter reaction conditions, however, the reaction of polyisobutenes with ⁇ -double bonds ( ⁇ -olefin) or even with saturated end groups is also readily possible.
  • the polyisobutene and the phosphorus pentahalide usually initially react to polyisobutene orthophosphonic acid tetrahalides.
  • the orthophosphonic acid tetrahalide is generally hydrolyzed. sensitive to sea and its cleaning and isolation is correspondingly complex.
  • step b1 the product of the reaction of polyisobutene and phosphorus pentahalide is therefore reacted with a suitable halogen scavenger (step b1)).
  • Halogen scavengers are to be understood in the context of the present invention as meaning those compounds which react with orthophosphonic acid tetrahalides to give phosphonic acid dihalides, ie to those polyisobutenephosphonic acids according to the invention in which IR 1 and R 2 in the phosphonic acid radical are halogen.
  • Preferred halogen scavengers are water, inorganic bases, alcohols, carboxylic acids, carboxylic anhydrides, phosphonic acids, phosphorus pentoxide and sulfur dioxide.
  • water is used as a halogen scavenger, it is preferably used in stoichiometric amounts, based on the conversion of orthophosphonic acid tetrahalide to phosphonic acid dihalide, and the reaction is carried out at the lowest possible temperatures and with the shortest possible reaction times in order to carry out the reaction at the phosphonic acid dihalide level to stop.
  • the reaction temperature is preferably about 0 to 10 ° C. Ice water is particularly preferably used.
  • the reaction takes place at preferably low temperatures, ie at temperatures in the range from -20 ° C. to 40 ° C., particularly preferably from -10 ° C. to room temperature, and with relatively short reaction times.
  • Suitable alcohols are those with 1 to 10 carbon atoms and 1 to 4 hydroxyl groups, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, cy- clohexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol and their positional isomers, also ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, glycerol, trimethylolpropane and pentaerythriol.
  • R 7 to R 10 , R 12 , k, 1 and m are as defined in formula IV.
  • R 7 and R 9 are preferably H and R 8 and R 10 are H or
  • C 1 -C 4 -alkyl in particular for H or methyl and especially for H.
  • k and m preferably stand for a number from 1 to 3 and in particular for 1.
  • 1 preferably stands for a number from 1 to 300, particularly preferably from 1 to 40, in particular from 1 to 10 and especially from 1 to 4.
  • the reaction of the orthophosphonic acid tetrahalides with carboxylic acids or carboxylic acid anhydrides generally leads initially only to the stage of the phosphonic acid dihalides.
  • the dihalides can also be further converted to the free phosphonic acids with low fatty acids, for example with C 2 -C ⁇ o-carboxylic acids.
  • the reaction with carboxylic acid anhydrides generally remains at the level of the phosphonic acid dihalides.
  • Suitable carboxylic acids are mono- and dicarboxylic acids with 1 to 10 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, oxalic acid, malonic acid and succinic acid.
  • Suitable carboxylic acid anhydrides are the anhydrides of the above-mentioned carboxylic acids, for example acetic anhydride, propionic anhydride and succinic anhydride, with acetic anhydride being preferred.
  • halogen scavengers are carboxylic anhydrides, in particular acetic anhydride, sulfur dioxide, phosphorus pentoxide and the polyisobutenephosphonic acid corresponding to the polyisobutene orthophosphonic acid tetrahalide with respect to the polyisobutene residue.
  • carboxylic anhydrides in particular acetic anhydride, sulfur dioxide, phosphorus pentoxide and the polyisobutenephosphonic acid corresponding to the polyisobutene orthophosphonic acid tetrahalide with respect to the polyisobutene residue.
  • the molar ratio of orthophosphonic acid tetrahalide to halogen scavenger is preferably 1: 1 to 1:10, particularly preferably 1: 1 to 1: 5 and in particular 1: 1 to 1: 3.
  • the molar ratio of orthophosphonic acid tetrahalide to halogen scavenger is preferably 1: 1 to 1:10, particularly preferably 1: 1 to 1: 5 and in particular 1: 1 to 1: 2 ,
  • halogen scavengers can also be used in a mixture »
  • the reaction mixture from the reaction of the polyisobutene with the phosphorus pentahalide is preferably mixed with the halogen scavenger without purification or isolation of the orthophosphonic acid tetrahalide formed, it being possible to add the mixture successively or in one portion. A gradual addition is preferred.
  • the addition of the halogen scavenger and its reaction can take place at the same temperature as the preparation of the orthophosphonic acid tetrahalide, the addition / reaction temperature depending on the particular halogen scavenger.
  • the addition and reaction with water or alcohols is preferably carried out at rather low temperatures, with water preferably in a temperature range from about 0 to 10 ° C and with alcohol preferably in a temperature range from -20 ° C to 40 ° C, if the reaction to the stage of the phosphonic acid dihalide is to be stopped.
  • a higher addition and / or reaction temperature can also be selected, for example in the range from 0 ° C. to the boiling point of the solvent used, preferably from room temperature to the boiling point of the solvent, particularly preferably from room temperature to 100 ° C. and in particular from room temperature to 80 ° C.
  • reaction mixture can then be worked up by customary methods.
  • excess halogen scavengers or their reaction products which have not yet been removed in the course of the reaction can be removed by distillation or extraction, as can any solvents used.
  • Phosphonic acid derivatives that may have been formed are, for example, digested, extracted or filtered and optionally dried, e.g. B. cleaned with sodium or magnesium sulfate.
  • reaction products of the polyisobutenorthophosphonic acid tetrahalides obtained by the reaction with the halogen scavenger, in particular the phosphonic acid dihalides, but also optionally formed phosphonic acid monoalkyl ester monohalides, phosphonic acid dialkyl esters or free phosphonic acid, are then, if desired, by reaction with water, at least one alcohol, at least one thiol and / or further derivatized (step cl)).
  • the reaction of polyisobutenephosphonic dihalides with alcohols leads to different products depending on the molar ratio of the reactants and the reaction conditions.
  • the reaction of phosphonic acid dihalides with an alcohol without simultaneous removal of the hydrogen halide formed in this way often leads to phosphonic acid monoesters.
  • the phosphonic acid dihalide is reacted with an alcoholate or if the alcohol is used in the presence of a tertiary amine, the corresponding phosphonic acid monohalide monoester is often obtained, in particular if alcohol or alcoholate is used in deficit.
  • the phosphonic acid dihalide is used in excess with an alcohol and at the same time the hydrogen halide liberated is removed or it is bound with an appropriate If acid scavengers are used, the corresponding phosphonic diesters are generally formed.
  • Suitable alcohols are the alcohols listed as halogen scavengers, furthermore alcohols with 11 to 20 carbon atoms and 1 to 4, preferably 1 to 2 hydroxyl groups and in particular 1 hydroxyl group. Examples include undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, ocadecanol, nonadecanol and eicosyl alcohol and their positional isomers.
  • the statements made with regard to preferred alcohols in the case of the halogen scavengers apply here correspondingly, polyether polyols of the formula VI.a being particularly preferred.
  • polyether polyols are preferred in which R 7 and R 9 are H and R 8 and R 10 are H or C 1 -C 4 -alkyl, in particular H or methyl and especially H, k and m are a number of 1 to 3, in particular 1, 1 is a number from 1 to 300, particularly preferably from 1 to 40, in particular from 1 to 10 and especially from 1 to 4 and R 12 is H, methyl or ethyl and especially methyl stands.
  • Amino alcohols having 2 to 20 carbon atoms, 1 to 3 amino groups and 1 to 3 hydroxyl groups are also suitable.
  • the amino alcohols preferably contain a hydroxy group and an amino group. This is preferably a tertiary amino group.
  • suitable amino alcohols are 2-aminoethanol, 2-N, N-dimethyl- and 2-, N-diethylaminoethanol, 3-aminopropanol, 3-N, N-dimethyl- and 3-N, N-diethylaminopropanol and the higher homologues of it.
  • Mercapto alcohols are also suitable, especially those in which the thio group is etherified.
  • suitable mercapto alcohols are 2-mercaptoethanol, 2- (methylmercapto) ethanol, 2- (ethylmercapto) ethanol, 3-mercapto-l-propanol, 3-mercapto-2-propanol, 3- (methylmercapto) -l-propanol, 3- (methylmercapto) -2-propanol, 3-ethyl-mercapto) -l-propanol, 3- (ethylmercapto) -2-propanol, bis- (2-hydroxyethyl) sulfide and like.
  • mercapto alcohols are preferably not used.
  • Aromatic hydroxy compounds such as optionally substituted phenols, naphthols or benzyl alcohols, are also suitable.
  • Suitable substituted aromatic alcohols are those which have 1 to 3 substituents which are selected from halogen, Ci-C ß- alkyl and Ci-C ⁇ - alkoxy.
  • Suitable alcoholates are the corresponding alkali metal, alkaline earth metal, heavy metal and ammonium alcoholates, the alkali metal alcoholates, in particular the sodium or potassium alcoholates, and the ammonium alcoholates being preferred.
  • Suitable tertiary amines are aliphatic amines, such as triethylamine, tripropylamine or ethyldiisopropylamine, aromatic amines, such as N, N-dimethylaniline, and heterocyclic amines, such as pyrrole, pyridine, 2, 6-dimethylpyridine, 2, 6-tert-butylpyridine, quinoline , DBU and DBN.
  • Suitable acid scavengers are, in particular, the above-mentioned tertiary amines, furthermore secondary amines, such as diethylamine, dipropylamine, diisopropylamine, N-methylaniline and piperidine, and also inorganic bases, such as alkali and alkaline earth metal hydroxides, alkali metal hydrogen carbonates and alkali metal carbonates.
  • the reaction is preferably carried out in a suitable solvent.
  • suitable solvents are suitable, for example aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane or cyclooctane, chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, di- or trichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, Nitrobenzene or chlorobenzene, ethers such as diethyl ether, dipropyl ether, diisopropyl ether or tert-butyl methyl ether, cyclic ethers such as tetrahydrofuren or dioxane, ketones such as acetone or methyl ethyl ketone, carboxylic acid derivatives such as ethyl acetate, methyl acetate or
  • Preferred solvents are aliphatic hydrocarbons, especially hexane, chlorinated aliphatic hydrocarbons, especially methylene chloride and Chloroform, aromatic hydrocarbons, especially toluene, and cyclic ethers, especially tetrahydrofuran, and mixtures thereof.
  • the alcohols themselves are also suitable as solvents insofar as they are liquid under the given reaction conditions and can be removed after the reaction has ended. Mixtures of such alcohols with the solvents mentioned above are also suitable.
  • the reaction of the phosphonic acid dihalides with the alcohol is preferably carried out at a temperature from -10 ° C. to the boiling point of the reaction mixture, particularly preferably from -10 ° C. to 30 ° C.
  • the molar ratio of phosphonic acid dihalide to the alcohol used depends on whether a monoester, a diester or a mixed diester is to be produced. If a monoester or a mixed diester is to be prepared, dihalide and alcohol are used in a molar ratio of preferably 1: 0.8 to 1.5, particularly preferably 1: 0.8 to 1.2 and in particular approximately 1: 1 used. If diesters of the same alcohols are to be produced, the molar ratio of dihalide to alcohol is preferably 1: 1.8 to 3, particularly preferably 1: 1.8 to 2.5 and in particular approximately 1: 2.
  • the reaction of the phosphonic acid dihalide with the alcohol takes place, for example, in such a way that the dihalide and, if appropriate, the tertiary amine or an acid scavenger different therefrom are placed in a solvent and the alcohol is then added.
  • the reaction mixture is worked up by customary methods, for example by distillative or extractive removal of the solvent, any excess alcohol and / or acid scavenger, if appropriate after filtering off its reaction products.
  • Phosphonic acid dihalides can also be reacted with an alcohol and an amine in phosphonic acid monoester monoamides, for example by first reacting the dihalide with the alcohol as described above to form the phosphonic acid onoester monohalide or optionally further to the phosphonic acid monoester and reacting the monoester halide or the monoester with the amine or by reversing the dihalide is first reacted with the amine as described below to form the phosphonic acid monohalogenide or, if appropriate, further to the phosphonic acid monoamide and then the reaction product with the alcohol is converted into the
  • Phosphonic acid monoester monoamide transferred.
  • the dihalide can also be reacted with a mixture of alcohol and amine become.
  • suitable and preferred alcohols, amines, reactant ratios and reaction conditions reference is made to the comments already made and with regard to the amines to the following comments.
  • phosphonic acid dihalides can be converted into mixed phosphonic acid (0, S) diesters with an alcohol and a thiol.
  • suitable and preferred thiols reference is made to the following explanations. However, preferably no thiols are used.
  • Amides of two different amines are obtained, for example, by first reacting the polyisobutenephosphonic acid dihalide with a first amine to give the corresponding polyisobutenephosphonic acid monohalide monoamide and then reacting this with a second amine to give the mixed diamide.
  • Suitable primary amines are both mono- and polyamines with 1 to 20 carbon atoms.
  • Primary amines are amines NR a R b R c in which two of the radicals R a , R b or R c are H.
  • Suitable primary monoamines are methylamine, ethyl laminate, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, heptadececamine
  • Nonadecylamine Eicosylamin as well as Cyclooctylamin and Cyclodecylamin.
  • Hydroxy- or alkoxy-substituted amines such as 2-hydroxyethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-hydroxypropylairtine, 3-methoxypropylamine, 3-ethoxypropylamine and the like are also suitable.
  • Preferred primary monoamines are ethylamine, butylamine, 2-ethylhexylamine and 2-hydroxyethylamine.
  • Primary aromatic amines such as aniline are also suitable.
  • Suitable primary polyamines are those of the formula VI.b.
  • R 7 to R 13 and k and m are as defined in formula IV and 1 is a number from 0 to 1000.
  • R 7 and R 9 are preferably H.
  • R 8 and R 10 are preferably H or -CC 4 alkyl, in particular H or methyl and especially H.
  • R 11 is preferably H.
  • k and m are preferably a number from 1 to 3, in particular 1 »1, preferably stands for a number from 0 to 300, particularly preferably from 0 to 40, in particular from 0 to 10 and especially from 0 to 4.
  • R 12 and R 13 are preferably H.
  • Particularly preferred primary polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine as well as 3-N, N-dimethylaminopropylamine and 3-N, N-diethylaminopropylamine.
  • Secondary amines are both mono- and polyamines with 1 to 20 carbon atoms. Secondary amines are amines NR a R b R c in which one of the radicals R a , R b or R c is H.
  • Suitable secondary monoamines are, for example, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-tert-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, di (2-ethylhexyl) amine, dinonylamine and didecylamine and N-methylamine , N-ethylcyclohexylamine and dicyclohexylamine, also piperidine, piperazine and morphine.
  • Preferred secondary monoamines are dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dipentylamine, dihexylamine and di- (2-ethylhexyl) amine.
  • Hydroxy- or alkoxy-substituted amines such as bis (2-hydroxyethyl) amine, bis (2-methoxyethyl) amine and bis (2-ethoxyethyl) amine, are also suitable.
  • Secondary aromatic amines such as N-methylaniline or diphenylamine, are also suitable.
  • Suitable secondary polyamines are those of the formula
  • R 14 represents a radical of the formula VII
  • R 7 to R 11 and k and m are as defined in formula IV,
  • R 12 represents H or -CC 6 alkyl
  • R 13 represents Ci-Cg-alkyl
  • R 15 represents Ci-Cg-alkyl or a radical of the formula VII.
  • R 7 and R 9 are preferably H.
  • R 8 and R 10 are preferably H or C ⁇ -C 4 alkyl, in particular H or methyl, and especially H.
  • R 11 is preferably H.
  • k and m are preferably for a number from 1 to 3, in particular for 1. 1 preferably stands for a number from 0 to 300, particularly preferably from 0 to 40, in particular from 0 to 10 and especially from 0 to 4.
  • R 15 preferably stands for a radical of formula VII.
  • Particularly preferred secondary amines are diethylamine, diisopropylamine, bis (2-hydroxyethyl) amine and bis (3-N ', N'-dimethylamino-propyl) amine.
  • Primary amines in particular primary polyamines, are preferably used in the process according to the invention.
  • the reaction is preferably carried out in a suitable solvent.
  • suitable and preferred solvents are the solvents mentioned for the reaction of phosphonic acid dihalide with an alcohol.
  • the reaction is preferably carried out at a temperature from 0 ° C. to the boiling point of the reaction mixture, particularly preferably from 0 ° C. to 50 ° C.
  • the molar ratio of phosphonic acid dihalide to amine depends on the desired reaction product and on the type of amine. If a phosphonic acid monohalide monoamide is to be produced, the molar ratio of dihalide to secondary amine is preferably 1: 1.6 to 3, particularly preferably 1: 1.6 to 2.4 and in particular approximately 1: 2. The molar ratio of dihalide to primary amine is preferably 1: 1.6 to 3, particularly preferably preferably 1: 1.6 to 2.4. If a diamide is to be produced, the molar ratio of dihalide to secondary amine is preferably 1: 1.8 to 6, particularly preferably 1: 1.8 to 5 and in particular approximately 1: 4. The molar ratio of dihalide to primary amine is preferably 1: 1.8 to 6, particularly preferably 1: 1.8 to 5.
  • reaction of the phosphonic acid dihalide with an amine takes place, for example, by introducing the dihalide in a solvent and then adding the amine to the mixture. After the reaction has ended, the reaction mixture is worked up by customary methods, for example by distillative or extractive removal of the solvent and any excess amine and filtration of the ammonium salts formed.
  • Suitable thiols are those having 1 to 20 carbon atoms, such as methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl r octyl, nonyl or decylthiol and the higher homologs and positional isomers.
  • Polythioether polythiols of the formula VI.c are also suitable
  • R 7 to R 12 and k, 1 and m are as defined in formula IV.
  • R 7 and R 9 are preferably H.
  • R 8 and R 10 are preferably H or -CC 4 alkyl, in particular H or methyl and especially H.
  • k and m are a number from 1 to 3, in particular for 1.
  • 1 is preferably a number from 1 to 300, particularly preferably from 1 to 40, in particular from 1 to 10 and especially from 1 to 4.
  • aromatic thiols for example thiophenol itself and thiophenols which have 1 to 3 substituents which are selected from halogen, C 1 -C 6 -alkyl and C C-C 6 -alkoxy.
  • the reaction is preferably carried out in a suitable solvent.
  • suitable and preferred solvents are the solvents mentioned for the reaction of phosphonic acid dihalide with an alcohol.
  • the reaction is preferably carried out at a temperature of from -20 ° C. to the boiling point of the reaction mixture, particularly preferably from 0 ° C. to 50 ° C.
  • the molar ratio of phosphonic acid dihalide to the thiol used depends on whether a mono-, a dithioester or a mixed dithioester is to be prepared. If a monothioester or a mixed dithioester is to be prepared, dihalide and thiol are used in a molar ratio of preferably 1: 0.8 to 1.5, particularly preferably 1: 0.8 to 1.2 and in particular approximately 1: 1 used. If dithioesters of the same thiols are to be prepared, the molar ratio of dihalide to thiol is preferably 1: 1.8 to 3, particularly preferably 1: 1.8 to 2.5 and in particular approximately 1: 2.
  • Polyisobutenephosphonic acids which are either produced directly from the corresponding orthophosphonic acid tetrahologenides or from phosphonic acid dihalides, can in turn be derivatized. For example, they can be derivatized to the corresponding salts by reaction with alkali metal and ammonium hydroxides or carbonates, with alkaline earth carbonates and with heavy metal carbonates or acetates.
  • the heavy metal salts especially the lead and silver salts, can be converted to the corresponding esters by reaction with an alkyl or aryl halide.
  • the phosphonic acid esters can also be obtained by reacting the corresponding phosphonic acids with diazoalkanes.
  • the phosphonic acid esters can be obtained by reacting the phosphonic acids or their salts with dimethyl sulfate.
  • the phosphonic acid dihalides can be converted into other phosphonic acid dihalides by means of halogen exchange.
  • a polyisobutenephosphonic dichloride can be used Reaction with an alkali fluoride, zinc fluoride, sodium hexafluorosilicate, antimony (III) fluoride or hydrogen fluoride can be converted into the corresponding phosphonic acid difluoride. If two phosphonic acid dihalides with different halogen atoms are reacted with one another, mixed phosphonic acid dihalides are obtained, for example.
  • the orthophosphonic acid tetrahalide obtained in the reaction of a polyisobutene with a phosphorus pentahalide is reacted with water, at least one alcohol, at least one amine and / or at least one thiol (step b2)) »
  • the reaction is preferably carried out in such a way that the reaction is not stopped at the stage of the phosphonic acid dihalide, but instead the derivatization products of the phosphonic acid dihalide listed above are formed directly.
  • the first embodiment in which the orthophosphonic acid tetrahalide is first reacted with a halogen scavenger (variant bl) and cl)), is particularly preferred.
  • the polyisobutenephosphonic acid derivatives according to the invention which are obtainable by the process according to the invention and by other processes can generally be derivatized in many ways.
  • the phosphonic acid can be reacted with a phosphorus oxyhalide or with a phosphorus pentahalide to give the corresponding phosphonic acid dihalide, which, as above described can be further derivatized.
  • Phosphonic acid monoesters and phosphonic acid monoamides can also be converted into a phosphonic acid halide by reaction with a phosphorus oxyhalide or with a phosphonic acid pentahalide, which can also be derivatized as described above.
  • the phosphonic acid itself can also be converted into the phosphonic acid mono- or diamide by reaction with an amine.
  • the phosphonic acid mono- or diamides read can be converted to the phosphonic acid mono- or diesters by reaction with an alcohol.
  • the diesters of phosphonic acid can be converted into the corresponding phosphonamides by reaction with an amine.
  • polyisobutenephosphonic acids according to the invention can also be obtained by other processes.
  • polyisobutenes terminated with an alkyl halide group can be converted to the polyisobutenorthophosphonic acid tetrahalides by reaction with a phosphorus trihalide and an aluminum trihalide which corresponds to the halogen atom.
  • a phosphorus trihalide and an aluminum trihalide which corresponds to the halogen atom.
  • Another object of the present invention is a composition containing polyisobutenephosphonic acid, obtainable by
  • step bl) optionally reacting the reaction product obtained in step bl) with water, at least one alcohol, at least one thiol and / or at least one amine, or
  • step b2) reaction of the reaction product obtained in step a) with water, at least one alcohol, at least one thiol and / or at least one amine.
  • the statements made above apply to suitable polyisobutenes, halogen scavengers, alcohols, amines and thiols and suitable or preferred embodiments of the process.
  • no thiols are used in step c1) and in step b2), ie the polyisobutenephosphonic acid-containing composition according to the invention preferably contains no polyisobutenephosphonic thioesters, ie no polyisobutenephosphonic acids in which IR 1 or R 2 are SR 3 in the rest ,
  • the expression “essentially” means that the composition according to the invention contains at most 1000 ppm, particularly preferably at most 100 ppm, in particular at most 50 ppm and especially at most 5 ppm, polyisobutenephosphonic acid thioester.
  • the composition according to the invention preferably contains no phosphonic acid in which the radicals R 3 and R 4 are C 2 -C 4 o 0 rj-alkyl which is interrupted by an S group.
  • the composition containing polyisobutenephosphonic acid according to the invention has the lowest possible sulfur content, eg. B. a sulfur content of at most 20 mol%, preferably at most 10 mol%, particularly preferably at most 5 mol%, more preferably at most 1000 ppm, even more preferably at most 500 ppm, in particular from at most 100 ppm , specifically from a maximum of 50 ppm sulfur and even more specifically from a maximum of 5 ppm.
  • the indication of the sulfur content does not relate to elemental sulfur, but quite generally to sulfur-containing compounds, which are calculated back to their sulfur content.
  • the polyisobutenephosphonic acid-containing composition according to the invention optionally contains further reaction products which result from the production process.
  • reaction products include, for example, phosphonimides, esters of polyesterified polyols and much more.
  • This composition which may consist of several components, is suitable for numerous applications and does not have to be laboriously cleaned.
  • the present invention also relates to a composition with a sulfur content of at most 1000 ppm, preferably at most 50 ppm, particularly preferably at most 10 ppm and in particular at most 5 ppm of sulfur, comprising at least one polyisobutenephosphonic acid according to the invention and at least one carrier.
  • the polyisobutenephosphonic acid according to the invention is selected from those in which, in the rest of the formula I, neither R 1 nor R 2 stand for SR 3 and furthermore neither R 3 nor R 4 stand for a C 2 -C 4 ooo-alkyl radical which a grouping S is interrupted.
  • Suitable carriers are all customary inert solid or liquid carrier materials for surface-active substances.
  • Suitable solid carriers are, for example, customary large surface-active substances, such as activated carbon, alumina, silica gel, diatomaceous earth, talc, kaolin, clays or silicates.
  • polymers eg polymers of mono- and diolefins, such as polyethylene and polypropylene, polymers of aromatics , such as polystyrene, poly- (p-methylstyrene) and poly (- ethylstyrene), and copolymers of these olefins and / or aromatics and mixtures of the aforementioned homo- and copolymers are suitable.
  • Mixtures such as dispersing and suspending agents, are also suitable as carriers.
  • Suitable inert carriers are customary inert solvents, for example the aprotic solvents mentioned in connection with the process according to the invention, and carrier oils which are described in more detail below.
  • composition according to the invention preferably contains the polyisobutenephosphonic acid in an amount of 0.01 to 99% by weight, particularly preferably 0.1 to 99% by weight, based on the total weight of the composition.
  • the present invention furthermore relates to the use of the polyisobutenephosphonic acid according to the invention or the polyisobutenephosphonic acid-containing compositions according to the invention for the surface modification of. organic or inorganic material.
  • the statements made above regarding the polyisobutenephosphonic acid according to the invention or the respective polyisobutenephosphonic acid-containing compositions apply accordingly.
  • the choice of suitable polyisobutenephosphonic acids depends in each case on the particular intended use and application medium and can be determined in a particular case by a person skilled in the art.
  • the polyisobutenephosphonic acid according to the invention or the polyisobutenephosphonic acid-containing compositions according to the invention is used as a corrosion inhibitor, friction reducer, emulsifier, dipergator, adhesion promoter, wetting agent, wetting agent, flushing agent or printing ink additive, in addition to improving the dyeability, printability, adhesive properties or impact resistance, in particular of plastics , e.g. B. the polymers mentioned in the polymer composition according to the invention below, and used as an additive or printing ink additive in printing processes.
  • polyisobutenephosphonic acid according to the invention or the polyisobutenephosphonic acid-containing compositions according to the invention are intended to improve the rheological properties, eg. B. the viscosity, the colorant composition.
  • these should the tack, the tack stability, the cash on delivery Improve color, water absorption and / or impact resistance of the printed substrate.
  • optical properties, e.g. B. gloss, the printed substrate can be improved by their use.
  • Organic materials suitable for surface modification with the polyisobutenephosphonic acid according to the invention or with the compositions containing polyisobutenephosphonic acid according to the invention are, for example, plastics, in particular the polymers mentioned in the polymer composition according to the invention below, especially in the form of plastics, cellulose, for example in the form of Paper or cardboard, textiles made from natural or synthetic fibers, leather, wood, mineral oil products such as fuels, fuels or lubricants, and additives for such mineral oil products such as lubricity improvers and cold flow improvers.
  • Suitable inorganic materials are, for example, inorganic pigments, metal, glass and basic inorganic materials, such as cement, gypsum or calcium carbonate.
  • surface modification is understood to mean the change in the interface properties of the media mixed with the polyisobutenephosphonic acid derivatives according to the invention or the composition containing polyisobutenephosphonic acid.
  • Interfaces are surfaces that separate two immiscible phases (gas-liquid, gas-solid, liquid-solid, liquid-liquid, solid-solid). This includes the adhesive, adhesive or sealing effect, the flexibility, scratch or fracture resistance, the wettability and the wettability, sliding properties, friction, corrodibility, dyeability, printability or gas permeability etc. of the application media.
  • the polyisobutenephosphonic acid according to the invention or the polyisobutenephosphonic acid-containing compositions according to the invention is preferably used as a corrosion inhibitor, friction reducer, emulsifier, dispersant, adhesion promoter, wetting agent, wetting agent, flushing agent or printing ink additive. They are particularly preferably used as detergents, dispersants and / or corrosion inhibitors, in particular in fuel and lubricant additives or in fuel and lubricant compositions.
  • polyisobutenephosphonic acids are particularly preferably used in which, in the phosphonic acid radical of the formula IR 1 and R 2, independently of one another are OR 3 or NR 3 R 4 .
  • polyisobutenephosphonic acid-containing compositions are used which have the lowest possible sulfur content, for example those with at most 1000 ppm, preferably at most 500 ppm, particularly preferably at most 100 ppm, in particular at most 50 ppm and especially at most 5 ppm sulfur. Salts of these polyisobutenephosphonic acids are also suitable.
  • polyisobutenephosphonic acid according to the invention or the polyisobutenephosphonic acid-containing compositions according to the invention is also preferably used according to the invention as an ink additive in printing processes, in particular for paper, or to improve the surface behavior of plastics, such as polypropylene, in particular the dyeing behavior.
  • the present invention also relates to a fuel and lubricant additive containing at least one polyisobutenephosphonic acid according to the invention or a polyisobutenephosphonic acid-containing composition according to the invention.
  • preferred polyisobutenephosphonic acids are those in which IR 1 and R 2 in the phosphonic acid residue independently of one another represent OR 3 , SR 3 or NR 3 R 4 .
  • fuel additives particularly preferably contain polyisobutenephosphonic acids in which IR 1 and R 2 in the phosphonic acid xest independently of one another represent OR 3 or NR 3 R 4 .
  • preferred polyisobutenephosphonic acid-containing compositions are those which have the lowest possible sulfur content, for example those with at most 1000 ppm, preferably at most 500 ppm, particularly preferably at most 100 ppm, in particular at most 50 ppm and especially at most 5 ppm, sulfur.
  • the statements made above regarding the polyisobutenephosphonic acid according to the invention or the polyisobutenephosphonic acid-containing composition apply accordingly.
  • the present invention furthermore relates to a fuel and lubricant composition
  • a fuel and lubricant composition comprising a main amount of a hydrocarbon fuel or a lubricant and a polyisobutenephosphonic acid according to the invention or a polyisobutenephosphonic acid-containing composition according to the invention, each of which is defined as above, and optionally at least one further additive.
  • the statements made above regarding the polyisobutenephosphonic acid according to the invention or the polyisobutenephosphonic acid-containing composition according to the invention apply here correspondingly.
  • fuel also includes fuels, such as heating oils, in addition to the fuels in the actual sense.
  • fuels in the strict sense all commercially available petrol and diesel fuels are used. All commercially available heating oils can be used as fuels.
  • Preferred polyisobutenephosphonic acids are also those in which R 1 and R 2 independently of one another represent OR 3 , SR 3 or NR 3 R 4 .
  • preferred polyisobutenephosphonic acid-containing compositions are those which have the lowest possible sulfur content, for example those with at most 1000 ppm, preferably at most 500 ppm, particularly preferably at most 100 ppm, in particular at most 50 ppm and especially
  • the fuel and lubricant compositions according to the invention preferably contain the polyisobutenephosphonic acid according to the invention in an amount of from 5 to 5000 ppm, particularly preferably from 20 to 1000 ppm and in particular from 20 to 500 ppm.
  • the present invention relates to an additive concentrate containing an inventive polyisobutenephosphonic acid or an inventive polyisobutenephosphonic
  • polyisobutenephosphonic acids are those in which IR 1 and R 2 in the phosphonic acid residue independently of one another represent OR 3 , SR 3 or NR 3 R 4 .
  • fuel additive is a polyisobutenephosphonic acids that are those in which IR 1 and R 2 in the phosphonic acid residue independently of one another represent OR 3 , SR 3 or NR 3 R 4 .
  • fuel additive is a polyisobutenephosphonic acids.
  • 30 tetrates particularly preferably contain polyisobutenephosphonic acids in which IR 1 and R 2 in the phosphonic acid residue independently of one another represent OR 3 or NR 3 R 4 .
  • preferred compositions containing polyisobutenephosphonic acid are those which have the lowest possible sulfur content, for example
  • the polyisobutenephosphonic acid is preferably present in the additive concentrate according to the invention in an amount of 0.1 to 80% by weight, particularly preferably 10 to 70% by weight and in particular 30 to 60% by weight, based on the weight of the concentrate , Suitable diluents
  • solvents are aliphatic and aromatic hydrocarbons, such as solvent naphtha. Should the additive concentrates according to the invention be used in low-sulfur diesel or petrol fuels low-sulfur hydrocarbons are preferred as diluents in the additive concentrate.
  • the fuel and lubricant compositions according to the invention and the additive concentrates optionally contain, in addition to the polyisobutenephosphonic acid, other customary fuel and lubricant additives, preferably the additives described below:
  • Fuel and lubricant compositions or in the concentrates are to be mentioned, further additives with detergent action or with valve seat wear-inhibiting action, these containing at least one hydrophobic hydrocarbon residue with a number average molecular weight (M ⁇ ) of 85 to 20,000 and at least one polar grouping , selected from
  • Nitrogen atom has basic properties, or are terminated by carbamate groups,
  • Such additives based on reactive polyisobutene, which from the polyisobutene, which can contain up to 20 wt .-% n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylene pentamine can be produced, are known in particular from EP-A 244 616.
  • additives containing monoamino groups (a) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as are described in particular in DE-A 196 20 262.
  • Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (c) are preferably copolymers of C -C 4 Q-01efins with maleic anhydride with a total molecular weight of 500 to 20,000, the carboxyl groups of which are wholly or partly to the alkali metal or alkaline earth metal salts and a remaining one The rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are known in particular from EP-A 307 815.
  • Such additives, as described in WO-A 87/01126, can advantageously be used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Additives containing polyoxy-C 2 -C 4 -alkylene groupings (d) are preferably polyethers or polyetheramines which are obtained by reacting C 2 -C -cgo-alkanols, Cg- to C 30 -alkanediols, mono- or di-C 2 -C 3 o-alkylamines, -C-C 30 -alkylcyclohexanols or -C-C 3 Q-alkylphenols with 1 to 30 mol ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 416.
  • polyethers such products also meet carrier oil properties »Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates as well as the corresponding reaction products with ammonia.
  • Additives containing carboxylic acid ester groups (e) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm 2 at 100 ° C., as described in particular in DE-A 38 38 918 are.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol.
  • Such products also have carrier oil properties.
  • Derivatives with aliphatic polyamines such as ethylene diamine, diethylene triamine, triethylene tetramine or tetraethylene pentamine are of particular interest.
  • Such gasoline fuel additives are described in particular in US Pat. No. 4,849,572.
  • Additives containing groups (g) produced by conventional Mannich reaction of phenolic hydroxyl groups with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and primary mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentaminyl or dimethylamine ,
  • polyisobutene Mannich bases are described in particular in EP-A 831 141, to which reference is hereby made in full.
  • Suitable solvents or diluents are the diluents mentioned above for the concentrates according to the invention, for example aliphatic and aromatic hydrocarbons, such as solvent naphtha.
  • additive components that can be combined with the polyisobutenephosphonic acid according to the invention are, for example, conventional corrosion inhibitors, such as, for. B. based on film-forming ammonium salts of organic carboxylic acids or heterocyclic aromatics, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienylmanganese tricarbonyl, lubricity improvers (lubricity additives) such as certain fatty acids, alkenylsuccinic acid esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or hydroxyacetamides Dyes (markers). If necessary
  • Carrier oils can also be mentioned as further customary components.
  • mineral carrier oils in particular those of the viscosity class "Solvent Neutral (SN) 500 to 2000
  • polyalkanol alcohol polyetheramines as described, for example, in DE-199 16 512.2.
  • Another object of the present invention is a polymer composition containing a polymer and at least one polyisobutenephosphonic acid according to the invention.
  • the statements made above with regard to suitable and preferred polyisobutenephosphonic acids apply accordingly here.
  • both R 1 and R 2 in the phosphonic acid residue I of the polyisobutenephosphonic acid are OR 3 and especially OH.
  • Suitable polymers are, for example, polymers of mono- and diolefins and of aromatics and copolymers of these monomers.
  • Suitable polymers of mono- or diolefins are e.g. B. polypropylene, polyisobutene, polybutene-1, poly-4-methyl-pentene-1, polyisoprene or polybutadiene and polymers of cycloolefins, such as. B. of cyclopentene or norbornene; also polyethylene (which may optionally be cross-linked), e.g. B.
  • High density polyethylene high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low-density polyethylene Density (LLDPE), branched low density polyethylene (VLDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultra high molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low-density polyethylene Density
  • VLDPE branched low density polyethylene
  • copolymers of mono- and diolefins with one another are suitable, for.
  • B ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutene copolymers, ethylene-butene-1 copolymers, ethylene Hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutene-isoprene copolymers, and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; also mixtures of such copolymers among each other and with the aforementioned polymers, e
  • Suitable polyaromatics are, for example, polystyrene, poly- (p-methylstyrene) and poly- ( ⁇ -methylstyrene).
  • Copolymers of styrene or ⁇ -methylstyrene with dienes for. B. styrene butadiene; Mixtures of high impact strength from styrene copolymers and another polymer, e.g. B »a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene, e.g. B. styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
  • Graft copolymers of styrene or ⁇ -methylstyrene are also suitable, e.g. B. styrene on polybutadiene or styrene on polybutadiene-styrene copolymers.
  • binary and polynary blends of the aforementioned homo- and copolymers are suitable.
  • polyolefins in particular polyethylene and polypropylene and especially polypropylene »
  • the polymer composition according to the invention can be in the form of a particle, line, sheet or three-dimensional structure.
  • particle structure includes particles with a particle size of 1 nm to 10 mm, which are preferably dispersible or dispersed in a medium.
  • Line-shaped structure means in particular fibers, filaments, yarns, threads and the like.
  • Sheet-like structures are in particular woven fabrics, knitted fabrics, felts, nonwovens, nonwovens, foils and comparable two-dimensional structures. Foils are preferred.
  • Three-dimensional structures are generally shaped bodies of various dimensions.
  • Preferred configurations of the polymer composition according to the invention are sheet-like structures, especially foils, and moldings. Films, in particular polypropylene films, are particularly preferred.
  • the polyisobutenephosphonic acid is present in the polymer composition according to the invention in an amount of preferably 0.01 to 99% by weight, particularly preferably 0.1 to 99% by weight, based on the total weight of the polymer composition.
  • the polymer can be equipped with the polyisobutenephosphonic acid, for example, by the polymer, which is already in the form of a particle, line, sheet or three-dimensional structure, with a solution of the polyisobutenephosphonic acid in a manner customary for the type of structure, eg. B. treated by rinsing, dipping, spraying, splashing or similar methods.
  • the polyisobutenephosphonic acid is preferably added to the polymer, which is not yet in the form of the desired structure, and only then is the structure produced.
  • the polymer is mixed as a solid or in a softened form with the polyisobutenephosphonic acid and then the finished plastic material is processed by customary methods, for. B. to films, for example by extrusion, or to fiber materials, for example by melt spinning.
  • the polymer composition according to the invention in particular has a significantly better dyeing behavior than a corresponding polymer composition which does not contain the polyisobutenephosphonic acid according to the invention.
  • the present invention furthermore relates to a printing ink composition
  • a printing ink composition comprising at least one printing ink and at least one polyisobutenephosphonic acid according to the invention.
  • suitable and preferred polyisobutenephosphonic acids apply correspondingly here.
  • both R 1 and R 2 in the phosphonic acid residue I of the polyisobutenephosphonic acid stand for a residue OR 3 , where R 3 does not stand for H.
  • R 3 is a radical of the formula IV.a, where 1 is a number from 1 to 4.
  • Printing inks are understood to mean solid, pasty or liquid colorant preparations which are used in printing presses. Suitable printing inks depend on the printing processes in which they are used and on the material to be printed.
  • the material to be printed can be both absorbent and non-absorbent and one-dimensional in its extent, e.g. B. fibrous, two-dimensional (flat) or three-dimensional, z. B. cylindrical or conical, »Flat materials are such.
  • B. fibrous, two-dimensional (flat) or three-dimensional, z. B. cylindrical or conical, »Flat materials are such.
  • Cylindrical or conical materials are e.g. B. hollow body per, for example cans.
  • Preferred materials are paper and plastic films.
  • Suitable plastics are the polymers mentioned in the polymer composition according to the invention.
  • the ink composition according to the invention can be used in all common printing processes, such as. B. high pressure, such as letterpress and flexographic printing, planographic printing, such as offset printing, lithographic printing and light printing, gravure printing, such as squeegee printing and steel engraving, as well as printing, such as screen printing, frame, film and stencil printing.
  • the printing ink composition according to the invention is preferably used in offset printing.
  • Suitable colorants are both pigments and dyes. Suitable pigments and dyes are all colorants customary in the respective printing process.
  • the printing ink composition according to the invention generally contains a colorant composition customary for the respective printing process and a polyisobutenephosphonic acid according to the invention.
  • customary colorant compositions generally contain binders, which are usually referred to as printing varnishes, and additives, such as drying agents, diluents, wax dispersions and, if appropriate, catalysts or initiators for radiation drying.
  • binders which are usually referred to as printing varnishes
  • additives such as drying agents, diluents, wax dispersions and, if appropriate, catalysts or initiators for radiation drying.
  • the composition is determined by the printing process, the substrate to be printed and the quality sought in printing in terms of appearance, such as gloss, opacity, color tone and transparency, and physical properties, such as water, grease, solvent resistance, abrasion resistance and laminability, in selected individual.
  • varnishes for pasty offset, book and screen printing inks such.
  • Suitable varnishes for flexographic, gravure and screen printing inks are e.g.
  • the colorant composition is equipped with the polyisobutenephosphonic acid, for example, by intimately mixing these components. Alternatively, all individual components the colorant composition are mixed together with the polyisobutenephosphonic acid to form the printing ink composition according to the invention. However, individual components of the colorant composition can first be mixed with the polyisobutenephosphonic acid and then this mixture can be mixed with the remaining components.
  • the polyisobutenephosphonic acids according to the invention have excellent long-term storage stability and effectiveness in surface modification, for example for hydrophobizing organic materials, such as textiles or plastics, or of inorganic materials, such as gypsum, cement, calcium carbonate (for example in the form of mortar) or metals as corrosion inhibitors, Rei - Exercise reducers, emulsifiers or dispersants, adhesion promoters, wetting agents, network inhibitors, escape agents or printing ink additives as well as to improve the dyeability of organic materials, in particular plastics, and to improve the rheological and printing properties of printed material, in particular paper.
  • Low-sulfur or sulfur-free polyisobutenephosphonic acids or compositions containing polyisobutenephosphonic acid are particularly preferred for use in fuel and lubricant compositions.
  • the dyeability of polypropylene additized with polyisobutenephosphonic acids according to the invention with a cationic dye was investigated.
  • polypropylene Metocene ® X 50248 of the company Basell a product made by metallocene catalysis Ho- mopropylen was used.
  • the tests were carried out in a twin-screw extruder at a housing temperature of 180 ° C. and 200 rpm.
  • the nozzle performance was 1x4 mm.
  • the throughput was 5 kg / h, the polyisobutenephosphonic acids A and B being added at a throughput of 250 g / h.
  • the metering pump was operated at 100 to 200 g / h. In each case 5% by weight of the polyisobutenephosphonic acids A and B according to the invention were added to the polypropylene granules.
  • Plates were pressed from each granulate obtained after extrusion (approx. 160 x 160 x 2 mm; weight approx. 46 g; pressing time 4 minutes at 220 ° C., 1 minute each at 50, 100, 150 and 200 bar) .
  • Corresponding test panels were also produced from non-additive polypropylene granules. Coloring tests were carried out on the plates obtained.
  • the cationic dye Basacryl Red X-BL 300% was used as the dye.
  • Basacryl Red X-BL 300% was used as the dye.
  • Polyisobutenephosphonic acid triethylene glycol monomethyl ether diester C based on Glissopal 550 was used as polyisobutenephosphonic acid in an amount of 1% by weight, based on the total amount of the color composition.
  • a conventional printing ink called Webking 3020 Magenta from BASF AG was used as the test ink, which in addition to the colorant contained customary auxiliaries, such as varnishes.
  • Viscosity, tack, tack stability, water absorption and delta torque were determined by conventional methods known to the person skilled in the art.
  • the target viscosity was 35 to 42 Pas.
  • the target tack was 145 to 175.
  • the color additized with the polyisobutenephosphonic ester according to the invention has a more favorable set-off behavior than a non-additized color »
  • the ink additized according to the invention had no printing disadvantages.
  • a 0.2% solution of a polyisobutylphosphonic acid was prepared by mixing 898 parts by weight of distilled water, 100 parts of Emulan® HE 50 (nonionic emulsifier, BASF Aktienges., Ludwigshafen) and two parts of polyisobutylphosphonic acid from Example 2.1. 0
  • the breakthrough potential (in 0.6 mol / 1 NaCl and total Ca (0H) 2 ), the corrosion current and the polarization resistance were determined as basic electrochemical parameters for the sheets prepared according to 3.3.

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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention concerne des acides phosphoniques de polyisobutylène et leurs dérivés, un procédé de production de ces composés, et leur utilisation.
EP04709595A 2003-02-11 2004-02-10 Acide phosphonique de polyisobutylene et ses derives Withdrawn EP1594905A2 (fr)

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DE10305623 2003-02-11
DE10305623A DE10305623A1 (de) 2003-02-11 2003-02-11 Polyisobutenphosphonsäure und ihre Derivate
PCT/EP2004/001230 WO2004072024A2 (fr) 2003-02-11 2004-02-10 Acide phosphonique de polyisobutylene et ses derives

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005021093A1 (de) * 2005-05-06 2006-11-09 Basf Ag Verfahren zur Herstellung von Polyisobutyl-substituierten Cyclohexanolen
WO2006128796A2 (fr) * 2005-05-30 2006-12-07 Basf Aktiengesellschaft Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges et procedes pour colorer de telles compositions ou realiser une impression sur ces dernieres
DE102007060651B3 (de) * 2007-12-15 2009-06-25 Clariant International Limited Asphalten-Dispergatoren auf Basis von Phosphonsäuren
EP3505574B1 (fr) * 2017-12-28 2021-05-12 Imerys USA, Inc. Copolymères amphiphiles comme modificateurs de surface pour la production de poudres de carbonate de calcium améliorées
CN116178602B (zh) * 2022-12-12 2024-05-03 珠海格力电器股份有限公司 粘度指数改进剂、冷冻机油及工作流体组合物

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL98888C (fr) * 1957-01-30
GB852382A (en) * 1957-10-09 1960-10-26 Lubrizol Corp Process for the modification of olefin polymers
FR1218659A (fr) * 1957-12-27 1960-05-12 Union Carbide Corp élastomères contenant du phosphore
US3259656A (en) * 1963-07-29 1966-07-05 Lubrizol Corp Reaction of phosphorus trichloride with chlorinated hydrocarbon polymers of lower mono-olefins
US3320115A (en) * 1964-09-03 1967-05-16 Hercules Inc Process for bonding polyolefin to metal and article of manufacture
US4031017A (en) * 1976-04-07 1977-06-21 Standard Oil Company (Indiana) Phosphosulfurized hydrocarbon modified N-(hydroxy and alkyl-substituted benzyl) alkylene polyamine
US4244828A (en) * 1978-11-13 1981-01-13 Texaco Inc. Lubricating oil composition
US4578178A (en) * 1983-10-19 1986-03-25 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a petroleum hydrocarbon or petrochemical
US4778480A (en) * 1986-10-03 1988-10-18 Texaco Inc. Color stabilization additives for diesel fuel containing rare earth metals and oxygenated compounds
US5399276A (en) * 1989-07-26 1995-03-21 Mobil Oil Corporation Lubricant composition containing the reaction product of an olefinic compound and an alkoxylated-amine-phosphite
US5259656A (en) * 1992-01-31 1993-11-09 Carroll Larry W Golf cart enclosure
DE10142285A1 (de) * 2001-08-29 2003-03-20 Basf Ag Polymerzusammensetzung, enthaltend wenigstens ein mittelmolekulares reaktives Polyisobuten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004072024A2 *

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WO2004072024A3 (fr) 2004-11-04
US20060148662A1 (en) 2006-07-06
JP2006517241A (ja) 2006-07-20
WO2004072024A2 (fr) 2004-08-26

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